Replacement steric employed n-alkoxyamine

 

(57) Abstract:

The invention relates to a sterically obstructed amines, substituted at N atom, a group-O-E-HE-. Steric employed amines are particularly effective for the stabilization of polyolefins and compositions for automotive coatings against unwanted oxygen, high temperatures and photochemically active radiation, where the presence of these compounds in the group, HE gives them their important properties absent in the conventional group-O-E-. These compounds get through reaction of the corresponding N-Oxylog connection with alcohol in the presence of peroxide or organic hydroperoxide and a catalytic amount of a metal salt or metal-ligand complex. 4 N. and 19 C.p. f-crystals, 7 PL.

The present invention relates to compounds sterically obstructed amines, the N-atom is substituted by an N-alkoxyphenyl containing from one to three hydroxyl groups. These compounds are particularly effective for the stabilization of polyolefins, especially thermoplastic polyolefins, against undesirable action of oxygen, heat and photochemically active radiation. These compounds are also the ment environment.

Prior art

In the works of S. Nigam et al., J. Chem. Soc.Trans. Faradey Soc. 1, 1976, 72, 2324 and K.-D. Asmus et al., Int. J. Radiat. Biol., 1976, 29, 211 it was reported that 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine and 4-oxo-1-oxyl-2,2,6,6-tetramethylpiperidine were used to "capture" centered on the carbon radicals formed from methanol, ethanol, isopropanol and sec-butanol.

In U.S. patent No. 5627248 and in European patent application No. 135280 A2 described, respectively, bifunctional and monofunctional initiators of free radical polymerization "living" polymers, where some of these initiators include esters of sterically obstructed amines, substituted hydroxy groups. On the structure and properties of these compounds, which mainly differ from the compounds of the present invention.

In European patent application No. 427672 A1 and in U.S. patent No. 4972009 mentioned, but not given as examples, hydroxylamine and nitronovoe patterns, respectively, some of which contain1-C4-hydroxyamphetamine 2,2,6,6-tetramethylpiperidine derivatives. These structures are beyond the scope of the present invention.

In U.S. patent No. 5204473 described peristiani, containing only atoms of carbon and hydrogen. In structure, these compounds are completely different from the compounds of the present invention.

In U.S. patent No. 5004770 described steric employed amine compounds that are substituted at the N atom by alkoxygroup where these alkoxygroup are themselves unsubstituted. These compounds are especially valuable for use in polymers, including polybutadiene, polystyrene, resin plant copolymer (ABS), Polyacetal, polyamide, complex, polyester, polyurethane and polycarbonate.

In U.S. patent No. 5096950 also described compounds sterically obstructed amines, which are substituted at the N atom by alkoxygroup, and these alkoxygroup are themselves unsubstituted. It was found that these compounds can be used in polyolefins.

The compounds of the present invention are N-alkoxy-substituted derivatives of 2,2,6,6-tetraammineplatinum where alkoxygroup substituted by 1-3 hydroxy groups. The compounds of the present invention are also bridge N-alkoxy-substituted derivatives of 2,2,6,6-tetraammineplatinum where alkoxygroup, which is substituted one, two or three hydroxy groups, the two is to react with carboxylic acids, anhydrides or esters with the formation of complex monoamino or polyesters, or with isocyanates to form urethanes or polyurethanes.

Compounds of the present invention, due to its low basicity, which is also characteristic of simple unsubstituted N-alkoxysilane described in the two aforementioned patents are particularly valuable for the stabilization of polyolefins and compositions used for automotive coatings, where the activity of the stabilizers derived from more basic sterically obstructed amines, is significantly reduced due to its interaction with the polymer substrate or an acid catalytic system required for the curing of such a substrate.

Examples of polyolefin compositions, for which the compounds of the present invention are effective include: pyrogen-free polyolefins, where acidic residues, resulting from the decomposition of halogenated flame retardants, inactivate steric amines employed, not containing the group N-OR; films for greenhouses or film for agricultural mulch films, where acid residues of pesticides inhibit the activity of the stabilizers, the floor is the result of pigment with stabilizers of the main sterically obstructed amines prevent staining of the surfaces of the substrates. Examples of compositions for coatings, in which the compounds of the present invention are effective, can serve as a thermosetting acrylic resin, which are connected transverse relationship with melamine, which otverzhdajutsja using strong acids that interact with stabilizers, obtained from primary sterically obstructed amines. Compounds of the present invention are also effective for use in acrylic alkyd or polyester resins with isocyanate crosslinking agents and epoxy resins with carboxylic acid, anhydride or amine-crosslinking agents.

Thus, the compounds of the present invention are preferably used in compositions also containing co-stabilizers, flame retardants (e.g., Tris(3-bromo-2,2-bis-(methyl bromide)propyl)phosphate, oxide decabromodiphenyl, ethylene-bis-(tetrabromophthalimide) or ethylene-bis-(dibromomalonamide)), catalysts (e.g., acids such as toluensulfonate acid, metallic driers or amines), fillers; or they are used in agronomic purposes, where the pesticides come in contact with stabilized polymer. Preferred is a composition, where kompaniyami impact strength (PSUP), and the component (b) is a effective synergistic mixture consisting of:

(i) compounds of the formula (1) to(30); and

(ii) a flame retardant selected from the group comprising halogenated, phosphorus, boron, silicon and surmontera compounds, metal hydroxides, hydrates, metals, metallic oxides, and mixtures thereof.

Although unsubstituted N-OR-compounds described in U.S. patent No. 5004770 and 5096950 also successfully used in the compositions described above, however, the compounds of the present invention are significantly different both in its structure and in its properties from the above compounds due to the presence of one to three free hydroxy groups present on the N-alkoxyalkyl. These hydroxyl groups present in the compounds of the present invention, according to these compounds excellent antistatic properties, i.e. compatibility in more polar environments, such as systems based on polyurethanes and systems used in water-soluble coatings and in stabilizing the structures of the pigmented thermoplastic olefins used to cover cars.

Compounds of this image is the location and mixtures of polycarbonate/ABS compared with the previous N-TH connections; and

(b) messages high degree of compatibility in polyesters and polyamides compared to previous N-OE connections.

The purpose of the present invention

The present invention has two objectives, which are:

1) new compounds having in the 1-position is sterically constrained amine group-O-E-HE is, where HE is the group reports these compounds important properties;

2) composition, stable new compounds described above; and

3) the method of synthesis of new compounds.

Detailed description of the invention

The present invention relates to new compounds having 1-alkoxy-substituted derivatives of sterically obstructed amines, where alkoxygroup substituted by 1-3 hydroxy groups, as shown in the formulas (1) to(15); or to new compounds having bridged derivatives of sterically constrained 1-alkoxyamine where alkoxygroup substituted by 1-3 hydroxy groups, is shared by two molecules sterically constrained amine, as shown in formulas (16)-(28); or oligomeric or polymeric molecules sterically constrained amine, formed in the reaction complex dialkylamino esters or isocyanates with gidroksidom divinum or urethane derivative replacement N-aloxiprin 4-hydroxy-2,2,6,6-tetramethylpiperidine, as shown in the formula (30).

where G1and G2independently represent alkyl with 1-4 carbon atoms or G1and G2taken together, represent pentamethylene, and preferably each of the G1and G2is methyl;

E represents a straight or branched alkylene with 1-18 carbon atoms; cycloalkyl with 5-18 carbon atoms; cycloalkenyl with 5-18 carbon atoms; straight or branched alkylene with 1-4 carbon atoms substituted by phenyl or vennila substituted by one or two alkyl groups with 1-4 carbon atoms;

b is 1, 2 or 3, with the proviso that b cannot exceed the number of carbon atoms in E or L, and if b is 2 or 3, each hydroxyl group is linked to other carbon atoms, F or L; and two sterically difficult amine group, typically the 1;

R1represents hydrogen, hydroxyl or hydroxymethyl;

R2represents hydrogen, alkyl with 1-12 carbon atoms or alkenyl with 2-12 carbon atoms;

n is 1-4;

moreover, if n is 1,

R3represents alkyl with 1-18 carbon atoms, alkoxycarbonylmethyl with 4-18 carbon atoms, alkenyl with 2-18 carbon atoms, glycidyl, 2,3-dihydroxypropyl, 2-hydroxy or 2-(hydroxymethyl) substituted alkyl with 3 to 12 carbon atoms, where the specified alkyl interrupted by an oxygen atom acyl radical of aliphatic or unsaturated aliphatic carboxylic or carbamino acid containing 2-18 carbon atoms, acyl radicals of cycloaliphatic carboxylic or carbamino acid containing 7-12 carbon atoms, or acyl radical of an aromatic acid containing 7 to 15 carbon atoms;

if n is 2,

R3is alkylene with 2-18 carbon atoms, a divalent acyl radical of aliphatic or unsaturated aliphatic dicarboxylic or dicarbamate acid containing 2-18 carbon atoms, a divalent acyl radical cycloaliphatic dicarboxylic or dicarbamate acid containing 7-12 is in carbon;

if n is 3,

R3represents a trivalent acyl radical of aliphatic or unsaturated aliphatic tricarboxylic acid containing 6 to 18 carbon atoms, or a trivalent acyl radical of an aromatic tricarboxylic acid containing 9 to 15 carbon atoms;

if n is 4,

R3represents a tetravalent acyl radical of aliphatic, unsaturated aliphatic or cycloaliphatic tricarboxylic acid or tricarballylic acid containing 6-18 carbon atoms, or a tetravalent acyl radical of an aromatic tricarboxylic acid or tricarballylic acid containing 9 to 18 carbon atoms; or R3represents a trivalent acyl radical of Tris(allylcarbamate acid), a derivative of cyanuric acid containing 12 to 24 carbon atoms, such as 1,3,5-Tris[6-carboxymethoxy]-2,4,6-trioxo-s-triazine;

p is 1-3;

R4represents hydrogen, alkyl with 1-18 carbon atoms or acyl with 2 to 6 carbon atoms;

moreover, if p is 1,

R5represents hydrogen, alkyl with 1-18 carbon atoms, acyl radicals of aliphatic or unsaturated aliphatic ka is new or carbamino acid, containing 7-12 carbon atoms, an acyl radical of an aromatic carboxylic acid containing 7 to 15 carbon atoms, or R4and R5taken together, represent -(CH2)5CO-, phthaloyl or divalent acyl radical of maleic acid;

if p is 2,

R5is alkylene with 2-12 carbon atoms, a divalent acyl radical of aliphatic or unsaturated aliphatic dicarboxylic or dicarbamate acid containing 2-18 carbon atoms, a divalent acyl radical cycloaliphatic dicarboxylic or dicarbamate acid containing 7-12 carbon atoms, or a divalent acyl radical of an aromatic dicarboxylic acid containing 8 to 15 carbon atoms;

if p is 3,

R5represents a trivalent acyl radical of aliphatic or unsaturated aliphatic tricarboxylic acid containing 6 to 18 carbon atoms, or a trivalent acyl radical of an aromatic tricarboxylic acid containing 9 to 15 carbon atoms;

if n is 1,

R6represents alkoxy with 1-18 carbon atoms, alkenylacyl with 2-18 carbon atoms, -NH-alkyl with 1-18 carbon atoms or-N(alkyl)<18 carbon atoms, alkenylamine with 2-18 carbon atoms, -NH-alkylene-NH - with 2-18 carbon atoms or-N(alkyl)-alkylene-N(alkyl)- with 2-18 carbon atoms, or R6is 4-methyl-1,3-phenylendiamine,

if n is 3,

R6represents a trivalent alkoxyalkyl saturated or unsaturated aliphatic triol containing 3-18 carbon atoms;

if n is 4,

R6represents a tetravalent alkoxyalkyl saturated or unsaturated aliphatic tetraol containing 4-18 carbon atoms;

R7and R8independently represent chlorine; alkoxy with 1-18 carbon atoms; -O-T1; the amino group, substituted 2-hydroxyethyl; -NH(alkyl with 1-18 carbon atoms; -N(alkyl)T1where the alkyl group has 1-18 carbon atoms; or-N(alkyl)2with 2-36 carbon atoms;

R9represents a divalent oxygen atom, or R9represents a divalent nitrogen atom substituted by either hydrogen, or alkyl with 1-12 carbon atoms, or T1

R10represents hydrogen or methyl,

q is 2-8,

R11and R12independently represent hydrogen or a group of T2,

the XI with 1-12 carbon atoms; straight or branched alkyl with 1-4 carbon atoms substituted by phenyl; cycloalkyl with 5-8 carbon atoms; cycloalkenyl with 5-8 carbon atoms; alkenyl with 2-12 carbon atoms; glycidyl; allyloxy; straight or branched hydroxyalkyl with 1-4 carbon atoms; or silyl or silyloxy, three times independently substituted by hydrogen, by phenyl, by alkyl with 1-4 carbon atoms or alkoxy with 1-4 carbon atoms;

R14represents hydrogen or silyl, three times independently substituted by hydrogen, by phenyl, by alkyl with 1-4 carbon atoms or alkoxy with 1-4 carbon atoms;

d is 0 or 1;

h is 0-4;

k is 0-5;

x is 3-6;

y is 1-10;

z is an integer such that the compound had a molecular weight of from 1000 to 4000 g/mol (=atomic units, and.E.);

R15is morpholino, piperidino, 1-piperazinyl, alkylamino with 1-8 carbon atoms, especially branched, alkylamino with 3-8 carbon atoms, such as tert-octylamine, -N(alkyl)T1where alkyl has 1-8 carbon atoms, or-N(alkyl)2from 2-16 carbon atoms;

R16represents hydrogen, acyl with 2 to 4 carbon atoms; carbarnoyl, substituted by alkyl with 1-4 acommidate substituted R15provided that two Deputy R15can be various;

R17is chlorine, amino substituted by alkyl with 1-8 carbon atoms or a substituted T1; -N(alkyl)T1where alkyl has 1-8 carbon atoms; -N(alkyl)2from 2-16 carbon atoms; or a group of T3;

R18represents hydrogen; acyl with 2 to 4 carbon atoms; carbarnoyl, substituted by alkyl with 1-4 carbon atoms;

s-triazinyl, twice substituted by a group-N(alkyl)2from 2-16 carbon atoms; or s-triazinyl, twice substituted by a group-N(alkyl)T1with 1-8 carbon atoms;

L represents a straight or branched alkylene with 1-18 carbon atoms; cycloalkyl with 5-8 carbon atoms; cycloalkenyl with 5-8 carbon atoms; albaniles with 3-18 carbon atoms; straight or branched alkylene with 1-4 carbon atoms substituted by phenyl or by phenyl substituted by one or two alkilani with 1-4 carbon atoms;

in formulas (16)-(28), R1, R2, R7, R8, R9, R10, R13, R14, d, h, k, m, q and T1have the same meaning as in formulas(1)-(15);

R19represents hydrogen; alkyl with 1-18 carbon atoms; alkenyl with 2-18 atoms ug where specified alkyl is interrupted by oxygen; acyl radical of aliphatic or unsaturated aliphatic carboxylic or carbamino acid containing 2-18 carbon atoms; acyl radicals of cycloaliphatic carboxylic or carbamino acid containing 7 to 12 carbon atoms; or an acyl radical of an aromatic acid containing 7 to 15 carbon atoms;

R20is alkylene with 2-18 carbon atoms; divalent acyl radical of aliphatic or unsaturated aliphatic dicarboxylic or dicarbamate acid containing 2-18 carbon atoms; divalent acyl radical cycloaliphatic dicarboxylic or dicarbamate acid containing 7 to 12 carbon atoms; or a divalent acyl radical of an aromatic dicarboxylic acid containing 8 to 15 carbon atoms;

R21represents hydrogen, alkyl with 1-18 carbon atoms or acyl with 2 to 6 carbon atoms;

R22represents hydrogen; alkyl with 1-18 carbon atoms; acyl radical of aliphatic or unsaturated aliphatic carboxylic or carbamino acid containing 2-18 carbon atoms; acyl radicals of cycloaliphatic carboxylic or carbamino acid containing 7 to 12 carbon atoms; acyl radical of aromati is t -(CH2)5CO-, phthaloyl or divalent acyl radical of maleic acid;

R23represents hydrogen, alkyl with 1-4 carbon atoms or acyl with 2 to 6 carbon atoms;

R24is alkylene with 2-18 carbon atoms; divalent acyl radical of aliphatic or unsaturated aliphatic dicarboxylic or dicarbamate acid containing 2-18 carbon atoms; divalent acyl radical cycloaliphatic dicarboxylic or dicarbamate acid containing 7 to 12 carbon atoms; or a divalent acyl radical of an aromatic dicarboxylic acid containing 8 to 15 carbon atoms;

R25represents alkoxy with 1-18 carbon atoms; alkenylacyl with 2-18 carbon atoms; -NH-alkyl with 1-18 carbon atoms; or-N(alkyl)2with 2-36 carbon atoms;

R26is alkylenedioxy with 2-18 carbon atoms; Alka-nilindex with 2-18 carbon atoms; -NH-alkylene-NH - with 2-18 carbon atoms; or-N(alkyl)-alkylene-N(alkyl)- with 3-18 carbon atoms;

in formulas (29) and (30), G is centered on the carbon biradical, derived from primary, secondary or tertiary alcohol G-OH, where

z is defined above, and

G before enilan with 5-8 carbon atoms; akinyan with 3-18 carbon atoms; straight or branched alkylene with 1-4 carbon atoms substituted by phenyl or by phenyl substituted by one or two alkilani with 1-4 carbon atoms, provided that in the formula (29) consecutive steric employed radicals can be focused on the type of "head to head" or "head to tail";

T4represents hydrogen, or T4is

R27represents a straight or branched alkylene with 1-18 carbon atoms, cycloalkyl or cycloalkenyl with 5-8 carbon atoms, phenylene or-NH-alkylene-NH - with 2-18 carbon atoms, including 5-amino-1-aminomethyl-1,3 .3m-trimethylcyclohexane and-NH - xylylene-NH-;

R28represents alkyl with 1-4 carbon atoms;

or

R29represents straight or branched alkyl or-NH-alkyl with 1-18 carbon atoms or-NH-cycloalkyl with 5-8 carbon atoms; and

in addition, provided that in the formulae (1) and (2) if b equals 1, then E is not the stands, ethyl, 2-propylene or 2-methyl-2-propylene, as well as in the formula (2), if for every G1and G2represents methyl, the group-E-(OH)bis not 1-phenyl-2-hydroxyethyl.

Predpochtitel, and more preferably 1.

Of particular technological importance are compounds of the formulas (1) and (2), where b is equal to 1 and E represents a methylene, ethylene, 2-propylene or 2-methyl-2-propylene.

If b equals 1, then E-HE and L-OH are respectively centered on the carbon radical or biradical formed preferably from 2-methyl-2-propanol, 2-propanol, 2,2-dimethyl-1-propanol, 2-methyl-2-butanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-nonanol, 1-decanol, 1-dodecanol, 1-octadecanol, 2-butanol, 2-pentanol, 2-ethyl-1-hexanol, cyclohexanol, cyclooctanol, allyl alcohol, ventilago alcohol or 1-phenyl-1-ethanol; most preferably, if E-HE and L-OH are formed from 2-methyl-2-propanol or cyclohexanol.

If b equals 2, then E-HE and L-OH are respectively centered on the carbon radical or biradical, preferably formed from 1,2-ethanediol, 1,2-propane diol, 1,3-propane diol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propane diol, 1,2-cyclohexanediol, 1,3-cyclohexanediol or 1,4-cyclohexanediol; most preferably, if E-HE and L-OH are formed from 1,4-butanediol, 2,2-dimethyl-1,3-propane diol, 1,2-cyclohexanediol, 1,3-cyclohexa the config on the carbon radical or biradical, formed from glycerol, 1,1,1-Tris(hydroxymethyl)methane, 2-ethyl-2-(hydroxymethyl)-1,3-propane diol, 1,2,4-butanetriol or 1,2,6-hexanetriol; most preferably, if E-HE and L-OH are formed from glycerol, 1,1,1-Tris(hydroxymethyl) methane, 2-ethyl-2-(hydroxymethyl)-1,3-propane diol.

Preferably in formulas (29) and (30), -G-O formed from ethanol, ventilago alcohol, cyclohexanol or 2-methyl-2-propanol (=tert-boolavogue alcohol).

Preferably in the formula (3), m is 0, R1represents hydrogen or hydroxymethyl, a R2represents hydrogen; or m is 1, R1is hydroxy or hydroxymethyl, a R2represents hydrogen, methyl or ethyl.

Preferably in the formula (5) R2represents hydrogen or dodecyl.

Preferably in formula (6) n is 1-3, and if n is 1, R3represents allyl, glycidyl, acryloyl, methacryloyl, octadecanoyl, hexadecanoyl, deletion, methoxycarbonylpropionyl, ethoxycarbonylbutyl, methoxycarbonylmethyl or methoxycarbonylamino; or, if n is 2, R3is succinyl, glutaryl, adipoyl, sebacoyl, 1,6-hexadecanol, CIS - or TRANS-5-carbarnoyl-1-(carbamoylmethyl)-1,3 .3m-trim is l)-2,4,6-trioxo-s-triazine.

Preferably in the formula (7), p is 1 or 2, and if R is 1, R4represents hydrogen, a R5is butyl; or R4and R5taken together, represent a divalent acyl radical of maleic acid; or, if p is 2, R4is hydrogen or acetyl, a R5is the 1.6-hexanediol.

Preferably in the formula (8) n is 1 or 2, and if n is 1, R6is ethoxy, 6-methyl-1-heptyloxy, ethylamino, butylamino or octylamine; or if n is 2, R6represents 1,2-ethyoxy, 1,4-butanedione, ethylendiamine, hexamethylenediamine or 4-methyl-1,3-phenylendiamine.

Preferably in the formula (9) R7and R8independently represent chlorine, octylamine, tert-octylamine or amino group, substituted T1and ethyl, butyl or dodecyl; a R9represents a divalent nitrogen atom substituted by ethyl, bootrom or dodecyl.

Preferably in the formula (10) q is 2, 4 or 6, R7represents chlorine, octylamine, octadecylamine or amino group, substituted T1and ethyl, butyl or dodecyl; and R10represents hydrogen.

Preferably in the formula (11) n is 3, p is 2, R2not only is the genus.

Preferably in the formula (12) is 3, R9represents a divalent oxygen atom or a divalent nitrogen atom substituted by ethyl, bootrom or dodecyl, R13represents hydrogen or methyl, and if d is 0, x is 5 or 6, and if d is 1, x is 3 or 4.

Preferably in the formula (13) d is 0 or 1, h is 0-2, k is 0 or 3, y is 1 to 8, R9represents a divalent oxygen atom or a divalent nitrogen atom substituted by ethyl, bootrom or dodecyl; R13represents hydrogen, methyl, ethyl, methoxy or ethoxy; a R14represents hydrogen or trimethylsilyl.

Preferably in the formula (14) R9represents a divalent oxygen atom; R10represents hydrogen or methyl, m is 0, a z is an integer such that the molecular weight compounds were $ 1500-3000.E.

Preferably in the formula (15) q is 6, y is 1-7, R15represents tert-octylamine; morpholino; amino, substituted T1; and butyl, which may also be denoted as T1-butylamino; R16represents hydrogen; acetyl; ethylcarbitol; 2,4-bis(di butylamino)-s-triazine; 2,4-bis(diethylamino)-s-triazinyl; s-triazinyl, double-substituted T1- is ethylamino; R17is dibutylamino, diethylamino; T1-butylamino; or R17is T3where R18represents acetyl or ethylcarbitol.

Preferably in the formula (17) m is 0, R1represents hydrogen or hydroxymethyl, a R2represents hydrogen; or m is 1, R1represents hydroxy or hydroxymethyl and R2represents hydrogen or methyl.

Preferably in the formula (19) R2represents hydrogen or dodecyl.

Preferably in the formula (20) R19represents hydrogen, allyl, acryloyl, methacryloyl, octadecanoyl or hexadecanoyl.

Preferably in the formula (21) R20is succinyl, glutaryl, adipoyl, sebacoyl, 1,6-hexadecanol, or CIS - or TRANS-5-carbarnoyl-1-(carbarnoyl methyl)-1,3 .3m-trimethyl-cyclohexane.

Preferably in the formula (22) R21represents hydrogen, and R22represents hydrogen or butyl; or R21and R22taken together, represent a divalent acyl radical of maleic acid.

Preferably in the formula (23) R23is hydrogen or acetyl, a R24represents ethylene or hexamethylene.

Preferably the tx2">Preferably in the formula (25) R26represents 1,2-ethyoxy, 1,4-butanedione, ethylendiamine or hexamethylenediamine.

Preferably in the formula (26) R7and R8independently represent chlorine, octylamine, tert-octylamine, octadecylamine, T1-ethylamino, T1-butylamino or T1-dodecylamino, a R9represents a divalent nitrogen atom substituted by ethyl, bootrom or dodecyl.

Preferably in the formula (27) q is 2, 4 or 6, R7represents chlorine, octylamine, octadecylamine, T1-ethylamino, T1-butylamino or T1-dodecylamino, a R10represents hydrogen.

Preferably in the formula (28) d is 0 or 1, h is 0-2, k is 0 or 3, R9represents a divalent oxygen atom or a divalent nitrogen atom substituted by ethyl, bootrom or dodecyl, R13represents hydrogen, methyl, ethyl, methoxy or ethoxy, a R14represents hydrogen or trimethylsilyl.

Preferably in formula (29) R27is ethylene, trimethylene, tetramethylene, octamethylene, 1,6-diaminohexane or 5-amino-1-aminomethyl-1,3 .3m-trimethylcyclohexane; z is an integer such that the molecular weight compounds was the Sabbath., 1,4-cyclohexanediyl, -CH(C2H5)(CH2)- or-CH2C(CH3)2-.

Preferably in the formula (30) R29is pentadecyl, heptadecyl, butylamino or cyclohexylamino.

Even more preferred variant of the present invention are compounds of the formulas (1) to(30), where F-HE L-OH and-G-O formed from 2-methyl-2-propanol (=tert-butyl alcohol or cyclohexanol.

More preferably in formula (6), if n is 1, R3is acryloyl, methacryloyl, glycidyl, octadecanoyl, hexadecanoyl, methoxycarbonylpropionyl, ethoxycarbonylbutyl, methoxycarbonylmethyl or methoxycarbonylamino; or, if n is 2, R3is succinyl, glutaryl, adipoyl, sebacoyl, 1,6-hexadecanol, CIS - or TRANS-5-carbarnoyl-1-(carbamoylmethyl)-1,3 .3m-trimethylcyclohexane or toluene-2,4-decarbamoyl; or, if n is 3, R3is 1,3,5-Tris(6-carbamoylmethyl)-2,4,6-trioxo-s-triazine.

More preferably in formula (7) R is 1 or 2, and if R is 1, R4represents hydrogen, a R5represents hydrogen or butyl; or if p is 2, R4represents hydrogen, a R5is 1,6-ecotilling, R8represents chlorine or T1-butylamino, a R9represents a divalent nitrogen atom substituted by bootrom.

More preferably in formula (10) q is 6, R7is T1-butylamino, a R10represents hydrogen.

More preferably in formula (11) n is 3, p is 2 and one R11or R12is T2and the other is hydrogen.

More preferably in formula (12) k is 3, R9represents a divalent oxygen atom, R13represents hydrogen or methyl, and d is 0, x is 5 or 6, and if d is 1, x is 3 or 4.

More preferably in formula (13) d is 0 or 1, h is 0-2, k is 0 or 3, y is 1 to 8, R9represents a divalent oxygen atom, R13represents hydrogen, methyl, ethyl, methoxy or ethoxy, a R14represents hydrogen or trimethylsilyl.

More preferably in formula (15) q is 6, y is 1-7, R15is T1-butylamino; R16represents hydrogen, acetyl, ethylcarbitol, 2,4-bis(dibutylamino)-s-triazinyl, 2,4-bis(diethylamino)-s-triazinyl, s-triazinyl, double-substituted T1-butylamino, or s-triazinyl, once substituted diethylamino>butylamino; or R17is T3where R18represents acetyl or ethylcarbitol.

More preferably in formula (20) R19represents hydrogen, octadecanoyl or hexadecanoyl.

More preferably in formula (22) R21represents hydrogen, a R22represents hydrogen or butyl.

More preferably in formula (23) R23represents hydrogen, a R24is hexamethylene.

More preferably in formula (26) R7represents chlorine, octylamine or T1-butylamino, R8represents chlorine or T1-butylamino, a R9represents a divalent nitrogen atom substituted by bootrom.

More preferably in formula (27) q is 6, R7is T1-butylamino, a R9represents a divalent nitrogen atom substituted by bootrom.

More preferably in formula (29) R27is ethylene, trimethylene, tetramethylene or octamethylene; z is an integer such that the molecular weight compounds were $ 1500-2000.E.; a R28represents methyl.

More preferably in formula (30) R29is pentadecyl or heptadecyl.

H and-G-O-formed from 2-methyl-2-propanol (=tert-butyl alcohol).

Particularly preferred compounds of the formula (6) are compounds where, if n is 1, R3is acryloyl, methacryloyl, glycidyl, octadecanoyl, hexadecanoyl, methoxycarbonylpropionyl or ethoxycarbonylbutyl; and if n is 2, R3is succinyl, glutaryl, adipoyl or sebacoyl.

Particularly preferred compounds of the formula (7) are compounds where R4is hydrogen, and when R is 1, R5represents hydrogen or butyl, or if p is 2, R5is hexamethylene,

Particularly preferred compounds of the formula (9) are compounds where R7represents chlorine, octylamine or T1-butylamino, R8is T1-butylamino, a R9represents a divalent nitrogen atom substituted by bootrom.

Particularly preferred compounds of the formula (10) are compounds where q is 6, R7is T1-butylamino, and R10represents hydrogen.

Particularly preferred compounds of the formula (11) are compounds where n is 3, p is 2, and one of R11or R12is T2and the other is hydrogen.

the but 3 or 4, R9represents a divalent oxygen atom, and R13represents methyl.

Particularly preferred compounds of the formula (13) are compounds where k is 3, y is 4 to 8, R9represents a divalent oxygen atom, R13represents hydrogen or methyl, d, and h 0, R14represents hydrogen; or d is 1 and h is 0, a R14is trimethylsilyl.

Particularly preferred compounds of the formula (14) are compounds where m is 0, R9represents a divalent oxygen atom; R10represents hydrogen or methyl, a z is an integer such that the molecular weight compounds were $ 1500-3000.E.

Particularly preferred compounds of the formula (15) are compounds where q is 6, y is 1-7, R15is T1-butylamino; R16represents hydrogen, acetyl, ethylcarbitol, 2,4-bis(dibutylamino)-s-triazinyl, 2,4-bis(diethylamino)-s-triazinyl, s-triazinyl that double-substituted T1-butylamino, or s-triazinyl, which once replaced diethylamino or dibutylamino and once T1-butylamino; R17is dibutylamino, diethylamino or T3where R18represents acetyl Il>9represents hydrogen, octadecanoyl or hexadecanoyl.

Particularly preferred compounds of the formula (21) are compounds where R20is succinyl, glutaryl, adipoyl or sebacoyl.

Especially preferred compounds of formula (30) are compounds where R29is heptadecyl.

The present invention also relates to polymeric compositions or to a recording material (a) containing an effective stabilizing amount of one or more compounds selected from the compounds of formulas (1) to(30) above, (b) include compounds of formulas (1) and (2), where b is equal to 1 and E represents methyl, ethyl, 2-propyl or 2-methyl-2-propyl. Basically, an effective stabilizing amount of a compound of the present invention is from 0.01 to 10 wt.%, and particularly preferably from 0.05 to 5 wt.% the stabilizer component (b) based on the weight of component (a).

Preferred organic material in need of stabilization, is a natural, semisynthetic or synthetic polymer or a color-forming photographic material, in particular thermoplastic polymer or composition for coating.

Nai the first coating of automobiles and the automotive industry or automotive coatings based on urethane.

Compounds of the present invention, when their presence in the stabilized compositions provide excellent hydrolytic stability, stability during operation and storage, as well as good resistance to extraction.

Mainly organic materials which can be stabilized are:

1. The polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, and also polymers of cycloolefins, such as cyclopentene or norbornene, polyethylene (which may be, but not necessarily, crosslinked), e.g. high density polyethylene (HDPE), high density polyethylene and high molecular weight polyethylene (HDPE-WMPA), high density polyethylene and ultra-high molecular weight (HDPE-PASUM), medium-density polyethylene (PASP), low density polyethylene (LDPE)linear low density polyethylene (LLDPE), (PAOP) and (PESRP).

Polyolefins, i.e. the polymers of monoolefins, examples of which are given in the preceding paragraph, preferably polyethylene and polypropylene, can be obtained, and in particular the following methods:

a) ridicuolously using catalyst which typically contains one or more metals of Groups IVb, Vb, VIb or VIII of the Periodic table of elements. These metals usually have one or more ligands, typically oxides, halides, alcoholate, esters, ethers, amines, alkali, alkenyl and/or arily that can be or coordinated. These metal complexes may be present in free form or they may be fixed on substrates, typically on activated magnesium chloride, titanium chloride (III), aluminium oxide or silicon dioxide. These catalysts can be soluble or insoluble in the medium for polymerization. When these polymerization catalysts may be used as such or they can be used as an additional activators, usually in the form of metallkile, metal hydrides, alkylhalogenide metals, alkylated metals or alkylamino metals, and these metals are the elements of Groups Ia, IIA and/or IIIa of the Periodic table of elements. These activators can be appropriately modified in other ester, ether, aminovymi or silylamine groups. These catalysts are usually referred to as Phillips catalysts, catalysts Standard Oil Indiana, what isatori (YAKO).

2. Mixtures of the above polymers 1) for example, mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, such as copolymers of ethylene/propylene, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), copolymers of propylene/but-1-ene, a copolymer of propylene/isobutylene, copolymers of ethylene/but-1-ene, a copolymer of ethylene/hexene, copolymers of ethylene/methylpentene, copolymers, ethylene/Heptene, copolymers of ethylene/octene, copolymers, propylene/butadiene, copolymers of isobutylene/isoprene, copolymers of ethylene/alkylacrylate, copolymers of ethylene/alkylmethacrylamide, copolymers of ethylene/vinyl acetate and their copolymers with carbon monoxide or copolymers of ethylene/acrylic acid and their salts (ionomers), and also terpolymers of ethylene with propylene and a diene, such as, hexadiene, Dicyclopentadiene or ethylidene-borne; and mixtures of these copolymers with one another and with polymers mentioned above in (1), for example, copolymers of polypropylene/ethylene-propylene copolymers, LDPE/what I or statistical copolymers polyalkylene/carbon monoxide and their mixtures with other polymers, for example polyamides.

4. Hydrocarbon resins (for example, C5-C9) including hydrogenated modifications (for example, agents which impart stickiness), and a mixture of polyalkylene and starch.

5. Polystyrene, poly(p-methylsterol), poly(-methylsterol).

6. Copolymers of styrene or a-methylstyrene and dienes or acrylic derivatives, for example styrene/butadiene, styrene/Acrylonitrile, styrene/alkylmethacrylamide, styrene/butadiene/alkylacrylate, styrene/butadiene/alkylmethacrylamide, styrene/maleic anhydride, styrene/Acrylonitrile/methyl acrylate; mixtures of styrene copolymers with high impact strength and another polymer, such as polyacrylate, a diene polymer or terpolymer ethylene/propylene/diene; and block copolymers of styrene such as styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.

7. Graft copolymers of styrene or a-methylstyrene, for example styrene on polybutadiene, styrene copolymers polybutadiene-styrene or polybutadiene-Acrylonitrile; styrene and Acrylonitrile (or Methacrylonitrile) on polybutadiene; styrene, Acrylonitrile and methyl methacrylate on polybutadiene; styrene and butadiene; styrene or maleimide on polybutadiene; styrene and alkylacrylate or methacrylates on polybutadiene; styrene and Acrylonitrile on terpolymer ethylene/propylene/diene; styrene and Acrylonitrile on polyalkylacrylate or polyalkylacrylate, styrene and Acrylonitrile in the copolymers of acrylate/butadiene, as well as mixtures thereof with the copolymers listed in paragraph(6), for example, mixtures of copolymers known as resin plant copolymer (ABS), methacrylate-1,3-best choice copolymer (MBS), a copolymer of acrylic acid, styrene and Acrylonitrile (ASA) and Acrylonitrile/propylene/diene grafted copolymer (AES).

8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and commercially available brominated copolymer of isobutylene-isoprene (halogenosilanes rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene Homo - and copolymers of epichlorohydrin, in particular polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, grades, polivinilhlorid, polyvinylidene fluoride, and copolymers, such as copolymers of vinyl chloride/vinylidenechloride, vinyl chloride/vinyl acetate or vinylidene liability and polymethacrylates; polymetylmetacrylate, polyacrylamides and polyacrylonitrile modified with butyl acrylate to give the shock strength.

10. The copolymers of the monomers listed in paragraph(9), with each other or with each of the unsaturated monomers, such as copolymers of Acrylonitrile/butadiene, copolymers of Acrylonitrile/alkylacrylate, copolymers of Acrylonitrile/alkoxyalkanols or copolymers of Acrylonitrile/vinylchloride, or terpolymer Acrylonitrile/alkylmethacrylamide/butadiene.

11. Polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals, for example polyvinyl alcohol, polyvinyl acetate, polivinilbutiral, polyvinylether, polyvinylacetate, polyvinyl butyral, polyarylate or polyallylamine; and also their copolymers with olefins mentioned in paragraph(1).

12. The homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropyleneoxide or their copolymers with bis-glycidyloxy esters.

13. Polyacetals, such as Polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as co monomer; Polyacetals modified with thermoplastic polyurethanes, acrylates and polyamide.

15. Polyurethanes, derived from hydroxyterminated polyethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other hand, as well as their predecessors.

16. Polyamides and copolymers of polyamides derived from diamines and dicarboxylic acids and/or from aminocarbonyl acids or from the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides derived from m-xylocaine and adipic acid; polyamides obtained from a diamine and isophthalic and/or tertulias acid with or without an elastomer as modifier, for example poly-2,4,4-trimethylhexamethylenediamine or poly-m-phenylenedimaleimide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bound or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropyleneglycol or polytetramethylene; as well as polyamides or copolyamids, modified ethylene-propylene copolymer (EPDM) or resin plant of spallmucheen, the polyimides, polyamideimide, polyetherimide, complex polyetherimide, polyvidone and polybenzimidazole.

18. Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarbonic acids or the corresponding lactones, for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylcyclohexane and polyhydroxybenzenes, and also block copolymers of polyesters of ferocity, derived from polyethers with a hydroxy-group at the end; and also polyesters modified with polycarbonates or MBS.

19. Polycarbonates and carbonates, polyesters.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Crosslinked polymers derived from aldehydes on the one hand and from phenols, ureas and melamine, on the other hand, such as phenol/formaldehyde resins, urea/formaldehyde resins and melamine/formaldehyde resins.

22. Drying resin and neosuchia alkyd resins.

23. Unsaturated polyester resins resulting from the reaction of spoliation of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, as well as their ha is s from substituted acrylates, for example epoxyacrylate, urethane acrylates or acrylate polyesters.

25. Alkyd resins, polyester resins and acrylate resins crosslinked transverse relationship with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.

26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyloxy compounds, for example the reaction products glycidyloxy ethers of bisphenol a and bisphenol F, which are sewn transverse relationship with the standard hardeners such as anhydrides or amines, with or without the use of catalysts.

27. Natural polymers such as cellulose, rubber, gelatin and chemically modified derivatives of the homologues, such as cellulose acetates, propionate pulp and butyrate cellulose, or ethers of cellulose, such as methylcellulose, as well as rosin and derivatives thereof.

28. Mixtures of the above polymers (a multicomponent mixture), for example polypropylene/ethylene-propylene copolymer (PP/EPDM, polyamide/ethylene-propylene copolymer or resin plant copolymer, polyvinyl chloride/ethyl shall liviniere/methacrylate-1,3-best choice copolymer (PVC/MBS), polycarbonate plastic/resin plant copolymer (HRP/anti-lock brakes), polybutylenterephthalate/copolymer resin plant (pbtf was honored with/ABS), polycarbonate/copolymer of acrylic acid, styrene and Acrylonitrile (HRP/ASA), polycarbonate/polybutyleneterephthalate (HRP/PBT), polyvinyl chloride/chlorinated polyethylene (PVC/CCE), chlorinated polyethylene/acrylate, Polyoxymethylene/thermoplastic polyurethane, polycarbonate/thermoplastic polyurethane, Polyoxymethylene/acrylate, Polyoxymethylene/methacrylate-1,3-best choice copolymer, Polyphenylene oxyde/high-strength polystyrene, polyphenyloxide/PA 6.6 and copolymers, polyamide/polyethylene high density (HDPE), polyamide/polypropylene, polyamide/Polyphenylene oxyde, polybutadiene-leftalt/polycarbonate/copolymer resin plant, or polybutylenterephthalate/polyethylene-terephthalate/polycarbonate.

29. Natural and synthetic organic materials which are pure Monomeric compounds or mixtures of such compounds, for example mineral oils, oils of animal and vegetable origin, oils and waxes, or oils, fats and waxes based on synthetic esters (e.g. phthalates, adipates, phosphates and the which are usually used as spinning compositions, as well as aqueous emulsions of these materials.

30. Aqueous emulsions of natural or synthetic rubbers, such as natural latex or latexes carboxylating copolymers of styrene/butadiene.

31. Polysiloxane, such as soft hydrophilic polysiloxane described, for example, in U.S. patent No. 4259467; and hard organic polysiloxane described, for example, in U.S. patent No. 4355147.

32. Polietilene in combination with unsaturated acrylic polyacetylene resins or unsaturated acrylic resins. Unsaturated acrylic resins are urethane acrylates, polyester acrylates, vinyl or acrylic copolymers with unsaturated side groups and calironia the melamine. Polietilene derived from polyamines and ketones in the presence of an acid catalyst.

33. Composition curable under the action of radiation, and contains Ethylenediamine monomers or oligomers and polyunsaturated aliphatic oligomer.

34. Aproximadamente resin, such as permanent epoxy resin, structured melamine resin of high hardness, which is etherification functional epoxy group, takio from about 0.01 to about 5% by weight of the stabilized composition, although this number may vary, in particular depending on the substrate used and the purpose of the application. The preferred range is from about 0.05% to about 3%, especially preferably from 0.05 to about 1%.

The stabilizers of the present invention can be easily introduced into the organic polymers by standard methods at any suitable stage before getting out of it molded products. For example, the stabilizer may be mixed with the polymer in dry powder form, or a suspension or emulsion of the stabilizer may be mixed with a solution, suspension or emulsion of the polymer. The obtained stabilized compositions of the present invention may also contain, but not necessarily, from about 0.01 to about 5%, preferably from about 0.025 to about 2%, and especially preferably from about 0.1 to about 1 wt.% various suitable additives, such as the materials listed below, or mixtures thereof.

1. Antioxidants

1.1. Alkylated monophenol: for example, 2,6-di-tert-butyl-4-METHYLPHENOL, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenyl, 2,6-dicyclopentyl-4-METHYLPHENOL, 2-(-methylcyclohexyl)-alveoli, which have a linear or branched side chains, for example 2,6-di nonyl-4-METHYLPHENOL, 2,4-dimethyl-6-(1’-methylinden-1’-yl)phenol, 2,4-dimethyl-6-(1’-methylheptadecyl-1’-yl)phenol, 2,4-dimethyl-6-(1’-metaltrade-1’-yl)phenol and mixtures thereof.

1.2. Alkyltrimethylenedi, for example 2,4-dioctylfluorenyl-6-tert-butylphenol, 2,4-dioctylfluorenyl-6-METHYLPHENOL, 2,4-dioctylfluorenyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-non Il-phenol.

1.3. Hydrochinone and alkylated hydrochinone, for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl hydroquinone, 2,5-di-tert-amylketone, 2,6-diphenyl-4-octadecylphenol, 2,6-di-tert-butyl hydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydro-xitemlistener, bis-(3,5-di-tert-butyl-4-hydroxy-phenyl)-adipate.

1.4. Tocopherols, such as-tocopherol, -tocopherol, -tocopherol, -tocopherol and mixtures thereof (vitamin E).

1.5. Gidroksilirovanii thiodiphenylamine ethers, for example 2,2’-THIOBIS(6-tert-butyl-4-METHYLPHENOL), 2,2’-THIOBIS(4-op), 4,4’-THIOBIS(6-tert-butyl-3-methylthiophenol), 4,4’-THIOBIS(6-tert-butyl-2-METHYLPHENOL), 4,4’-THIOBIS-(3,6-di-sec-amylphenol), 4,4’-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.

1.6. Alkalinebattery, for example 2,2’-Metelkin)-phenol], 2,2’-Methylenebis(4-methyl-6-cyclohexylphenol), 2,2’-Methylenebis(6 nonyl-4-METHYLPHENOL), 2,2’-Methylenebis(4,6-di-tert-butylphenol), 2,2’-ethylidene(4,6-di-tert-butylphenol), 2,2’-ethylidene(6-tert-butyl-4-isobutylphenyl), 2,2’-Methylenebis[6-(-methylbenzyl)-4-Nonylphenol], 2,2’-Methylenebis[6-(,-dimethylbenzyl)-4-Nonylphenol], 4,4’-Methylenebis(2,6-di-tert-butylphenol), 4,4’-Methylenebis(6-tert-butyl-2-METHYLPHENOL), 1,1-bis(5-tert-butyl-4-hydroxy-2-were)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-METHYLPHENOL, 1,1,3-Tris(5-tert-butyl-4-hydroxy-2-were)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptan, ethylene glycol bis-[3,3-bis(3’-tert-butyl-4’-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)Dicyclopentadiene, bis[2-(3’-tert-butyl-3’-hydroxy-5’-methylbenzyl)-6-tert-butyl-4-were] terephthalate, 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis-(5-tert-butyl-4-hydroxy-2-were)-4-n-dodecylmercaptan, 1,1,5,5-Tetra(5-tert-butyl-4-hydroxy-2-methyl-phenyl)pentane.

1.7. O-, N - and S-benzyl compounds, for example 3,5,3’,5’-Tetra-tert-butyl-4,4’-dihydroxydiphenyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzimidazole, tridecyl-4-hydroxy-3,5-di-tert-is nil)dithiotreitol, bis(3,5-di-tert-butyl-4-hydroxy-benzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl-mercaptoacetate.

1.8. Hydroxybenzylidene malonate, such as dioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate, dioctadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate, deterimental-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)-malonate, bis[4-(1,1,3,3-TETRAMETHYLBUTYL)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

1.9. Aromatic hydroxybenzoate compounds, for example 1,3,5-Tris-(3,5-di-tert-butyl-4-hydroxy-benzyl)-2,4,6-tri-methyl-benzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-Tetra-methylbenzol, 2,4,6-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

1.10. Triazine compounds, for example 2,4-bis(artillerie)-6-(3,5-di-tert-butyl-4-hydroxyanisole)-1,3,5-triazine, 2-octyl-mercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanisole)-1,3,5-triazine, 2-artillerie-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-Tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-Tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-Tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-Tris(3,5-di-tert-butyl-4-hydroxyphenyl siltstone, for example dimethyl-2,5-di-tert-butyl-4-hydroxyethylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxy-benzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzyl-phosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzyl-phosphonate, calcium salt of monoethylene of ester 3,5-di-tert-butyl-4-hydroxybenzophenone acid.

1.12. Aceraminophen, for example 4-hydroxyacetanilide, 4-hydroxystearate, octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate.

1.13. Esters -(3,5-di-tert-butyl-4-hydroxy-phenyl)propionic acid with a monohydroxy or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, isooctanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propane diol, neopentylglycol, thiodiethanol, diethylene glycol, triethylene glycol, pentaerythritol, Tris(hydroxyethyl)isocyanurate, N,N’-bis(hydroxy-ethyl)oksamida, 3-Ticonderoga, 3-thiapentanal, trimethylpentanediol, three-methylol propane, 4-hydroxymethyl-1-FOSFA-2,6,7-dioxabicyclo[2.2.2]octane.

1.14. Esters -(5-tert-butyl-4-hydroxy-3-methyl-phenyl)propionic acid with a monohydroxy or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, ISM, togetherlike, diethylene glycol, triethylene glycol, pentaerythritol, Tris(hydroxyethyl)isocyanurate, N,N’-bis(hydroxyethyl)oksamida, 3-Ticonderoga, 3-thiapentanal, trimethylpentanediol, trimethylol propane, 4-hydroxymethyl-1-FOSFA-2,6,7-trioxa-bicyclo[2.2.2]octane.

1.15. Esters -(3,5-DICYCLOHEXYL-4-hydroxy-phenyl)propionic acid with a monohydroxy or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propane diol, neopentylglycol, thiodiethanol, diethylene glycol, triethylene glycol, pentaerythritol, Tris-(hydroxyethyl)isocyanurate, N,N’-bis(hydroxyethyl)oksamida, 3-Ticonderoga, 3-thiapentanal, trimethylpentanediol, trimethylolpropane, 4-hydroxymethyl-1-FOSFA-2,6,7-dioxabicyclo[2.2.2]octane.

1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl-acetic acid with a monohydroxy or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propane diol, neopentylglycol, thiodiethanol, diethylene glycol, triethylene glycol, pentaerythritol, Tris(hydroxyethyl)isocyanurate, 4-hydroxymethyl-1-FOSFA-2,6,7-dioxabicyclo[2.2.2]octane.

1.17. Amides -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, for example N,N’-bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)hexamethylenediamine, N,N’-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionic)trimethylenediamine, N,N’-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionic)hydrazide, N,N’-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)-ethyl]oksamid (Naugard®XL-1, supplied by Uniroyal).

1.18. Ascorbic acid (vitamin C).

1.19. Amine antioxidants, such as N,N’-aminobutiramida-p-phenylenediamine, N,N’-di-sec-butyl-p-phenylenediamine, N,N’-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N’-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N’-bis(1-methylheptan)-p-phenylenediamine, N,N’-DICYCLOHEXYL-p-phenylenediamine, N,N’-diphenyl-p-phenylenediamine, N,N’-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N’-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-(1-methylheptan)-N’-phenyl-p-phenylenediamine, N-cyclohexyl-N’-phenyl-p-phenylenediamine, 4-(p-toluensulfonyl)diphenylamine, N,N’-dimethyl-N,N’-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allylmethylamine, 4-isopropoxytitanium, N-phenyl-1-naphtylamine, N-(tert-octylphenyl)-1-naphtylamine, N-phenyl-2-naphthalenol, 4-nonavailability, 4-dodecanolide, 4-octadecylamine, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4’-diaminodiphenylmethane, 4,4’-diaminodiphenylmethane, N,N,N’,N’-tetramethyl-4,4’-diaminodiphenyl-methane, 1,2-bis[(2-were)amino]ethane, 1,2-bis(phenylamino)-propane, (o-tolyl)biguanide, bis[4-(1’3’-dimethylbutyl)phenyl]amine, tert-acceleratory N-phenyl-1-naphtylamine, a mixture of mono - and dialkylamines tert-butyl/tert-octyldiphenyl, a mixture of mono - and dialkylamines of nonindependent, a mixture of mono - and dialkylamines of dodecyldimethylamine, a mixture of mono - and dialkylamines isopropyl/isohexadecane, a mixture of mono - and dialkylamines tert-butyldiethanolamine, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazin, phenothiazines, a mixture of mono - and dialkylamines tert-butyl/tert-activedatainfo, a mixture of mono - and dialkylamines tert-activedatainfo, N-alliteration, N,N,N’,N’-tetraphenyl-1,4-geminorum-2-ene, N,N-bis(2,2,6,6-Tetra-methylpiperid-4-yl-hexamethylenediamine were, bis(2,2,6,6-tetramethylpiperidine-4-yl)sebacate, 2,2,6,6-tetramethylpiperidine-4-one, 2,2,6,6-tetramethylpiperidine-4-ol.

2. Absorbers of UV radiation and photostabilization

2.1. 2-(2’-Hydroxyphenyl)benzotriazoles, for example 2-(2’-hydroxy-5'-IU is)-benzotriazole, 2-(2’-hydroxy-5’-(1,1,3,3-TETRAMETHYLBUTYL)phenyl)-benzotriazole, 2-(3’,5’-di-tert-butyl-2’-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3’-tert-butyl-2’-hydroxy-5’-were)-5-chlorobenzotriazole, 2-(3’-sec-butyl-5’-tert-butyl-2’-hydroxyphenyl)benzotriazol, 2-(2’-hydroxy-4’-octyloxyphenyl)benzotriazole, 2-(3’,5’-di-tert-amyl-2’-hydroxyphenyl)benzotriazol, 2-(3’,5’-bis(,-dimethylbenzyl)-2’-hydroxyphenyl)benzotriazol, 2-(3’-tert-butyl-2’-hydroxy-5’-(2-octyloxyphenyl)phenyl)-5-chlorobenzotriazole, 2-(3’-tert-butyl-5’-[2-(2-ethylhexyloxy)-carbonylethyl]-2’-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3’-tert-butyl-2’-hydroxy-5’-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3’-tert-butyl-2’-hydroxy-5’-(2-methoxycarbonylethyl)-phenyl)-5-chlorobenzotriazol, 2-(3’-tert-butyl-2’-hydroxy-5’-(2-methoxycarbonylethyl)phenyl)-benzotriazole, 2-(3’-tert-butyl-2’-hydroxy-5’-(2-octyloxyphenyl)-phenyl)benzotriazol, 2-(3’-tert-butyl-5’-[2-(2-ethylhexyloxy)-carbonylethyl]-2’-hydroxy-phenyl)benzotriazol, 2-(3’-dodecyl-2’-hydroxy-5’-were-benzotriazol, 2-(3’-tert-butyl-2’-hydroxy-5’-(2-isooctylmercaptoacetate)phenylbenzothiazole, 2,2’-methylene-bis[4-(1,1,3,3-TETRAMETHYLBUTYL)-6-benzotriazol-2-infenal]; the reaction product of transesterification of 2-[3’-tert-2CH2-COO-CH2CH2]2where R=3’-tert-butyl-4’-hydroxy-5’-2H-benzotriazol-2-ylphenyl, 2-[2’-hydroxy-3’-(,-dimethylbenzyl)-5’-(1,1,3,3-TETRAMETHYLBUTYL)-phenyl]-benzotriazole; 2-[2’-hydroxy-3’-(1,1,3,3-dimethylbenzyl)-5’-(,-TETRAMETHYLBUTYL)phenyl]-benzotriazole.

2.2. 2-Hydroxybenzophenone, for example 4-hydroxy-, 4-methoxy-, 4-octyloxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4,2’,4’-trihydroxy - and 2’-hydroxy-4,4’-dimethoxypropane.

2.3. Esters of substituted and unsubstituted benzoic acids, for example 4-tert-butyl-fenilsalitsilat, fenilsalitsilat, antifederalist, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylation, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, for example ethyl, cyano,-diphenylacetate, isooctyl--cyano-,-diphenylacetate, methyl--carbomethoxyamino, methyl--cyano--methyl-p-methoxycinnamate, butyl--cyano--methyl-p-methoxycinnamate, methyl-carbomethoxy-p-methoxycinnamate and N-(-carbomethoxy--cyanovinyl)-2-methylindolin.

2.5. Nickel compounds, for example n the ligands or without them, such as n-butylamine, triethanolamine or N-cyclohexyldimethylamine, dibutil-dithiocarbamate Nickel, Nickel salts monoalkyl esters, for example methyl or ethyl ester of 4-hydroxy-3,5-di-tert-butylbenzylphthalate acid, Nickel complexes of ketoximes, such as 2-hydroxy-4-methyl-phenylenediacrylate, Nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazol with additional ligands or without them.

2.6. Steric employed amines, for example bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-Pipa-rider)succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-butyl-3,5-di-tert-butyl-4-hydroxy-benzylmalonate, the condensation products of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensation products of N,N’-bis-(2,2,6,6-tetramethyl-4-piperidyl)diamine and 4-tert-octylamine-2,6-dichloro-1,3,5-triazine, Tris(2,2,6,6-tetramethyl-4-piperidine)nitrilotriacetate, tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylic, 1,1’-(1,2-ethandiyl)-bis(3,3,5,5-tetramethylpiperidine), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-sterilox-2,2,6,6-tetramethylene ethyl-1,3,8-treetopia(4,5)decane-2,4-dione, bis(1-octyloxy-2,2,6,6-tetramethylpiperidine)sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidine)succinate, linear or cyclic condensation products of N,N’-bis(2,2,6,6-tetramethyl-4-piperidyl)diamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, condensation products of 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethyl-piperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylene)ethane, condensation products of 2-chloro-4,6-di(4-n-butylamino-1,2,2,6,6-tetramethylpiperidine)-1,3,5-triazine and 1,2-bis(3-aminopropylene)ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-treetopia[4,5]-decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dione, 3-dodecyl-1-(2,2,6,6-pentamethyl-4-piperidyl)-pyrrolidin-2,5-dione, mixture of 4-hexadecylamine - and 4-sterilox-2,2,6,6-tetramethylpiperidine, condensation products of N,N’-bis-(2,2,6,6-tetramethylpiperidine)diamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, condensation product of 1,2-bis(diaminopropionic)ethane and 2,4,6-trichloro-1,3,5-triazine and also 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS reg no.[136504-96-6]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylamine, N-(2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylamine, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxaspiro[4,5]decane, a reaction product 7,7,9,9-tetramethyl-2-cyclodecyl-1-C-phenyl)ethen, N,N’-bis-formyl-N,N’-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine were complex fluids 4-methoxy-metromanila acid with 1,2,2,6,6-pentamethyl-4-hydroxy-piperidine, poly[methylpropyl-3-hydroxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane, a reaction product of a copolymer of maleic anhydride and olefin with 2,2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine.

2.7. Oxamide, for example 4,4’-distractionware, 2,2’-diethoxyaniline, 2,2’-dioctyloxy-5,5’-di-tert-butoxylated, 2,2’-didodecyl-5,5’-di-tert-butoxylated, 2-ethoxy-2’-ethyloxazole, N,N’-bis(3-dimethylaminopropyl)oksamid, 2-ethoxy-5-tert-butyl-2’-etoxazole and its mixture with 2-ethoxy-2’-ethyl-5,4’-di-tert-butoxyaniline, a mixture of o - and p-methoxybenzylidene of oxanilide and mixtures of o - and p-ethoxybenzylidene of oxanilide.

2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazine, for example 2,4,6-Tris(2-hydroxy-4-octyloxyphenyl)1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimetilfenil)1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimetilfenil)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-proproxyphene)-6-(2,4-dimetilfenil)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-were)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-di-were)-1,3,5-triazine is si)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxyphenyl)-phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[4-(dodecyloxy/tridecylamine-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimetilfenil)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxyethoxy)phenyl]-4,6-bis(2,4-dimetilfenil)-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)-phenyl-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6-Tris-[2-hydroxy-4-(tributoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine, 2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropoxy]phenyl}-4,6-bis(2,4-dimetilfenil)-1,3,5-triazine.

3. The decontamination officers metals, for example N,N’-diphenyloxide, N-salicylal-N’-salicyloylhydrazine, N,N’-bis(salicyloyl)-hydrazine, N,N’-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionic)-hydrazine, 3-salicylamide-1,2,4-triazole, bis(benzylidene)-oxalidaceae, oxanilide, isophthalaldehyde, subcommunicated, N,N’-diacetylmorphine, N,N’-bis-(salicyloyl)oxalidaceae, N,N’-bis(salicyloyl)thiopropionate.

4. The phosphites and phosphonites, for example triphenylphosphite, diphenylacetate, phenyldichlorophosphine, Tris(nonylphenyl)-pofit, trilaurylamine, trioctadecyl, disfear-butylphenyl)-pentaerythritoltetranitrate, bis(2,6-di-tert-butyl-4-were-pentaerythritoltetranitrate, diisodecylphthalate, bis(2,4-di-tert-butyl-6-were)pentaerythritoltetranitrate, bis(2,4,6-Tris(tert-butyl-phenyl)pentaerythritoltetranitrate, tristearate triphosphate, tetrakis(2,4-di-tert-butylphenyl)-4,5’-biphenylenediisocyanate, 6-isooctane-2,4,8,10-Tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphospholane, bis(2,4-di-tert-butyl-6-were)methylphosphate, bis(2,4-di-tert-butyl-6-were)ethylphosphate, 6-fluoro-2,4,8,10-Tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphospholane, 2,2’,2’-nitrilo[triethyl-Tris(3,3’,5,5’-Tetra-tert-butyl-1,1’-biphenyl-2,2’-diyl)postit], 2-ethylhexyl(3,3’-5,5’-Tetra-tert-butyl-1,1’-biphenyl-2,3’-diyl)FOSFA, 5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxa-fostiras.

Especially preferred are the following phosphites:

Tris(2,4-di-tert-butylphenyl)fosfat (Irgafos® 168, Ciba-Geigy), Tris(nonylphenyl)FOSFA,

5. Hydroxylamine, for example N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylsebacate, N,N-di-lauryldimonium, N,N-detraditionalisation, N,N-dihexadecyl, N,N-dictatorially, N-hexadecyl-N-octadecyltriethoxysilane, N-grams of the fat.

6. Nitron, for example N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-metallitron, N-octyl-alpha reptilian, N-lauryl-alpha undecillion, N-tetradecyl-alpha tredecillion, N-hexadecyl-alpha pentadecane, N-octadecyl-alpha heptadecane, N-hexadecyl-alpha heptadecyl Nitron, N-octadecyl-alpha pentadecane, N-heptadecyl-alpha heptadecane, N-octadecyl-alpha hexadecahedron, Nitron, derived from N,N-dialkylhydroxylamines derived from amine gidilounge animal fat.

7. Ticinella, such as delayintolerant or distearyldimethylammonium.

8. Peroxide acceptors, for example esters-thio-dipropionate acids, for example lauric, stearyl, ministerului or tridecylamine esters, mercaptobenzimidazole or zinc salt of 2-mercaptobenzimidazole, dibutyldithiocarbamate zinc, dictatorially, pentaerythritoltetranitrate(-dodecylmercaptan)propionate.

9. Polyamide stabilizers, for example copper salt in combination with iodides and/or phosphorus compounds and salts of divalent manganese.

10. Basic co-stabilizers, for example melamine, polyvinylpyrrolidone, dicyandiamide, treelistener derived mo the metals of higher fatty acids, for example calcium stearate, zinc stearate, beginat magnesium, stearate, ricinoleic sodium and potassium palmitate, pyrocatechol antimony or pyrocatechol zinc.

11. The nuclei of crystallization, for example inorganic substances, such as talc, metallic oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates, preferably of alkaline-earth metals; organic compounds such as mono - or polycarboxylic acids and their salts, such as 4-tert-butylbenzoic acid, adipic acid, diphenyloxy acid, sodium succinate or sodium benzoate; polymeric compounds such as ionic copolymers (ionomers). Especially preferred are 1,3:2,4-bis(3’,4’-dimethylbenzylidene)sorbitol, 1,3:2,4-di(parameterdirection)sorbitol and 1,3:2,4-di(benzylidene)sorbitol.

12. Fillers and reinforcing fillers, for example calcium carbonate, silicates, glass fibers, glass spheres, asbestos, talc, kaolin, mica, barium sulfate, oxides and metal hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.

13. Other additives, for example plasticizers, oil, emulsifiers, pigments, rheolog the ticks and gas developing agents.

14. Benzofuranol and indolinone, for example, compounds described in U.S. patent No. 4325863; U.S. No. 4338244; U.S. No. 5175312; U.S. No. 5216052; U.S. No. 5252643; DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102 or 3-[4-(2-acetoacetate)phenyl]-5,7-di-tert-butylbenzofuran-2-it, 5,7-di-tert-butyl-3-[4-(2-staurolite)phenyl]benzofuran-2-it, 3,3’-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)-benzofuran-2-he], 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2 he, 3-(4-acetoxy-3, 5dimethylphenyl)-5,7-di-tert-butylbenzofuran-2 he, 3-(3,5-dimethyl-4-pivaloyloxymethyl)-5,7-di-tert-butylbenzofuran-2 he, 3-(3,4-dimetilfenil) 5,7-di-tert-butylbenzofuran-2 he, 3-(2,3-dimetilfenil) 5,7-di-tert-butylbenzofuran-2-it.

15. Oxides of amines, for example derivatives of amine oxides described in U.S. patent No. 5844029 and 5880191, the oxide dodecylamine, the oxide tridecylamine, the oxide trichodermin and the oxide trioxadecyl. In U.S. patent No. 5844029 and 5880191 described the use of oxides of saturated hydrocarbon amine for the stabilization of thermoplastic resins. In these patents indicate that these thermoplastic compositions may also contain a stabilizer or mixture of stabilizers selected from phenolic antioxidants, light stabilizers based on sterically smoothly and ticinella. Examples of amine oxides together with other stabilizers for the stabilization of polyolefins in these works are not given.

Co-stabilizers oxides of amines are compounds of the formula (I)

where E1and E2independently represent straight or branched alkyl with 6-36 carbon atoms, aryl with 6-12 carbon atoms, aralkyl with 7-36 carbon atoms, alkaryl with 7-36 carbon atoms, cycloalkyl with 5-36 carbon atoms, arcticooler with 6-36 carbon atoms or cycloalkenyl with 6-36 carbon atoms;

E3represents straight or branched alkyl with 1-36 carbon atoms, aryl with 6-12 carbon atoms, aralkyl with 7-36 carbon atoms, alkaryl with 7-36 carbon atoms, cycloalkyl with 5-36 carbon atoms, arcticooler with 6-36 carbon atoms or cycloalkenyl with 6-36 carbon atoms; provided that at least one of E1E2and E3contains carbon-hydrogen bond; and

where these alkyl, kalkilya, alarilla, cycloalkyl, alkylcyclohexane and cycloalkylation group may be interrupted 1-16 groups-O-, -S-, SO-, -SO2-, -COO-, -OCO-, CO-, -N4-, -CONE4- and-NE4CO-or where these alkyl, you 1-16 groups, selected from TH4, -SE4-SOOE4-OSOE4-SOY4, -N(E4)2, -CON(E4)2, -NG4COE4and 5 - and 6-membered ring containing the group C(CH3)(CH2Rx)NL1(CH2Rx)(CH3), Or where these alkyl, kalkilya, alarilla, cycloalkyl, arcticola and cycloalkylation group interrupted and substituted by the above groups; and

where E4independently represents hydrogen or alkyl with 1-8 carbon atoms;

Rxrepresents hydrogen or methyl, preferably hydrogen;

L1is a straight or branched C1-30alkyl group, a group-C(O)R30where R30is a straight or branched C1-30alkyl group or a group or SIG30where R30is a straight or branched C1-30alkyl group; and

where these aryl groups may be substituted by 1-3 halogen atoms, alkyl with 1-8 carbon atoms, alkoxy with 1-8 carbon atoms, or combinations thereof.

The preferred compound of formula (I) is a compound where E1and E2independently represent a benzyl or substituted benzyl. E1, the t also alkyl groups with 8-26 carbon atoms, and most preferably alkyl groups with 10-26 carbon atoms, and E3preferably represents an alkyl group with 1-22 carbon atoms, and most preferably methyl or substituted methyl. Also preferred are amine oxides in which E1E2and E3represent the same alkyl group 6-36 carbon atoms. Preferably all of the above balances for E1E2and E3are saturated hydrocarbon residues or saturated hydrocarbon residues containing at least one of the aforementioned groups-O-, -S-, -SO-, -CO2-, -CO - or-CON-. Each specialist can be considered for other suitable residues for each of the E1E2and E3not beyond the scope of the present invention.

Rich amine oxides can also be poly(aminoacid). The notion of poly(aminoacid) refers to the oxides of tertiary amines containing at least two tertiary amine oxide in the molecule. Examples of poly(aminoacids), also called poly(oxides of tertiary amines) are the analogues of oxides of tertiary amines aliphatic and cycloaliphatic diamines, such as, e.g. what they like, for example, diaminoanthraquinone and diaminoanisole.

As examples can also serve as the oxides of tertiary amines derived from oligomers and polymers of the above diamines. Suitable amine oxides are the oxides of amines attached to polymers, such as polyolefins, polyacrylates, complex polyesters, polyamides, polystyrenes, etc., If the amine oxide is attached to the polymer, the average number of amine oxide in the polymer can vary widely, because not all of the polymer chain must contain an amine oxide. All of the above amine oxides can, but not necessarily, contain at least one of the groups-O-, -S-, -SO-, -CO2-, -CO - or-CONE4-. In the preferred embodiment, each of the tertiary amine oxide is attached to the polymer oxides of tertiary amine contains1-balance.

Group E1E2and E3formula (I) can be attached to a molecule containing a sterically hindered amine. Steric employed amines known in the art, and the amine oxide of the present invention can be attached to steric difficulties of Amin in any way and in any position of the structure of sterically constrained Amin. Steric ZAT the General formula (II) and (III):

where L1and Rxdefined above. Such amines are amine oxides containing more than one sterically constrained amine and more than one saturated amine oxide molecule. Sterically hindered amine can be attached to poly(tertiary amine oxide), or it can be attached to the polymeric substrate, as described above.

Co-stabilizers, with the exception of benzopyranones listed in paragraph 11, add, for example, in concentrations of 0.01-10% on the total mass of the stabilized material.

In addition, the preferred composition, in addition to components (a) and (b) include other additives, and in particular phenolic antioxidants, light stabilizers, process stabilizers.

Particularly preferred additives are phenolic antioxidants (item 1 of the list), steric employed amines (item 2, 6 on the list), phosphites and phosphonites (item 4 of the list) and peroxidases connection (item 5 of the list).

Additional additives (stabilizers), which are also particularly preferred are benzofuran-2-ones, such as, for example, compounds described in US-A-4325863, US-A-4338244 or US-A-5175312.

,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanoate-tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), di-n-octadecyl-3,5-di-tert-butyl-4-hydroxyethylphosphonate, 1,3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, thiodiethanol(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1,3,5-trimethyl-2,4,6-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 3,6-dioxa-octamethylene(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate), 2,6-di-tert-butyl-p-cresol, 2,2’-ethylidene(4,6-di-tert-butyl-phenol), 1,3,5-Tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl)-isocyanurate, 1,1,3-Tris(2-methyl-4-hydroxy-5-tert-butylphenyl)-butane, 1,3,5-Tris[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)ethyl] isocyanurate, 3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitol, hexamethylenebis(3,5-di-tert-4-hydroxyhydrocinnamate), 1-(3,5-di-tert-butyl-4-hydroxyamino)-3,5-di(octylthio)-s-triazine, N,N’-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), bis(ethyl-3,5-di-tert-butyl-4-hydroxy-benzylphosphonate) calcium, ethylenebis[3,3-di-(3-tert-butyl-4-hydroxyphenyl)butyrate], octyl-3,5-di-tert-butyl-4-hydroxy-benzylmercaptan, bis(3,5-di-tert-butyl-4-hydroxygen-cynnamoyl)hydrazide, and N,N’-bis[2-(3,5-di-tert-butyl-4-hydroxy-hydrocinnamate)ethyl]oksamid.

The most preferred phenolic antioxidant-4-hydroxyhydrocinnamate, 1,3,5-trimethyl-2,4,6-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-Tris(3,5-di-tert-butyl-4-hydroxy-benzyl)isocyanurate, 2,6-di-tert-butyl-p-cresol or 2,2'-ethylidene-bis(4,6-di-tert-butylphenol).

Of particular interest are compounds sterically obstructed amines selected from the group including: bis-(2,2,6,6-tetramethylpiperidine-4-yl)sebacate, bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate, di(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate, 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-sterilox-2,2,6,6-tetramethylpiperidine, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-diazaspiro[4.5]decane-2,4-dione, Tris(2,2,6,6-tetramethylpiperidine-4-yl)nitrilotriacetate, 1,2-bis(2,2,6,6-tetramethyl-3-oxopiperidin-4-yl)ethane, 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxidiser[5.1.11.2]heneicosan, the polycondensation product of 2,4-dichloro-6-tert-octylamine-s-triazine and 4,4’-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine), polycondensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, polycondensation product of 4,4’-hexamethylenebis(amino-2.2,6,6-tetramethylpiperidine) and 1,2-dibromoethane, tetrakis(2,2,6,6-tetramethylpiperidine-4-yl)-1,2,3,4-butanetetracarboxylic, tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl)-1,2,3,4-bucanero the l of piperidine), N,N’,N’,N’’-tetrakis[(4,6-bis(butyl-1,2,2,6,6-pentamethylpiperidin-4-yl)-amino-s-triazine-2-yl]-1,10-diamino-4,7-dosagecan, the polycondensation product of 2,4-dichloro-6-morpholino-s-triazine and 4,4’-hexamethylenebis(amino-1,2,2,6,6-pentamethylpiperidine), mixed [2,2,6,6-tetramethylpiperidine-4-yl/,,’,’-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]-undecane) diethyl]-1,2,3,4-butanetetracarboxylic, mixed [1,2,2,6,6-pentamethylpiperidin-4-yl/,,’,’-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]-undecane)diethyl]-1,2,3,4-butanetetracarboxylic, octamethylene bis(2,2,6,6-tetramethylpiperidine-4-carboxylate), 4,4’-ethylenebis(2,2,6,6-tetramethylpiperidine-3-one), N-2,2,6,6-tetramethyl-piperidine-4-yl-n-dodecylamine, N-2,2,6,6-pentamethyl-piperidine-4-yl-n-dodecylamine, N-1-acetyl-2,2,6,6-Tetra-methylpiperidin-4-yl-n-dodecylamine, 1-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-treetopia[4,5]-decane-2,4-dione, di-(1-octyl-hydroxy-2,2,6,6-tetramethylpiperidine-4-yl)sebacate, di-(1-cyclohexyl-hydroxy-2,2,6,6-tetramethylpiperidine-4-yl)succinate, 1-octyloxy-2,2,6,6-tetramethyl-4-hydroxypiperidine, poly{[6-tert-octylamine-s-triazine-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)-aminohexanoate-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)-imino], 2,46-Tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-ylamino-s-triazine, the oligomer of N-{[2-(N-2,2,6,6-tetramethylpiperidine-4-yl)butylamino]-s-triazine-4-yl}-N,N’-bis(2,2,6,6-tetramethylpiperidine-4-yl)-1.6-hexanediamine with the end of 2,4-bis(dibutylamino)-s-triazine-6-yl, N,N’,N"-Tris{2,4-bis[N-(1,2,2,6,6-pentamethylpiperidin-4-yl)butylamino]-s-triazine-6-yl}-3,3’-ethylendiaminetetraacetic, N,N’,N’-Tris{2,4-bis[N-(1,2,2,6,6-pentamethylpiperidin-4-yl)butylamino]-s-triazine-6-yl}-3,3’-ethylendiaminetetraacetic and N,N’,N’,N’’-tetrakis{2,4-bis[N-(1,2,2,6,6-pentamethylpiperidin-4-yl)butylamino]-s-triazine-6-yl}-3,3’-ethylendiaminetetraacetic; N,N’,N’-Tris{2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)butylamino]-s-triazine-6-yl}-3,3’-ethylendiaminetetraacetic, N,N’,N’-Tris{2,4 bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)butylamino]-s-triazine-6-yl}-3,3’-ethylendiaminetetraacetic, N,N’,N’,N’’-tetrakis{2,4-bis[N-(1-cyclohex-siloxy-2,2,6,6-tetramethylpiperidine-4-yl)-butylamino]-s-triazine-6-yl}-3,3’-ethylendiaminetetraacetic; oligomer of N-{2-[(1-propoxy-2,2,6,6-tetramethylpiperidine-4-yl)butylamino]-s-triazine-4-yl}-N,N’-bis(1-propoxy-2,2,6,6-tetramethylpiperidine-4-yl)-1.6-hexanediamine, with the end of 2,4-bis(dibutylamino)-s-triazine-6-yl, or condensation products of 2-morpholino-4,6-dichloro-s-triazine with N,N’-bis(1,2,2,6,6-pentamethylpiperidin-4-yl)-1,6-hexa(2,2,6,6-tetramethylpiperidine-4-yl)sebacate, bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate, di-(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5-di-tert-butyl-4-hydroxy-benzyl)butylmalonate, the polycondensation product of 1-(2-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, polycondensation product of 2,4-dichloro-6-tert-octylamine-s-triazine with 4,4’-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine), N,N’,N’,N’’-tetrakis[(4,6-bis(butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino)-s-triazine-2-yl]-1,10-diamino-4,7-dosagecan, di-(1-octyloxy-2,2,6,6-tetramethylpiperidine-4-yl)sebacate, di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)succinate, 1-octyloxy-2,2,6,6-tetramethyl-4-hydroxypiperidine, poly-{[6-tert-octylamine-s-triazine-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)aminohexanoate-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)-imino] or 2,4,6-Tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)-n-butylamino]-s-triazine.

The composition of the present invention may in addition contain other absorber of UV radiation, selected from the group consisting of s-triazines, oxanilide, hydroxybenzophenones, benzoates and-cyanoacrylates.

In particular, the composition of the present invention may, additionally, contain effective stabilizer rejeski difficult amine or mixtures thereof.

Preferably 2-hydroxy-2H-benzotriazol selected from a group including:

2-(2-hydroxy-3,5-di-tert-amylphenol)-2H-benzotriazole;

2-[2-hydroxy-3,5-di (- dimethylbenzyl)phenyl]-2H-benzotriazole;

2-[2-hydroxy-3-(- dimethylbenzyl)-5-tert-octylphenyl]-2H-benzotriazole;

2-{2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-OCTA-(ethylene-oxy)carbonyl)ethyl]phenyl}-2H-benzotriazole; and

2-{2-hydroxy-3-tert-butyl-5-[2-(octyloxy) carbonyl)ethyl]-phenyl}-2H-benzotriazole.

Preferably 2-hydroxyphenyl-2H-benzotriazol can also be selected from the group including:

(a) 5-trifluoromethyl-2-(2-hydroxy-3-Cumyl-5-tert-octylphenyl)-2H-benzotriazole;

(b) 5-trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole;

(c) 5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole;

(d) 2,2’-methylene-bis[6-(5-trifluoromethyl-2H-benzotriazol-2-yl)-4-tert-op];

(e) methylene-2-[4-tert-octyl-6-(2H-benzotriazol-2-yl)phenol]-2’-[4-tert-octyl-6-(5-trifluoromethyl-2H-benzotriazol-2-yl)phenol];

(f) 3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyvitamin acid;

(d) methyl-3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-g is cinnamate;

(i) 5-trifluoromethyl-2-[2-hydroxy-5-(3-hydroxypropyl)phenyl]-2H-benzotriazole;

(j) 5-trifluoromethyl-2-[2-hydroxy-5-(3-acryloyloxy)-phenyl]-2H-benzotriazole;

(k) 5-trifluoromethyl-2-[2-hydroxy-5-(3-methacryloxypropyl)-phenyl]-2H-benzotriazole;

(I) 5-trifluoromethyl-2-[2-hydroxy-5-(3-acrylamidoethyl)-phenyl]-2H-benzotriazole;

(m) 5-trifluoromethyl-2-[2-hydroxy-5-(3-methacrylatesulfopropyl)-phenyl]-2H-benzotriazole;

(n) 5-trifluoromethyl-2-(2-hydroxy-3-Cumyl-5-tert-butylphenyl)-2H-benzotriazole;

(o) 5-trifluoromethyl-2-(2-hydroxy-3-Cumyl-5-nonylphenyl)-2H-benzotriazole;

(p) 5-trifluoromethyl-2-[2-hydroxy-3-Cumyl-5-(2-hydroxyethyl)-phenyl]-2H-benzotriazole;

(q) 5-trifluoromethyl-2-[2-hydroxy-3-Cumyl-5-(3-hydroxypropyl)phenyl]-2H-benzotriazole;

(r) 5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-amylphenol)-2H-benzotriazole;

(s) - 5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;

(t) 5-trifluoromethyl-2-(2-hydroxy-3-dodecyl-5-were)-2H-benzotriazole;

(u) 5-trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(3-hydroxypropyl)phenyl)-2H-benzotriazole;

(v) 5-trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole;

(y) 5-fluoro-2-(2-hydroxy-3,5-di-cumylphenol)-2H-benzotriazole;

(z) 5-butylsulfonyl-2-(2-hydroxy-3,5-di-cumylphenol)-2H-benzotriazole;

(AA) 5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;

(bb) 5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole; and

(it) 5-phenylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole.

Preferably the other of Tris-aryl-s-triazine selected from the group including:

2,4-bis(2,4-dimetilfenil)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine;

2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-s-triazine;

2,4-bis(2,4-dimetilfenil)-6-[2-hydroxy-4-(3-do-/tri-decyl-hydroxy-2-hydroxypropoxy)phenyl]-s-triazine; and

2-(2-hydroxyethylamino)-4,6-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)amino]-s-triazine.

Other stabilizing materials of the present invention is the recording material. Such materials are implied, for example, the materials described in Research Disclosure 1990, 31429 (pages 474 to 480) for photographic and other methods of reprography.

New recording materials include, for example, other imaging systems, microci material for inkjet printing.

New photographic material can be black and white or color photographic material; however, preferred is a color photographic material. A more detailed description of the structure of a color photographic material and components, which can be used in this new material can be found, inter alia, in US-A-5538840, column 27 line 25 column 106 line 16, and in the cited publications here; these sections US-A-5538840 introduced into the present description by reference. In these papers described the use of new compounds, mainly for absorbers of UV radiation or stabilizers based on sterically obstructed amines. Other important components, especially, the actual pigment substances, described in US-5578437.

Varnishes based on acrylic resins which can be stabilized against light, moisture and oxidation in accordance with the present invention, are standard hot drying varnishes based on acrylic resins or thermosetting resins including acrylic/melamine systems are described, for example, N. Kittles "Lehrbuch & Beschichtungen", vol.1, Part 2, pp.735 and 742 (Berlin 1972), "Lackkunstharze" (1977), H. Wagner & H. F. Sarx, pp.229-238, and S. Paul's "Surface Coatings: Science and Technology", (1985).

Poliefirnaya drying, described, for example, H. Wagner & H. F. Sarx, Op. cit., pp.86-99.

Lacquers based on alkyd resins which can be stabilized against light and humidity in accordance with the present invention, are standard hot drying varnishes that are used, in particular, for automotive coatings (automotive varnish), for example lacquers based on alkyd/melamine resins and alkyd/acrylic/melamine resins (see H. Wagner & H. F. Sarx, "Lackkunstharze" (1977), pp. 99-123). Other cross-linking agents are glycoluril resin, blocked or non-blocked isocyanates or epoxy resins. Other lacquers which can be stabilized are lucky having a crosslinking functional group such as a carbamate and a siloxane.

Lucky stabilized in accordance with the present invention are suitable for coating on a metal surface and toning finishing coatings on hard surfaces, especially for retouching and coatings on various roll materials. Lucky stabilized in accordance with the present invention, preferably applied in a standard way by two methods, either by applying a single coating, or Eitie, and then on top of this coating is applied a top coat of clear varnish.

Although in its main aspect, the present invention relates to kislotosoderjasimi thermoablative finishing coatings, it should also be noted that the compounds of the present invention suitable for use in acatalasemia acid thermosetting resins such as epoxy, epoxy-polyester, vinyl, alkyd, acrylic and polyester resins, optionally modified with silicon, isocyanates or isocyanurates. Epoxy and epoxy-polyester resins are resins, structured suitable cross-linking groups such as acids, acid anhydrides, amines, etc., In accordance with this, the epoxide can be used as a crosslinking agent for the various systems based on acrylic or polyester resins, which can be modified by the presence of reactive groups on the structure of the main chain.

Number of connections-stabilizer of the present invention is from 0.1 to 5 wt.%, by weight of binder, solvent free, and preferably from 0.5 to 2 wt.%. The binder may be dissolved or dispersed in the standard is assured in the methods of applying double coating compounds of the present invention can be included in the transparent coating or as a transparent coating, and in pigmented primer coating.

For maximum resistance to light can be advantageous simultaneous use of other suitable light stabilizers. Examples of absorbers of UV radiation are benzophenone, benzotriazole, derivatives of acrylic acid, oxalanilide, aryl-s-triazine or types of metal-containing compounds (for example, michelangelesque connection). In systems with dual coating these additional light stabilizers can be added in the transparent coating and/or pigmented primer coating.

When using such combinations of stabilizers number of all light stabilizers constitutes from 0.2 to 20%, preferably from 0.5 to 5 wt.% by weight of film-forming resin.

If it is desirable to use water-soluble, miscible with water or dispersible in water coverage, I get the ammonium salt of the acid groups present in the resin. Powder composition for coating can be obtained by reaction of glycidylmethacrylate with the selected alcohol components.

It is also expected that compounds of the present invention should be particularly valuable in and uppy HE will give these connections are the best compatibility and properties, suitable for the specified aquatic environment.

Compounds of the present invention can also be used to stabilize the acid catalyzed thermoset resins, which are described in U.S. patent No. 5112890, relevant sections of which are introduced in the present description by reference.

These resins are used in the hot drying enamels or lacquers hot drying. It is well known that the stabilizers based on sterically obstructed amines are effective for the stabilization of organic substrates, including polymers, in order to protect them from the adverse effects of oxygen and radiation. Such light stabilizers based on sterically obstructed amines have been used to stabilize thermostructural alkyd or acrylic metal-containing varnishes hot drying (see U.S. patent 4426472) and to stabilize kislotosoderjasimi hot drying varnishes based thermostructural acrylic polyester or alilovic resins (see U.S. patent No. 4344876 and 4426471). None of the light stabilizers based on sterically obstructed amines described in these patents, has no structures with O-substituted hydroxyl group, which is substituted retene and in addition, they are even less basic than the connection NOR described in U.S. patent 5112890, as seen from the working Example 114 of this application.

In its industrial application of enamel with a high content of solids derived from structured acrylic polyester, urethane or alkyd resins, otverzhdajutsja with additional acid catalyst. Light stabilizers containing a basic nitrogen group, are usually less suitable for this application. The salt formation between the acid catalyst and sitosterolemia leads to incompatibility or insolubility and precipitation of salts, as well as to decrease the degree of cure, to reduce light protection actions and poor resistance to moisture.

Kislotosoderjasimi thermotherapies enamel must be stabilized to message them acceptable functions at the end-use. Used stabilizers are sterically difficult amines, preferably amines substituted on the N atom of inert blocking group to prevent deposition of the primary amine acid catalyst with simultaneous slow curing, where pointed to by the>stabilizatory necessary for the message utverzhdennym enamels a long-term preservation stability (as determined by luster, as measured by the gloss meter with the reflection of light at an angle 20° (20°-Shine), impeccable appearance, cracking or the white fly); stabilizers should not slow down the curing (normal heat treatment when applying automotive coatings at 121°C; and low-temperature maintenance heat treatment at 82°C), as measured by hardness, adhesion, resistance to solvent and moisture; and this enamel should not turn yellow after curing, and change its color under the action of light radiation should be minimized; in addition, these stabilizers should be soluble in organic solvents commonly used for coatings, such as methylmercaptan, xylene, n-exilerated, alcohol, etc.

The light stabilizers of the present invention based on sterically obstructed amines with N-atom O-substituted part containing a free hydroxyl group, meets each of these requirements, taken separately or in combination with absorbers of UV radiation to give svetozarauladocy, providing the parki to polymeric systems, able to cure in ambient conditions. For example, suitable resins are alkyd, acrylic, polyester and epoxy resins, are described in the work of S. Paul's "Surface Coating: Science and Technology" (1985), pp. 70-310. Various acrylic and modified acrylic resins described in the work of N. Kittles "Lehrbuch der Lacke unde Beschichtungen", Vol.1, Part 2, on pages 735 and 742 (Berlin 1972), and in "Lackkunstharze" (1977) by Wagner and H. F. Sarx, Op. cit, pages 229-238. Typical structured polyester resins that can be stabilized against the action of light and moisture, are described, for example, in H. Wagner and H. F. Sarx, Op. cit., on page 86-99. Non-modified and modified alkyd resins which can be stabilized are standard resins, which are used in finished goods for sale, repair coatings and top coatings cars. For example, these coatings are made on the basis of alkyd resins, alkyd/acrylic resins and alkyd/silicone resins (see H. Wagner & H. F. Sarx, Op. cit., pp. 99-123), optional structured isocyanates or epoxy resins.

In addition, various compositions for coatings based on acrylate lacquer described in U.S. patent No. 4162249. Other acrylic/alkyd resins with polyisocyanate doba is Picadilly group, described in U.S. patent No. 4525521.

Coatings cured at ambient temperature and stabilized by the compounds of the present invention can be used for application to metal surfaces and as tinting decorative coatings for use on hard surfaces, especially for retouching. Lucky stabilized in accordance with the present invention, preferably applied in a standard way by two methods, either by applying a single coating or by spraying a double coating. In the latter method first applied pigmentaria primer coating, and then on top of this coating is applied a top coat of clear varnish. When using a dual coating compounds of the present invention the type of sterically obstructed amines can be introduced into a transparent coating or in both, both transparent and pigmentaria primer coating.

The present invention also relates to a wear-resistant composition for coating suitable for coating on top of the polycarbonates. Such coatings are described in U.S. patent No. 5214085 contain silicrylic, water, colloidal silicon dioxide, fotonica what to prolonged sunlight, humidity, yellowing caused by change of temperature, stratification and formation of microcracks, as well as lower transparency.

To improve the technological properties of systems for coating, cured at ambient temperature, were used stabilizers on the basis of related sterically obstructed amines, taken separately and in combination with UV absorbers. Despite such improvements, even the urgent need in the way of additional easing of photo-oxidation and photodegradation of these systems for coatings cured at ambient temperatures, and hence the need to improve efficiency by preserving the physical integrity of these coatings. Such efficiency can be achieved by preventing the increase of brittleness, cracking, corrosion, erosion, loss of gloss, haze and yellowing of the coating.

It was found that the above improvements can be achieved by substitution of the N-atom steric difficult amine group-OR, and by the use of such derivatives in systems for coatings cured at ambient temperature and is described in U.S. patent No. you are even less main, than the compounds described in U.S. patent No. 5124378, and are particularly suitable for solving this problem. In particular, the physical integrity of the coating is retained to a higher degree along with a significant reduction in loss of gloss and yellowing. Accordingly, the present invention relates to the use of NOR-compounds of the present invention, where the group R, in addition, substituted hydroxyl group, optionally in combination with other stabilizers intended for stabilization of systems for coatings cured at ambient temperatures and manufactured on the basis of alkyd resins; thermosetting acrylic resins; acrylic alkido; acrylic alkyd or polyester resins, optionally modified with silicon, isocyanates, isocyanurates, kamiminami or oxazolidinone; and epoxy resins, structured carboxylic acids, anhydrides, polyamines or mercaptans; as well as systems based on acrylic and polyester resins modified with reactive groups in the main polymer chain and structured epoxides, where the specified stabilization directed against the destructive action of light, moisture and oxygen.

The present invention also relates to UV-curable systems for coatings, which are unsaturated acrylic resins, polyurethane acrylates, epoxyacrylate, polyester acrylates, unsaturated polyester/styrene resins and similarity.

Powder coating

The present invention also relates to powder compositions for coating, which must be resistant to photodegradation. Resin systems that can be used are glycidyl methacrylate or acrylic hybrids with functional acrylate group, or acrylic hybrids, structured dibasic acids or anhydrides; acrylic or polyester resin with an acid functional or anhydrite functional group, structured TGIC; acrylic or polyester resin with a hydroxyl functional group, or they can be applied over water-soluble or solvent primer coating.

Stable coating may also contain a UV absorber, comprising one of the foregoing compounds.

System, cured under the action of radiation

The present invention also relates to systems, cured under the action of radiation. These systems should include:

a) Ethylenediamine polymerised compounds

b) at least one photoinitiator,

C) one or more stabilizing compounds of the present invention.

Composition for coating may also include a UV-absorbing stabilizer, presents one of the above classes.

This coating may also include pigments or other coloring agents to impart opacity or aesthetic properties.

Ethylenediamine curable compounds may contain one or more olefinic double bonds. They may be low molecular weight (Monomeric) or high molecular weight (oligomeric) connections.

Typical examples of monomers containing one double bond are alkyl or hydroxyethylacrylate or methacrylates, for example methyl-, ethyl", butyl, 2-e of the ditch are Acrylonitrile, acrylamide, methacrylamide, N-substituted (meta)acrylamide, vinyl esters such as vinyl acetate, vinyl ethers such as isobutylphenyl ether, styrene, alkylthiol, halogenation, N-vinyl pyrrolidone, vinyl chloride and vinylidenechloride.

Examples of monomers containing more than one double bond are diacrylate of ethylene glycol, diacrylate propylene glycol, diacrylate neopentyl glycol, diacrylate of hexamethyleneimine, diacrylate bisphenol a, 4,4’-bis(2-acryloyloxyhexyloxy)diphenylpropane, triacrylate of trimethylolpropane, triacrylate and tetraacrylate of pentaerythritol, pentaerythritoltetranitrate ether, vinylacetat, divinylbenzene, divinylbenzene, diallylphthalate, triethylphosphate, triallylisocyanurate or Tris(2-acrylonitril)isocyanurate. Examples of high molecular weight (oligomeric) polyunsaturated compounds are calironia epoxy resin, calironia polyesters, calironia polyurethanes and calironia polyesters. Other examples of unsaturated oligomers are unsaturated polyester resins, which are usually derived from maleic acid, phthalic acid and one or more diols, and which have a molecular weight of more than about 500. Nenas the joining are esters Ethylenediamine carboxylic acids and polyols or polyepoxides, and polymers containing Ethylenediamine group in the main chain or in side chains, including unsaturated polyesters, polyamides and polyurethanes and their copolymers, copolymers of polybutadiene and butadiene, copolymers of polyisoprene and isoprene, polymers and copolymers containing (meta)acrylic groups in side chains, and also mixtures of one or more of such polymers.

Illustrative examples of unsaturated carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, taconova acid, cinnamic acid, unsaturated fatty acids such as linolenic acid or oleic acid. Preferred are acrylic and methacrylic acid.

Suitable polyols are aromatic, preferably aliphatic and cycloaliphatic polyols. Aromatic polyols typically are hydroquinone, 4,4’-dihydroxydiphenyl, 2,2’-bis(4-hydroxyphenyl)propane, and novolak and Cresols. Polyepoxide are polyepoxide on the basis of these polyols, preferably based on aromatic polyols and epichlorohydrin. Other preferred polyols are polymers and copolymers which contain hydroxyl groups in dimethacrylate or their copolymers. Other suitable polyols are complex oligoesters, bearing a hydroxyl end groups.

Illustrative examples of aliphatic and cycloaliphatic polyols are alkylenedioxy containing preferably 2-12 carbon atoms, including ethylene glycol, 1,2 - or 1,3-propandiol, 1,2-, 1,3 - or 1,4-butanediol, pentandiol, hexanediol, octanediol, dodecanediol, diethylene glycol, triethylene glycol, polyethylene glycols having a molecular weight of preferably 200-1500, 1,3-cyclopentanediol, 1,2-, 1,3 - or 1,4-cyclohexanediol, 1,4-dihydroxyphenylglycol, glycerol, Tris-hydroxyethyl)amine, trimethylamin, trimethylolpropane, pentaerythritol, dipentaerythritol and sorbitol.

The polyols may be partially or fully tarifitsirovana the same or different unsaturated carboxylic acids; and in this case the free hydroxyl group of the partial esters can be modified, for example tarifitsirovana or esterified with other carboxylic acids.

Illustrative examples of esters are trimethylolpropane, Triethylenetetramine, trimethylolpropane, trimethylenetrinitramine, dimethacrylate tetramethyleneglutaric, pentaerythritoltetranitrate, dipentaerythritol, dipentaerythritol, dipentaerythritol, dipentaerythritol, dipentaerythritol, tripentaerythritol, pentaerythritoltetranitrate, pentaerythritoltetranitrate, dipentaerythritol, dipentaerythritol, tripentaerythritol, pentaerythritoltetranitrate, dipentaerythritol, dipentaerythritol, dipentaerythritol, diacrylate of ethylene glycol, 1,3-potentialities, 1,3-potentialtheorie, 1,4-mutandaaldactone, triacrylate sorbitol, tetraacrylate sorbitol, modified pentaerythritol triacrylate, cerametallic sorbitol, pentakill sorbitol, hexarelin sorbitol, acrylates and methacrylates complex oligoether, di - and triacrylate glycerol, 1,4-cyclohexanediamine, bicarinate and mimetically of polyethylene glycol having a molecular weight of 200-1500, and mixtures thereof. Polyfunctional monomers and oligomers are compounds supplied, for example, UCB Chemicals, Smyrna, Georgia and Sartomer, Exton, Pennsylvania.

Suitable Ethylenediamine curable compounds are also the amides of identical or different nental 2-6, and more preferably 2-4 amino groups. Examples of such polyamines are Ethylenediamine, 1,2 - or 1,3-Propylenediamine, 1,2-, 1,3 - or 1,4-butylenediamine, 1,5-pentanediamine, 1,6-hexylaniline, octylaniline, dodecylamine, 1,4-diaminocyclohexane, ISOPHORONEDIAMINE, phenylenediamine, biphenylamine, bis (a-amino-ethyl)ether, Diethylenetriamine, Triethylenetetramine, bis (aminoethoxy)ethane or bis(-aminopropoxy)ethane. Other suitable polyamines are polymers and copolymers, which may contain additional amino group in the side chain, and oligoimide containing terminal amino groups.

Examples of such unsaturated amides are: methylenebisacrylamide, 1,6-hexamethyleneamine, diethylenetriaminepentaacetate, bis(methacryloyloxy)ethane-methacrylamidoethylene, N-[(hydroxyethoxy)ethyl]acrylamide.

Suitable unsaturated polyesters and polyamides are usually obtained from maleic acid and diols or diamines. Maleic acid may be partially replaced by other dicarboxylic acids such as fumaric acid, taconova acid, Tarakanova acid, musicanova acid or carmelina acid. To regulate the reactivity of the polyol and concern for the impact of different amounts of saturated dicarboxylic acids, such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophtalic acid, succinic acid or adipic acid. Unsaturated polyesters can be used together with ethyleneimine the comonomers, such as styrene. Polyesters and polyamides may also be derived from dicarboxylic acids and Ethylenediamine diols or diamines, in particular of long-chain diamines, usually containing from 6 to 20 carbon atoms. The polyurethanes are generally derived from saturated or unsaturated diisocyanates and unsaturated and saturated diols.

Suitable polyester acrylates or calironia polyesters obtained by reaction of the oligomers, usually epoxides, urethanes, polyethers or polyesters with acrylates, such as hydroxyethylacrylate or hydroxypropylamino.

Polybutadiene and polyisoprene, and their copolymers are known compounds. Suitable comonomers are olefins such as ethylene, propene, butene, hexene, (meth)acrylate Acrylonitrile, styrene or vinyl chloride. Polymers containing (meth)acrylate group in its side chain, are also known compounds.

Usually they are the reaction products epoxidization derivatives, which tarifitsirovana (meth)acrylic acid, or Homo - and copolymers of (meth)acrylates, which tarifitsirovana hydroxyalkyl(meth)acrylates.

The preferred monomers, typically, are alkyl - or hydroxyethylacrylate or methacrylates, styrene, diacrylate of ethylene glycol, diacrylate propylene glycol, diacrylate neopentyl glycol, diacrylate of hexamethyleneimine or diacrylate bisphenol a, 4,4’-bis(2-acryloyloxyhexyloxy)diphenylpropane, trimethylolpropane, pentaerythritoltetranitrate or tetraacrylate, and preferably acrylates, styrene, diacrylate of hexamethyleneimine or diacrylate bisphenol a, 4,4’-bis(2-acryloyloxyhexyloxy)diphenylpropane, trimethylolpropane.

Especially preferred (oligomeric) polyunsaturated compounds are acrylates of polyester or unsaturated polyester resins, which are derived from maleic acid, fumaric acid, phthalic acid and one or more diols and have molecular weight component usually from about 500 to 3000.

Preferred unsaturated carboxylic acids are acrylic acid and methacrylic acid.

Photopolymerizable connection use/P>

To unsaturated photopolymerizing compounds can also be added to the binder. Adding binders are particularly useful in the case when photopolymerizable compounds are liquid or viscous substances. The amount of binder may range from 5 to 95%, preferably 10-90%, and most preferably 40-90% by weight of the entire composition. The choice of binder depends on the intended use and desired properties, such as the ability of the composition to decompose in water-organic solvents, the ability to adhesion on the substrate and susceptibility to the action of oxygen.

Suitable binders are typically materials having a molecular weight of from about 5000 to 2000000, and preferably 10000-1000000. Typical examples are: Homo - and copolymers of acrylates and methacrylates, including copolymers of methyl methacrylate/ethyl acrylate/methacrylic acid, poly(alkyl methacrylates), poly(alkylacrylate); simple and complex esters of cellulose such as cellulose acetate, acetobutyrate cellulose, methylcellulose, ethylcellulose; butyral, polyvinylformal, cyklinowanie rubber, polyethers such as polyethylene oxide, polypropylene is illorin, copolymers of vinyl chloride/vinylidenechloride, copolymers of vinylidenechloride with Acrylonitrile, methyl methacrylate and vinyl acetate, polyvinyl acetate, copoly(ethylene/vinyl acetate), polymers such as polycaprolactam and poly(hexamethylenediamine), polyesters, such as poly(terephthalate glycol) and poly(succinate of hexamethyleneimine).

Unsaturated compounds can also be used in a mixture with photopolymerizable film-forming components. These components may be physically drying polymers or their solutions in organic solvents, such as nitrocellulose or acetobutyrate cellulose. Photopolymerizable unsaturated monomers may be a component of the curable mixture, obtained by free-radical ion polymerization, such as curing the mixture obtained by free-radical cationic polymerization. Of great interest are also systems that are subjected to cycles as thermo-and photo-induced curing, such as powder coatings, laminates, some adhesives and encapsulating coating.

The mixture of prepolymer with polyunsaturated monomers which, in addition, contain the m defines the properties of the paint film, and by varying these properties specialist may affect properties utverzhdenii film. Polyunsaturated polymer acts as a crosslinking agent, which makes this paint film insoluble. Monounsaturated monomer acts as a reactive diluent, which may be reduced viscosity without the use of solvent. In addition, properties utverzhdenii compositions, such as curing rate, the density of the polymer network and surface properties depend on the choice of monomer.

Unsaturated polyester resins are typically used in two-component systems in combination with monounsaturated monomer, preferably styrene units.

The binary system of electron-rich/electron-deficient monomers are often used in viscous pigmented coatings. For example, system vinyl ester/unsaturated polyester used in powder coatings, and the system styrene/unsaturated polyester used in gel coats.

The preferred method is a method where Ethylenediamine curable compounds are a mixture of (i) at least about the BPO is the way, where Ethylenediamine curable compounds are a mixture of (i) unsaturated polyesters, especially those derived from maleic acid, fumaric acid and/or phthalic acid and one or more diols and have molecular weight, typically comprising from about 500 to 3000 and (ii) acrylates, methacrylates or styrene, or combinations thereof.

Of particular interest is also the method where Ethylenediamine curable compounds are a mixture of (i) unsaturated polyesters and (ii) acrylates or methacrylates, or combinations thereof.

Other interest method is a method where Ethylenediamine curable compounds are a mixture of (i) unsaturated acrylates complex polyester and (ii) acrylates or methacrylates, or combinations thereof.

The synthesis of compounds

Compounds of the present invention can be obtained by reaction of the hydride of anti-and halogen-substituted alcohol, which are formed centered on the carbon radicals, which are captured nitrostilbene connections.

Compounds of the present invention can be also obtained peregruppirovaniya due to photochemical or thermal degradation of complex PROXIFIER or dealkylated in the presence of alcohol. Connection with bridge connections described above can be formed in the case when two nitroxyl radicals are associated with the same solvent molecule, especially at the low amount of solvent.

A preferred method of preparing compounds of the present invention involves the reaction of sterically constrained N-oxyamino with centered on the carbon radical, generated by mixing an aqueous or alcohol solution of a metal ion such as Fe2+, Fe3+,Cu2+or C+and peroxide, such as tert-butylhydroperoxide or hydrogen peroxide in the presence of an alcoholic solvent at a temperature of 20-80°C. Particularly effective is the combination of ferric chloride(2), iron chloride(3) or iron sulfate(2), and especially ferric chloride(2) or ferric chloride(3) and hydrogen peroxide. Water can be added to the alcohol at the beginning of the reaction to increase the solubility of the metal salt or dissolution of the alcohol, which becomes solid at the reaction temperature. To the reaction mixture can be added ligand, such as 2,2’-dipyridyl, 2,2’:6’,2’-terpyridyl. Two nitroxyl radical can sometimes contact the same mole is built previously. The formation of compounds with bridging communication occurs mainly under reduced amount of solvent.

Some of the replacement N-alkoxysilane of the present invention can react with monofunctional or bifunctional esters, acids or anhydrides or isocyanates with formation of polymeric derivatives of ester or urethane.

Thus, another objective of the present invention is to develop a method for the synthesis of N(hydroxyalkoxy)-substituted sterically obstructed amines of the formula IV:

where G1and G2independently represent alkyl with 1-4 carbon atoms, or G1and G2taken together, represent pentamethylene;

T represents a divalent organic residue required to form a five - or six-membered ring containing sterically hindered nitrogen atom and two Quaternary carbon atoms, substituted G1and G2;

E is (b+1)-valent alkalinity radical with 2-18 carbon atoms; alkenylamine radical with 3-19 carbon atoms; cycloalkenyl radical with 5-12 carbon atoms; cycloalkanones radical with 5-12 atoms ug is uma alkilani with 1-4 carbon atoms; and

b is 1, 2 or 3, with the proviso that b cannot exceed the number of saturated carbon atoms in E, and if b is 2 or 3, each hydroxyl group is linked to another carbon atom in E;

moreover, this method involves:

the reaction of sterically zatrudnennogo N-oxyamino formula V

with the alcohol of formula VI

in the presence of peroxide or organic hydroperoxide and a catalytic amount of a metal salt or metal-ligand complex.

N-axelavia the compounds of formula V can be obtained by reaction of the corresponding sterically constrained N-H-amine with hydrogen peroxide and sodium tungstate as described E. G. Rosantsev et al., in Synthesis, 1971, 192; or hydroperoxide and molybdenum (VI), as described in U.S. patent No. 4691015.

More specifically, the method of the present invention involves the reaction mixture 5-100 mol of the alcohol of formula VI, 1-15 mol of hydrogen peroxide or organic hydroperoxide 0.001 to 0.5 mol of metal salt or complex of the metal-ligand" mol N-Oxylog the compounds of formula V. This reaction is preferably carried out at a temperature in the range from 20 to 100°C.

Alcohol can perform two RIT nonequivalent carbon-hydrogen bonds, which are reactive in the method of the present invention. So, for example, tert-butyl alcohol can give only one product, whereas tert-amyl alcohol can give three different reaction product. When alcohol becomes solid at the reaction temperature, or when the metal salt or complex of the metal-ligand" is not well soluble in alcohol, can be used as a co-solvent. Typical co-solvents are water, methanol and ethylene glycol.

In the method of the present invention is mainly used in less than stoichiometric amount, based on the amount of peroxide, transition metal salt or metal-ligand complex, where the metals are selected from Groups IVA, VA, VIIA, VIIIA and IB (transition metals, metals, has the lowest atomic mass for this group are Ti, V, Mn, Fe, Co, Mi, si) of the Periodic table of elements. The most effective catalysts are iron(II), iron(II), copper(I) and copper(II). This metal may be present in the form of a simple salt, such as chloride or sulfate of a metal, metal salt and an organic acid such as acetic acid, or metal oxides, which may also contain a cation of Group IA or IIA Periodical, such as 2,2’-dipyridyl, ethylenediaminetetraacetic acid or its disodium salt, oxide, triphenylphosphine or the anion of acetylacetone. These metal-ligand complexes are commercially available or they can be obtained in situ by mixing the metal salt with the ligand. The number of ligand may be less than the quantity necessary for the formation of a full range of metal based on its oxidation state. Salt of the metal or metal-ligand complex may be associated with a solid carrier such as silica gel, so that it could be isolated and reused.

To the reaction mixture can be added mineral acid or sulfonic acid in the amount of up to 1 mole per mole of nitroxyl part.

The method of the present invention can be carried out in an atmosphere of air or in an inert atmosphere, such as nitrogen or argon.

There are several options for implementing the method of the present invention. One option involves adding a solution of aqueous hydrogen peroxide or organic hydroperoxide to a mixture of sterically constrained N-oxyamino, alcohol and co-solvent (if used) and acid (if it ispoveduyu temperature support by limiting the speed of adding peroxide and/or through the use of baths for heating or cooling. After addition of the peroxide, the reaction mixture is stirred until then, until the original N-ansilove compound of formula V will not be expended or until until it is converted into a compound of formula IV. Tracking the reaction is best done by using thin-layer chromatography, gas chromatography or liquid chromatography. In the course of the reaction can be added an additional amount of metal salt or metal-ligand complex. After adding to the reaction mixture of the initial quantity of peroxide for the reaction is completed to the reaction mixture may be dropwise added an additional amount of peroxide.

The second variant of the method of the present invention involves the simultaneous addition of separate solutions of peroxide and nitrocellulose connection to the mixture of the alcohol co-solvent (if used), acid (if used) and the metal salt or metal-ligand complex. Nitrocellulose compound can be dissolved in water or in an alcohol solvent used in this reaction. Before adding peroxide in the reaction mixture can be introduced a number nitrocellulose connection, and by adding peroxide.

Another variant of the method of the present invention involves the simultaneous addition of separate solutions of peroxide and water or alcohol solution of metal salt or metal-ligand complex to a mixture nitrocellulose compounds, alcohol, co-solvent (if used) and acid (if used). Before adding peroxide in the reaction mixture may be added a certain amount of metal.

Another variant of the method of the present invention involves the simultaneous addition of separate solutions of peroxide and water or alcohol solution nitrocellulose connection or an aqueous or alcohol solution of metal salt or metal-ligand complex to alcohol, the co-solvent (if used) and the acid (if used). Before adding peroxide in the reaction mixture can be added part nitrocellulose connection and/or a metal salt or metal-ligand complex. Before you finish adding the peroxide must be added all the rest of nitrocellulose connection.

If this reaction is acid, this acid may be added in one portion at the beginning of the reaction, LII; or all of the acid may be added during the reaction. Some xylote or all of the acid may be mixed with the salt of the metal, if the metal salt is added in the form of a solution in the reaction.

If the metal-ligand complex are in situ, the metal salt and the ligand is most effective to mix before contacting nitroxylenes connection.

At the end of the reaction before allocating any residual products of the peroxide should be subjected to thorough decomposition.

Preferred methods

In formulas (IV) and (V) G1and G2preferably represent methyl. T preferably represents 2-hydroxy-1,3-PROPANEDIOL or 2-oxo-1,3-propandiol.

If b equals 1, then S(HE) is centered on the carbon radical formed preferably from 2-methyl-2-propanol (=tert-butyl alcohol), 2-propanol, 2,2-dimethyl-1-propanol, 2-methyl-2-butanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-nonanol, 1-decanol, 1-dodecanol, 1-octadecanol, 2-butanol, 2-pentanol, 2-ethyl-1-hexanol, 1-octanol, cyclohexanol, cyclooctanol, allyl alcohol, fine-delovogo alcohol or 1-phenyl-1-ethanol; and most predpochtitel">If b is 2-E-(OH)2is a centered on the carbon radical formed preferably from 1,2-propane diol, 1,3-propane diol, 1,2-butanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propane diol, 2,5-dimethyl-2,5-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol or 1,4-cyclohexanediol; and most preferably, if the radical-O-(OH)2formed from 1,4-butanediol, 2,2-dimethyl-1,3-propane diol, 1,2-cyclohexanediol, 1,3-cyclohexanediol or 1,4-cyclohexanediol.

If b is equal to 3,- E-(OH)2is a centered on the carbon radical formed preferably from 1,1,1-Tris(hydroxymethyl)ethane, 2-ethyl-2-(hydroxymethyl)-1,3-propane diol, 1,2,4-butanetriol or 1,2,6-hexanetriol; and most preferably, if the radical-O-(OH)3formed from 1,1,1-Tris(hydroxymethyl)ethane or 2-ethyl-2-(hydroxymethyl)-1,3-propane diol.

b is preferably equal to 1 or 2; and most preferably 1.

The preferred products of the method of the present invention are compounds of the formulas (1) to(30) above.

The preferred peroxides are hydrogen peroxide, the product of the merger of urea and hydrogen peroxide, tert-butylhydroperoxide, tert-aming the accession of urea and hydrogen peroxide; and the most preferred is hydrogen peroxide.

Hydrogen peroxide may be present in an amount of 15-50% by weight solution in water, and preferably in the amount of 30-50% by weight solution in water.

Preferably the metal is selected from metals of Groups IVA, VA, VIIA, VIIIA and IB of the Periodic table of elements. More preferred are iron(II), iron(III), copper(1), copper(II), cobalt(II), cobalt(III), manganese(II) manganese(III), vanadium(II), vanadium(III), cerium(III) or titanium(III). Most preferred are iron(II), iron(III), copper(I) and copper(II).

Preferred counterions for the above metals are chloride, sulfate, acetylacetonate (ASAS), acetate, citrate, oxalate, nitrate, perchlorate, cyanide, hydroxide, phosphate, pyrophosphate and oxide.

The preferred ligands for the above metals are 2,2’-dipyridyl, 2,2’:6,2’-terpyridyl, 1,10-phenanthroline, ethylenediaminetetraacetic acid, disodium salt atlandia-montereysalinas acid, pyridine, picolina acid, 2-pyrazinecarboxamide acid, aromatic diimine formed in the reaction of aniline or substituted anilines with 1,2-diketones, such as 2,3-butandiol or oxide triphenyltin the iron(3), iron phosphate(3), pyrophosphate of iron(3), phosphate(2), ferrous sulfate(2), ferrous sulfate(3), iron acetate(2), citrate of iron(3), iron oxalate(2), iron nitrate(3), perchlorate iron(2), chloride copper(2) chloride copper(3) copper sulfate(2), manganese chloride(2), metavanadate sodium, chloride, titanium(2), chloride of vanadium(II), and chloride of vanadium(III). The most preferred metal salts are ferric chloride(2), ferric chloride(3), iron acetylacetonate(3), phosphate(3), pyrophosphate of iron(3), phosphate(2), ferrous sulfate(2), ferrous sulfate(3) and copper sulfate(3).

Preferred metal-ligand complexes are complexes formed from salts of iron(II), iron(III), copper(I) or copper(II) and 2,2’-dipyridyl, triphenylphosphine oxide, ethylenediaminetetraacetic acid or the disodium salt of ethylenediaminetetraacetic acid. The most preferred metal-ligand complex is a complex formed from ferric chloride(2) or ferric chloride(3) and 2,2’-dipyridyl.

Preferred acids are hydrochloric acid, sulfuric acid, methanesulfonate acid, oxalic acid, triperoxonane acid, polyphosphoric acid and phosphoric acid; the most preferred acids are IU is about an alcoholic solvent for the method of the present invention depends, to some extent, on the relative number of atoms of the reactive hydrogen in an alcohol reagent and steric blockage of aminohydroxylation connection. The reaction is usually carried out at a ratio of 5-100 moles of solvent per mole nitrocellulose part, preferably at a ratio of 10 to 50 mol per mole of nitroxyl parts, and most preferably at a ratio of 10-30 moles of solvent per mole of nitroxyl part. May also be a co-solvent, which is preferably selected from water, methanol, ethylene glycol or mixtures thereof.

The preferred amount of hydrogen or organic hydroperoxide is 1-20 mol per mole of nitroxyl parts, more preferred amount is 1-5 mol of peroxide per mole of nitroxyl part, and the most preferred amount is 1-3 moles of peroxide per mole of nitroxyl part.

The preferred amount of metal salt or metal-ligand complex is 0.001 to 0.5 molar equivalents per mole of nitroxyl part; the most preferred ratio is the ratio of 0.001 to 0.05 mol of metal salt or metal-ligand complex per mole of nitroxyl part.

If able equivalents per mole of nitroxyl part, and most preferred is a ratio of 0.01 to 0.5 molar equivalents of acid per mole of nitroxyl part.

The reaction is usually carried out at a temperature of 20 to 100°C; and preferably at 60 to 100°C.

The following examples are only for illustrative purposes and should not be construed as a limitation of the method of the present invention. Room temperature is considered to be the temperature between 20 and 25°C.

Abbreviations:

v - part./vol.;

w - part./mass.;

1H-NMR - nuclear magnetic resonance (NMR)1H;

m/z - mass spectrometry (atomic units);

A. E. - molecular mass in g/mol (= atomic units).

In the Example, P1-P is illustrated a new method to produce compounds of the present invention.

In the Example, P1 is illustrated the use of ferric chloride(3) in the method of the present invention.

Example P1

4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

A solution of 9.4 g (140 mmol) of 50% aqueous hydrogen peroxide mixed with 20 ml of tert-butyl alcohol was added over four hours at 45 to 50°C to the mixture 3,44 g (20.0 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethyl maintained at 45 to 50°C for 19 hours. Analysis by gas chromatography showed the presence of less than 1% of the original nitrocellulose connection.

Example 2 describes the management of a metal catalyst on a solid medium.

Example P2

4-hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

2,2’-Dipyridyl (0.16 g, 1.0 mmol) and 2.54 g (0.80 mmol) of 5% ferric chloride on silica gel was stirred with 30 ml of tert-butyl alcohol, which was heated to 45°C. To the mixture was added 3,44 g (20.0 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-Tetra-methylpiperidine and 10 ml of water. To the reaction mixture for four hours at 45 to 50°C was added a solution of 9.4 g (138 mmol) of 50% aqueous hydrogen peroxide mixed with 20 ml of tert-butyl alcohol. The temperature was maintained at 45 to 50°C for 30 minutes. Analysis by gas chromatography showed that the original nitrocellulose connection completely reacted with the formation of more than 90% of the target connection.

The silica gel was separated by filtration and the above experiment was repeated using the selected silica gel. After the reaction mixture for 4.5 hours was added almost all the amount of peroxide gas chromatogra for 19 hours at 45 to 50°With only 5% of the original nitrocellulose connection.

Example P3

The reaction of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine with isopropyl alcohol

2,2’-Dipyridyl (0.156 g, 1 mmol) was added to a mixture of 0.20 g (1 mmol) of iron chloride tetrahydrate in 30 ml of isopropyl alcohol at 40°C. To the mixture was added 3,44 g (20 mmol) 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine and 10 ml of water. To the above mixture for seven hours at 40 to 45°C was added a solution of 9.4 g (138 mmol) of 50% aqueous hydrogen peroxide in 20 ml of isopropyl alcohol. The crude reaction mixture was cooled and subjected to reaction with 0.5 g of sodium borohydride. Analysis using gas chromatography/mass spectrometry showed that the main component of the reaction mixture is 4-hydroxy-1-(2-hydroxypropoxy)-2,2,6,6-tetramethylpiperidine (m/z = 231).

Example P4

The reaction of 1-oxyl-2,2,6,6-tetramethylpiperidine-4-one with tert-amyl alcohol

2,3’-Dipyridyl (0,078 g, 0.50 mmol) was added to a mixture of 0.99 g (5.0 mmol) of ferric chloride tetrahydrate in 150 ml of tert-amyl alcohol at 25°C. To this mixture was added 0.2 g of tetrabutylammonium chloride and 17.2 g (101 mmol) of 1-oxyl-2,2,6,6-tetramethyl-piperidine-4-it. To the above mixture for three hours at 25-30°C. was added a solution of 29.5 g (434 mmol what th mixture is thoroughly extracted with ethyl acetate to obtain and 23.4 g of orange oil. Analysis was carried out using gas chromatography/mass spectrometry indicated that the oil contains three main reaction product is approximately in the ratio 2:2:1 (% of area). These three products are consistent with the reaction products of the original nitrocellulose connection with each of the possible carbon radicals formed from tert-amyl alcohol.

Example P5

The reaction of 1-oxyl-2,2,6,6-tetramethylpiperidine-4-one with 1-butanol

Repeating the procedure of Example P4 using 150 ml of n-butyl alcohol instead of tert-amyl alcohol. After treatment of the reaction mixture were received of 19.2 g of orange oil. Analysis was carried out using gas chromatography/mass spectrometry indicated that the three components of the mixture correspond to reaction products source nitrocellulose connection with the radical formed by removal of hydrogen from 1-butanol.

Example P6

The reaction of 1-oxyl-2,2,6,6-tetramethylpiperidine-4-it neopentylglycol

Repeating the procedure of Example 4 using a mixture of 400 ml of 2,2-dimethyl-1,3-propane diol (=neopentyl glycol) and 55 ml of water instead of tert-amyl alcohol. After processing the reaction mixture was awarded 14, the scrap

Repeating the procedure of Example P4 using a mixture of 150 ml of 2-octanol instead of tert-amyl alcohol. Then added peroxide for six hours at 25-30°C and the reaction mixture was stirred over night at room temperature. After treatment of the reaction mixture were received and 19.4 g of orange oil. Analysis was carried out using gas chromatography/mass spectrometry, showed that the five components of the mixture corresponded to the reaction products of the original nitrocellulose connection with radicals formed in the removal of hydrogen from 2-octanol.

In the Examples R8-R described the use of mineral acids with various salts of iron in the method of the present invention.

Example P8

4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

A solution of 17.2 g (100 mmol) 4-hydroxy-1-oxyl-2,2,6,6-Tetra-methylpiperidine dissolved in 40 ml of water, and three quarters of a solution of 25.0 g (of 0.37 mol) of 50% aqueous hydrogen peroxide were added simultaneously for three hours at 40°C to a mixture of 1.12 g (4.0 mmol) of iron sulfate heptahydrate, 25 ml of water, 0.5 ml of 98% sulfuric acid and 200 ml of tert-butyl alcohol. After completion of the merger of nitroxyl real 1/4 part of the peroxide solution was added over 1 hour at 40°C. After one hour the reaction mixture was added dropwise a solution of 2.9 g (40 mmol) of 50% aqueous hydrogen peroxide. After 1.3 hours to the mixture in one portion was added a solution of 0.14 g (0.5 mmol) of iron sulfate heptahydrate(2), 0.15 ml of 98% sulfuric acid and 1-2 ml of water. The reaction mixture was stirred for another 40 minutes at 40°C. After the peroxides were split under the action of sodium sulfite, the reaction mixture was treated with sodium hydroxide and sodium borohydride, and then concentrated. The residue was dissolved in ethyl acetate and passed through silica gel to obtain 20.5 g (84%) of target compound as a white solid.

Example P9

4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

A solution of 34.5 g (200 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine dissolved in 75 ml of water, and a solution of 49.5 g (0.73 mol) of 50% aqueous hydrogen peroxide at the same time for seven hours at 40°C was added to a mixture of 1.61 g (8.1 mmol) of ferric chloride tetrahydrate, 50 ml of water, 1.6 ml of 37% hydrochloric acid and 390 ml of tert-butyl alcohol. After about 4 hours added to the reaction mixture solution was added to 0.22 g (1.1 mmol) of ferric chloride tetrahydrate, 0.2 ml of 37% hydrochloric acid and 1-2 ml of water. The reaction of MCA 0.11 g (0.55 mmol) of ferric chloride tetrahydrate, 0.1 ml of 37% hydrochloric acid and 1-2 ml of water and a solution of 5.8 g (85 mmol) of 50% aqueous hydrogen peroxide by heating the reaction mixture at 40°C. the Reaction mixture was filtered to remove solids, reduce sodium sulfite, was treated with sodium hydroxide and sodium borohydride, and concentrated. The residue was dissolved in ethyl acetate and passed through silica gel to obtain 42.6 g (yield 87%) of target compound as a white solid.

Example P10

4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

A solution of 17.2 g (100 mmol) 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine dissolved in 50 ml of water, and a solution of 25.3 g (of 0.37 mol) of 50% aqueous hydrogen peroxide for 3-3 .5 hours at 40°C were simultaneously added to a mixture of 0.27 g (1.0 mmol) of uranyl ferric chloride, 25 ml of water, 1.1 ml of 37% hydrochloric acid and 200 ml of tert-butyl alcohol. After about 2 hours added to the reaction mixture was added 0.5 ml of 37% hydrochloric acid. When you are finished adding peroxide was added 1.2 ml of 37% hydrochloric acid and the reaction mixture was heated at 40-50°C for 3.5 hours. The reaction mixture was stirred over night at room temperature. The reaction was completed by adding two is as described in Example P9 and received a 21.5 g (yield 88%) of target compound as a white solid. Gas chromatography showed that the product was pure by more than 96%.

Example P11

4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

A solution of 17.2 g (100 mmol) 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine dissolved in 40 ml of water, and three quarters of a solution of 25.0 g (of 0.37 mol) of 50% aqueous hydrogen peroxide for 2.5 hours at 40°C were simultaneously added to a mixture of 1.46 g (4.1 mmol) of iron acetylacetonate, 25 ml of water, 0.5 ml of 98% sulfuric acid and 200 ml of tert-butyl alcohol. After adding nitroxyl to the reaction mixture was added 0.18 g (0.5 mmol) of iron acetylacetonate. The remaining one quarter of the peroxide solution was added during one hour at 40°C. After heating for two hours gas chromatography showed that the reaction mixture remained less than 10% nitrocellulose connection. To the reaction mixture was added sulfuric acid (0.3 ml) and a solution of 4.9 g (72 mmol) of 50% aqueous hydrogen peroxide, and the reaction mixture was stirred over night at room temperature. After processing, carried out as described in Example P9, got 18,1 g (yield 74%) of target compound as a white solid.

Example R

4-Hydroxy-1-(the population of sulfuric acid for 1.5 hours after addition of the peroxide remained 69% source nitrocellulose connection. It was different from the data obtained in Example P11, where for the comparable time, there was only 10% nitrocellulose connection.

Example P13

1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-one

To a mixture of 17.0 g (100 mmol) of 1-oxyl-2,2,6,6-tetramethylpiperidine-4-it, 0,994 g (5 mmol) chloride tetrahydrate, iron, and 1 ml of 37% sulfuric acid, 360 ml of tert-butyl alcohol and 120 ml of water in a period of 7.5 hours added to 23.6 g (347 mmol) of 50% aqueous hydrogen peroxide. The reaction mixture was saturated with potassium chloride, and the aqueous layer was extracted with tert-butyl alcohol. The combined organic layers were concentrated to obtain an orange oil. This oil was dissolved in methylene chloride and purified using flash chromatography on silica gel using hexane:ethyl acetate (4:1)(about/on). The obtained yellow oil was led with the receipt of 8.3 g of a white solid substance with so pl. 57-60°C. the isolated product was injected into the gas chromatograph and found that he has the same retention time, which is similar to the sample target of the connection.

In the Examples R, R and P16 illustrates the influence of different ligands of the formula (IV):

on the formation of the compound of Example P13.

P) tetrahydrate of ferric chloride and 150 ml of tert-butyl alcohol consistently at 35°C was added 1.18 g (5.0 mmol) of N,N’-(1,2-dimethyl-1,2-etadirect)bis-(benzoylamino), where in formula IV, X is hydrogen, and 17.0 g (100 mmol) of 1-oxyl-2,2,6,6-tetramethylpiperidine-4-it. To the above mixture for eight hours at 35 to 40°C was added a solution of 47.5 g (700 mmol) of 50% aqueous hydrogen peroxide mixed with 60 ml of tert-butyl alcohol. The reaction mixture was stirred for another 16 hours at 40°C. Analysis by gas chromatography indicated the presence of less than 4% of the original nitroxyl. Solids were removed by filtration and the filtrate was subjected to reaction with aqueous solution of sodium sulfite to decompose excess peroxide. The reaction mixture was carefully extracted with ethyl acetate and after concentration was received with 21.4 g of a crude product containing more than 93% of the target compounds, as it was shown by gas chromatography.

Example R

1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-one

Repeating the procedure of Example R using 1.48 g (5 mmol) N,N’-(1,2-dimethyl-1,2-etadirect)bis(4-methoxybenzamide), where in formula IV, X is methoxy, instead of N,N’-(1,2-dimethyl-1,2-etadirect)bis(benzenamine), where in formula IV, X is hydrogen. Upon completion of the reaction analysis by gas chromatography indicated the th product which contained 97% of the target compounds, as it was shown by gas chromatography.

Example P16

1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-one

Repeating the procedure of Example R using 5.0 mmol N,N’-(1,2-dimethyl-1,2-etadirect)-bis(4-chlorobenzene-amine), where in formula IV, X is chlorine, instead of N,N’-(1,2-dimethyl-1,2-etadirect)bis(benzenamine), where in formula IV, X is hydrogen.

Example R17

4-Benzyloxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

A solution of 18.4 g (0.27 mol) of 50% aqueous hydrogen peroxide mixed with 50 ml of tert-butyl alcohol was added over two hours to a mixture 24,9 g (0,090 mol) of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine, 7,13 g (being 0.036 mol) of ferric chloride tetrahydrate, 3.7 g (0,030 mol) pikolinos acid and 150 ml of tert-butyl alcohol at 60°C. After the addition of peroxide, the reaction temperature was maintained at 60°C for 5 hours. The reaction mixture was filtered to remove solids and the filtrate was stirred for 30 minutes with 1 liter of 10% aqueous solution of sodium sulfite to decompose excess peroxide. An aqueous solution three times were extracted with methylene chloride and objetivo oil. After purification using flash chromatography on silica gel using a mixture of hexane:ethyl acetate (4:1)(V/V) was obtained 12.0 g of oil of amber. NMR and mass spectrometry analyses confirmed that this product is the target of the connection.

In the Example P18 shows the effect observed in the absence of Pikalyovo acid of Example R17.

Example P18

4-Benzyloxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

A solution of 20.4 g (0.30 mol) of 50% aqueous hydrogen peroxide mixed with 25 ml of tert-butyl alcohol within three hours was added to a mixture of 27.6 g (0.10 mol) of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine, 7,13 g (being 0.036 mol) of ferric chloride tetrahydrate and 115 ml of tert-butyl alcohol at 40°C. After the addition of peroxide, the reaction temperature was maintained at 40°C. for twenty hours. The crude reaction mixture was purified using flash chromatography on silica gel, resulting in a received 16.2 g of the target compound.

Example P19

The reaction of bis(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl)sebacate with neopentyl alcohol

Aqueous hydrogen peroxide was added to a mixture of bis(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl)sebacate 4-hydroxy-1-oxyl-2,2,6,6-tetramethyl piperidine with neopentylglycol

Aqueous hydrogen peroxide was added to a mixture of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl)sebacate and ferric chloride in neopentylglycol the method described in Example P18.

Example P21

The reaction of 4-octadecanoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine with tert-amyl alcohol

Aqueous hydrogen peroxide was added to a mixture of 4-octadecanoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferric chloride in tert-amyl alcohol by the method described in Example P18.

Example P22

The reaction of 4-octadecanoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine with tert-butyl alcohol

Aqueous hydrogen peroxide was added to a mixture of 4-octadecanoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferric chloride to tert-butyl alcohol by the method described in Example P18.

Example R23 Is Applied

The reaction of 4-benzyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine with propylene glycol

Aqueous hydrogen peroxide was added to a mixture of 4-benzyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and tetrahydrate of ferric chloride in propylene glycol by the method described in Example P18.

Example R24

The reaction of 1-oxyl-2,2,6,6-tetramethylpiperidine-4-it triethyleneglycol

Water blanch vocale way described in Example P18.

Example P25

The reaction of bis(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl)sebacate with 2-propanol

Aqueous hydrogen peroxide was added to a mixture of bis(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl)sebacate and tetrahydrate of ferric chloride in 2-propanol by the method described in Example P18.

Example R

The reaction of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine with 1,4-butanediol

Aqueous hydrogen peroxide was added to a mixture of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and tetrahydrate of ferric chloride in 1,4-butanediol as described in Example P18.

Example P27

The reaction of 4-hexyloxy-1-oxyl-2,2,6,6-tetramethyl piperidine with pinkola

Aqueous hydrogen peroxide was added to a mixture of 4-hexyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and iron chloride tetrahydrate in penacola the method described in Example P18.

Example P28

The reaction of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine with 2-ethyl-1-hexanol

Aqueous hydrogen peroxide was added to a mixture of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine and tetrahydrate of ferric chloride in 2-ethyl-1-hexanol the method described in Example P18.

In the Examples R-R shown eff-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

To a mixture of a metal salt, acid, if used, 25 ml of water and 200 ml of tert-butyl alcohol, supported at a temperature of 35 to 45°C, was added 50% aqueous hydrogen peroxide solution at a speed of adding approximately 100 mmol per hour, and simultaneously added a solution of 17.2 g (100 mmol) 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine dissolved in 40-45 ml of water, at a speed of adding 35-50 mmol per hour. After addition of all reagents, the reaction mixture was kept at 35 to 45°C, and in some cases the reaction mixture was stirred over night at room temperature. The reaction course was monitored by gas chromatography. The results are shown in table.1.

Example R

1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-one

A solution of 1.0 g (15 mmol) of 50% aqueous hydrogen peroxide in 5 ml of tert-butyl alcohol was added within 30 minutes at 60°C to a mixture of 0.5 g (2.9 mmol) of 1-oxyl-2,2,6,6-tetramethylpiperidine-4-she, 0.1 g (0.16 mmol) of the chloride N,N’-bis(3,5-di-tert-butylchloride)-1,2-cyclohexanediamine(II) (catalyst Jacobson) and 10 ml of tert-butyl alcohol. The reaction mixture was stirred over night at 60°C. Gas chromatography indicated Pris the si)-2,2,6,6-tetramethylpiperidine-4-one

Repeating the procedure of Example R using 0.25 g (1.05 mmol) of uranyl chloride cobalt(II) instead of the catalyst Jacobson. Gas chromatography indicated the presence in the reaction mixture 9% of the target connection.

Example R

4-hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

A solution of 0.25 g (1.0 mmol) sulfate pentahydrate copper(II) in 5 ml of water was added to a solution of 0.16 g (1.0 mmol) of 2,2’-dipyridyl in 120 ml of tert-butyl alcohol. To this solution was added 8.6 g (50 mmol) 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine. To the reaction mixture for three hours at 23-40°C was added dropwise a solution of 13.6 g (200 mmol) of 50% aqueous hydrogen peroxide mixed with 13 ml of tert-butyl alcohol. Then the mixture was stirred at room temperature for 72 hours. Gas chromatography indicated the presence in the reaction mixture 9% of the target connection.

Example R42 Cable Line

4-hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

To a mixture of 0.79 g (8.0 mmol) of copper chloride(1), 50 ml of water, 1.6 ml of 37% hydrochloric acid and 400 ml of tert-butyl alcohol within six hours at 35-45°C. were simultaneously added a solution of 34.5 g (200 mmol) of 4-hydroxy-1-oxyl-2,2,6,ion mixture was stirred over night at room temperature. This reaction mixture was heated to 40 to 45°C and treated with a solution of 1.78 g of copper chloride(1), 4,4 ml of 37% hydrochloric acid and 85 g (1.25 mol) of 50% aqueous hydrogen peroxide for the reaction is completed the remaining nitrocellulose connection. After processing by the method described in Example P9, received and 38.6 g of a brownish solid substance containing 88% of the target compounds, as it was shown by analysis using gas chromatography.

Example P43

4-hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

A solution of 17.2 g (100 mmol) 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine dissolved in 50 ml of water, and a solution of 31.5 g (0.46 mol) of 50% aqueous hydrogen peroxide at the same time for 3 and 4.5 hours, respectively, was added to the mixture to 0.69 g (4.0 mmol) chloride dihydrate, copper(II), 25 ml of water, 0.8 ml of 37% hydrochloric acid and 200 ml of tert-butyl alcohol at 35-50°C. the Reaction mixture is kept at 45 to 50°With and treated the entire amount of 0.32 g of chloride dihydrate, copper(II), 0.6 ml of 37% hydrochloric acid and 35.5 g (0.52 mol) of 50% aqueous hydrogen peroxide for the reaction is completed the remaining nitrocellulose connection. After processing by the method described in Example P9, received 17.1 g whitish solid product of the/P>

Example R

4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

A solution of 17.2 g (100 mmol) 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine dissolved in 50 ml of water, and a solution of 29.3 g (0.43 mol) of 50% aqueous hydrogen peroxide at the same time for 3 and 4.25 hours, respectively, was added to a mixture of 1.0 g (4.0 mmol) sulfate pentahydrate copper(II), 25 ml of water, 0.6 ml of 98% sulfuric acid and 200 ml of tert-butyl alcohol at 35-50°C. the Reaction mixture is kept at 45 to 50°With and treated the entire amount of 0.44 g of the pentahydrate of copper sulfate(II), 0.4 ml of 98% sulfuric acid and 6.7 g (98 mmol) of 50% aqueous hydrogen peroxide for the reaction is completed the remaining nitrocellulose connection. After processing by the method described in Example P9, got to 19.1 g of a white solid substance containing 95% of the target compounds, as it was shown by analysis using gas chromatography.

Example P45

4-hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

A solution of 7.4 g (109 mmol) of 50% aqueous hydrogen peroxide in 10 ml of water dropwise over five hours at 43-60°C was added to the mixture obtained by successive addition of 5 ml water, 0.5 ml of glacial acetic acid ,166 g (0.95 mmol) of iron acetate. Then to the reaction mixture at 60°C was added to a fresh solution of 4.4 g (65 mmol) of 50% aqueous hydrogen peroxide and 4 ml of water. The resulting mixture was stirred over night at room temperature.

Analysis by gas chromatography showed that the reaction mixture contains 52% of the target compounds and 41% of unreacted raw product by mass, the initial content of nitroxyl.

Example P46

4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

Repeating the procedure of Example P9 using a mixture of ferric chloride (2) and ferric chloride (3).

Example R

4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

Repeating the procedure of Example P9 using a mixture of ferric chloride (3) and iron powder instead of ferric chloride (2).

In the Examples R48 and R described reaction, where instead of hydrogen peroxide used tert-butylhydroperoxide.

Example R48

4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

A solution of 5.2 g (30 mmol) 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine dissolved in 20 ml of water, and a solution of 7.8 g (61 mmol) of 70% aqueous tert-BU is and iron chloride(3), 8 ml of water, 0.2 ml of 37% hydrochloric acid and 60 ml of tert-butyl alcohol. After the addition the reaction mixture is kept at 45°C for one hour, and then stirred at room temperature for three days. Gas chromatography indicated the presence in the reaction mixture 3% target of the connection.

Example R

4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

Repeating the procedure of Example R48 using ferric chloride(2) instead of ferric chloride (3).

Example P50

4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

In this example, instead of 50% aqueous hydrogen peroxide, were added compound formed from urea and hydrogen peroxide.

Received the solution of 52.2 g (555 mmol) of the compound formed by the addition of urea and hydrogen peroxide and dissolved in 75 ml of water, and a solution of 3 ml of concentrated sulfuric acid dissolved in 29 ml of water. Portions of these two solutions simultaneously at a temperature of 40°C for two hours was added to a mixture of 0.17 g (61 mmol) chloride heptahydrate iron(2), 34,75 g (202 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine, 410 ml of tert-butelek was stirred overnight at 45°C for 16 hours. Other solutions of peroxide and acid were simultaneously added to the reaction mixture for seven hours at 45°C. Then was added concentrated sulfuric acid (1.8 ml) and the mixture was stirred at room temperature for 64 hours. After heating the reaction mixture at 45 to 50°C for 6.5 hours was added 1.8 ml of concentrated sulfuric acid and 0,101 g of iron sulfate heptahydrate(2). Then the reaction mixture was heated at 45°C for 16 hours to bring the concentration of nitroxyl to less than 1% of its initial value. This reaction mixture was treated in the manner described in Example 20, resulting in received of 38.1 g (yield 77%) of product as a white solid.

Analysis by gas chromatography showed that the reaction product contains approximately 94% of the target connection.

Example R51

4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

In the Examples 51-54 shows the effect of using different acids in the method of the present invention.

A solution of 17.2 g (100 mmol) 4-hydroxy-1-oxyl-2,2,6,6-Tetra-methylpiperidine in 35 ml of water and a solution of 23.3 g (342 mmol) of 50% aqueous hydrogen peroxide at the same time to terukuni acid and 200 ml of tert-butyl alcohol, which stood at 43°C. Shortly before you are finished adding to the mixture was added a solution 0,347 g (2.0 mmol) of iron acetate(2) and 1.25 g triperoxonane acid in 5 ml of water. Then during the 90 minutes was added a fresh portion of 5.1 g (75 mmol) of 50% aqueous hydrogen peroxide solution, and the reaction mixture was stirred for 15 hours at 42-45°C. the Reaction mixture was treated in the manner described in Example P9, and got to 17.5 g (yield 71%) of product as a white solid.

Analysis by gas chromatography showed that the reaction product contains approximately 92% of the target connection.

Example P52

4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

A solution of 17.2 g (100 mmol) 4-hydroxy-1-oxyl-2,2,6,6-Tetra-methylpiperidine in 35 ml of water and a solution of 23.3 g (342 mmol) of 50% aqueous hydrogen peroxide was also added for 2.5 hours and 15 hours respectively to the mixture 0,561 g (3.1 mmol) oxalate dihydrate iron (2), 20 ml of water, 1.26 g of dihydrate of oxalic acid and 200 ml of tert-butyl alcohol which is maintained at 43-65°C. After addition of the peroxide, the reaction mixture was stirred for seven hours at 50-60°C. To this reaction mixture was added to Uchenie seven hours at 65-80°C.

Analysis by gas chromatography showed that the reaction product contained about 86% of the target compounds and less than 4% of the original product based on the content of sterically constrained Amin.

Example P53

4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

A solution of 17.2 g (100 mmol) 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine in 35 ml of water and a solution of 23.3 g (342 mmol) of 50% aqueous hydrogen peroxide was also added for 2.5 hours and 6 hours respectively to the mixture 0,563 g (2.0 mmol) of iron sulfate heptahydrate (2), 20 ml of water, 1.3 g methanesulfonic acid and 200 ml of tert-butyl alcohol which is maintained at 45°C. After complete addition of the peroxide, the reaction mixture was stirred for two hours at 45°C.

Analysis by gas chromatography showed that the reaction mixture contained 85% of the target compounds and less than 2% of the original product based on sterically constrained Amin.

Example R

4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

The solution is 46.5 g (270 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tet-ramateertha of 120.5 g of tert-putilovo the aces and 11.5 hours, respectively, was added to a mixture of 3.5 g (12.9 mmol) of the chloride heptahydrate iron(3), 32 ml of water, 1.3 g of 85% phosphoric acid and 292 ml tert-butyl alcohol which is maintained at 80°C. After the addition of peroxide, the reaction mixture was stirred for 30 minutes at 80°C.

Analysis by gas chromatography indicated the presence of less than 1% of the original nitrocellulose connection. The excess peroxide was decomposed by adding sodium sulfite and the crude product was filtered and treated with sodium borohydride in 14-molar aqueous sodium hydroxide solution, resulting in a received target connection with 71% yield, as it was shown by analysis using gas chromatography.

Example P55

4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

This example shows that the metal salt solution may be added dropwise to the reaction mixture during the entire reaction.

A solution of 1.62 g (8.1 mmol) of ferric chloride tetrahydrate(2), 2 ml of 37% hydrochloric acid and 50 ml of water and the solution 35,7 g (525 mmol) of 50% aqueous hydrogen peroxide solution simultaneously for 13 hours and 16 hours, respectively) was added to a mixture of 34.5 g (200 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine in 100 ml of water and 400 ml of tert-butyl SC was heated at a temperature of 40 to 45°C for eight hours.

Analysis by gas chromatography showed that the reaction mixture contained 86% of the target compounds and less than 5% of the original nitrocellulose connection.

Example R

4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

In the Examples 56-57 shows the effect of increasing the reaction temperature.

A solution of 2 ml of 98% sulfuric acid in 30 ml of water and the solution is 27.1 g (398 mmol) of 50% aqueous hydrogen peroxide solution simultaneously for 5.5 hours added to the solution 0,119 g (0.43 mmol) of iron sulfate heptahydrate, 70 ml of water, 34,6 g (201 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine in 100 ml of water and 410 ml of tert-butyl alcohol which is maintained at a temperature of 43-45°C. After complete addition of the peroxide, the reaction mixture was heated at 45°C for 20 hours.

Analysis by gas chromatography showed that the reaction mixture contained 73% of the target compounds and 18% source nitrocellulose connection.

Example P57

4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

A solution of 27.7 g (407 mmol) of 50% aqueous solution of hydrogen peroxide and 90% solution of 2.2 ml of 98% sulfuric sour is agitate iron sulfate(2), 70 ml of water, 34,6 g (201 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine and 410 ml of tert-butyl alcohol which is maintained at a temperature 63-68°C. After 6.5 hours the entire peroxide was consumed.

Analysis by gas chromatography showed that the reaction mixture contained 76% of the target compounds and 12% source nitrocellulose connection.

Example R

4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

A solution of 10.0 g (58,1 mmol) 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine in 20 ml of water and a solution of 15 g (220 mmol) of 50% aqueous hydrogen peroxide solution simultaneously for 1.5 hours and 7 hours, respectively, was added to the solution 0,394 g (1.77 mmol) of iron phosphate tetrahydrate(3), 13 ml of water and 120 ml of tert-butyl alcohol which is maintained at a temperature 63-81°C. the Reaction mixture was stirred over night at room temperature. Then add a fresh portion of 1.0 g (15 mmol) of 50% aqueous hydrogen peroxide solution, and the reaction mixture was stirred for 24 hours at 80°to bring the number nitrocellulose connection is less than 1.5% of its original number. The excess peroxide was decomposed by adding sodium sulfite.

Example Road P59

4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

A solution of 10.1 g (58,7 mmol) 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine in 30 ml of water and a solution of 16.3 g (240 mmol) of 50% aqueous hydrogen peroxide solution simultaneously for 2 and 6 hours, respectively) was added to a solution of 1.31 g (1,76 mmol) of pyrophosphate of iron(3), 20 ml of water and 120 ml of tert-butyl alcohol which is maintained at a temperature of 60-79°C. the Reaction mixture was stirred over night at room temperature. To the reaction mixture solution was added 15 ml of tert-butyl alcohol, 0.34 g (0.46 mmol) of pyrophosphate of iron(3) and 3.8 g (56 mmol) of 50% aqueous hydrogen peroxide solution. Then the mixture was heated for ten hours at 75-80°C. Excess peroxide was decomposed by adding sodium sulfite. The reaction mixture was treated in the manner described in Example P9, which was obtained 10.2 g (yield 71%) of product as a white solid, which corresponded to the target connection, as it was shown by analysis using gas chromatography.

Example R

4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

This example shows the effect of obyedinyaet of copper sulfate(2), 1 ml of 98% sulfuric acid and 15 ml of water and a solution of 13.6 g (200 mmol) of 50% aqueous hydrogen peroxide solution simultaneously for 3.5 hours and 4.25 hours, respectively, was added to the solution obtained by the addition of 17.4 g (101 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine in 50 ml of water to a mixture of 0.14 g (0.50 mmol) of iron sulfate heptahydrate(2), 10 ml of water and 200 ml of tert-butyl alcohol. During the addition the reaction mixture is maintained at 40 to 45°C, and then stirred over night at room temperature.

Analysis by gas chromatography showed that 77% of the parent compound was converted into the target compound.

Example R

A mixture of bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]adipate and bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]glutarate

A solution of 159 g (2.34 mol) of 50% aqueous hydrogen peroxide solution was added dropwise to a mixture consisting of 168,4 g of a mixture of bis[1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl]adipate and bis[1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl]glutarate, obtained from a DBE-3® (doonally ester, DuPont, containing a mixture of dimethyladipate:dimethylglutaric in the ratio of approximately 9:1), 2,03 g (7.5 mmol) of the uranyl prohozhdenie throughout the reaction for 30 hours the temperature was raised to 70°C and to the mixture for six hours was added a solution of 71 g (1.04 mol) of 50% aqueous hydrogen peroxide. After stirring the mixture for 13 hours at 65°C. to this mixture for six hours added another 71-gram portion of 50% aqueous hydrogen peroxide, and the mixture was stirred for 17 hours at 65°C. Excess peroxide was decomposed by adding sodium sulfite. The mixture was filtered to remove solids and most of the tert-butyl alcohol and water were removed by co-distillation with heptane. The residue was extracted with ethyl acetate and the solution was washed with a saturated solution of sodium chloride. The solvent is evaporated and the residue was purified using flash chromatography on silica gel, elwira with a mixture of hexane/ethyl acetate, resulting in a received 84,1 g of a white solid substance with so pl. 131,5-133°C. there was obtained a second collection of 16.3 g of a white solid substance with so pl. 128-130°C.

NMR analysis showed that the structure of the white solid product corresponds to the structure of the desired reaction product adipate/glutarate.

Example R

A mixture of bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]adipate and bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]glutarate

Example P63

4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

A solution of 34.6 g (201 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tet-ramateertha in 50 ml of water and a solution of 25.2 g (370 mmol) of 50% aqueous hydrogen peroxide simultaneously within four hours and eight hours, respectively, was added to a mixture of 1.12 g (4.0 mmol) of iron sulfate heptahydrate(2), 20 ml of water and 1 ml methanesulfonic acid and 400 ml of tert-butyl alcohol, which is kept at 80 to 85°C. while adding peroxide to the reaction mixture solution was added 0,506 g (1.8 mmol) of iron sulfate heptahydrate and 0.3 ml methanesulfonic acid in 2 ml of water. After addition of the peroxide and the mixture was stirred at 80 to 85°C for 30 minutes. Gas chromatography showed the presence of less than 1% of the original nitroxyl. The reaction mixture was processed as described in Example P9, resulting in received of 40.8 g of a white solid prod the examples illustrated new connections:

Example 1

The reaction of 1-oxyl-2,2,6,6-tetramethyl-piperidine-4-it cyclohexanol

A solution of 55 g (0.49 mol) of 30% aqueous hydrogen peroxide for 4.25 hours was added dropwise to a mixture of 23.5 g (0.14 mol) of 1-oxyl-2,2,6,6-tetramethylpiperidine-4-it and 4.0 g (at 0.020 mol) of ferric chloride tetrahydrate(2) 14 g (0.14 mol) of cyclohexanol and 150 g of cyclohexane. During the addition the reaction temperature was maintained at about 40°C. After the addition of peroxide, the reaction mixture was stirred for three hours at 40°C. were Then added to the second portion of 30% aqueous hydrogen peroxide (10 g, 0.09 mol) and the reaction mixture was heated for seven hours at 40°C. After cooling the mixture to room temperature, was added sodium sulfite (5 g). The reaction temperature is carefully brought up to 60°C for one hour to decompose excess peroxide. After cooling, the organic layer was separated, dried with anhydrous magnesium sulfate and concentrated to obtain and 22.6 g of brown oil. This oil was dissolved in cyclohexane and was passed through silica gel, elwira first with cyclohexane and then with a mixture of ethanol/ cyclohexane (V/V) (1:2) to give 16.5 g of a yellow oil.

The analysis, conducted with Paradou, at least four of the isomer 1-(hydroxycyclohexyl)-2,2,6,6-tetramethylpiperidine-4-it.

Example 2

Bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl)]sebacate

A solution of 73 g (0.64 mol) of 30% aqueous hydrogen peroxide solution for 3.5 hours was added dropwise to a mixture of 30.0 g (0,059 mol) of bis(1-oxyl-2,2,6,6-tetramethylpiperidine-1-yl)sebacate and 4.7 g (0,024 mol) of ferric chloride tetrahydrate(2) in 150 g of tert-butyl alcohol and 6 g of water. During the addition of peroxide, the reaction temperature was maintained at approximately 40°C. After complete addition, the reaction mixture was stirred for 4 hours at 40°C. the Reaction mixture was diluted with 150 g of ethyl acetate. Then the solution was added 100 g of 20% aqueous solution of sodium sulfite and the reaction mixture was stirred for 1.5 hours at 45 to 60°C to decompose excess peroxide. The aqueous layer was extracted with 100 g of ethyl-acetate and the combined organic layers were washed with 200 g of 5% sulfuric acid. The solvent is evaporated and got to 39.4 g of light yellow liquid, which was purified using flash chromatography on silica gel, elwira mixture (4:1:5) (by volume) ethyl acetate:isopropanol:hexane, resulting in received of 19.1 g (yield 49%) target with the Example 3

The reaction of bis(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl)sebacate with cyclohexanol

A solution of 70 g (of 0.62 mol) of 30% aqueous hydrogen peroxide solution within 2.75 hours was added dropwise to the mixture 32,4 g (0,063 mol) of bis(1-oxyl-2,2,6,6-tetramethylpiperidine-yl)sebacate and 5.0 g (0,025 mol) of ferric chloride tetrahydrate(2) in 100 g of cyclohexanol. During the addition the reaction temperature was maintained at 40 to 45°C. Then the reaction mixture was stirred for five hours at 40°C, and during this time the reaction mixture in two equal portions was added fresh 50% aqueous solution of hydrogen peroxide (5.0 g, 0,074 mol). The next day the reaction mixture was heated to 40°C, was added another portion of 50% aqueous hydrogen peroxide solution (2.5 g, 0,037 mol) and the mixture was maintained at 40°C for five hours. To the mixture was added a solution of 100 g of 20% aqueous sodium sulfite and the reaction temperature was maintained at 70°C for 45 minutes to decompose the excess hydrogen peroxide. The combined organic layers were concentrated to obtain 151 g of the crude product. Then add water and residual cyclohexanol was removed by steam distillation. The remaining 50 g of the crude product was purified with the help of the

NMR analysis showed that this oil, in addition to other structural isomers specified subcatego connection, contains bis-[1-(TRANS-2-hydroxycyclohexyl)-2,2,6,6-tetramethylpiperidine-4-yl].

Example 4

The reaction of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine with cyclohexanol

A solution of 50 g (of 0.74 mol) of 50% aqueous hydrogen peroxide for 1.75 hours was added dropwise to a mixture of 35.0 g (0.20 mol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine and 10.0 g (0,050 mol) of ferric chloride tetrahydrate(2) in 100 g of cyclohexanol. During the addition the reaction temperature was maintained at approximately 40 to 45°C. After the addition of peroxide, the reaction mixture was stirred for five hours at 40°C. the Mixture was cooled to room temperature and the solution was added 100 g of 20% aqueous sodium sulfite. The reaction mixture was carefully heated at 60°C for one hour to decompose excess peroxide. Once added to the organic layer of acetone, the crude product was filtered to remove solids and the filtrate was concentrated. Then add water and residual cyclohexanol was removed by steam distillation. The crude product was purified using flash chromatograph the/P>

Mass spectrometric analysis showed that the oil obtained is a mixture of isomers of 1-(hydroxycyclohexyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine and 1-(dihydroxyacetone)-4-hydroxy-2,2,6,6-tetramethylpiperidine.

Example 5

The reaction of 2,4-bis[N-(1-oxyl-2,2,6,6-tetramethyl piperidine-4-yl)-butylamino-6-chloro-s-triazine with cyclohexanol

A solution of 30 g (0.44 mol) of 50% aqueous hydrogen peroxide was added during 2 hours to a mixture 39,4 g (0,070 mol) of 2,4-bis-[N-(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl)butylamino-6-chloro-s-triazine and 7.0 g (0.035 mol) of ferric chloride tetrahydrate(2) in 150 g of cyclohexanol at a temperature of 40 to 45°C. After the addition of peroxide, the reaction mixture was stirred for ten hours at 40°C and during this time was added another portion (19 g, 0.28 mol) of 50% aqueous hydrogen peroxide. Then added another portion of 50% aqueous hydrogen peroxide (25 g, and 0.37 mol) by heating the reaction mixture at 50 to 65°C for four hours. The reaction mixture was treated with a solution of 100 g of 20% aqueous sodium sulfite at 60°C for one hour to decompose the residual peroxide. The organic layer was concentrated to obtain a brown oil, which was received by 43.4 g of yellow solid.

Example 5A

2,4-Bis{N-[1-(TRANS-2-hydroxycyclohexyl)-2,2,6,6-tetramethylpiperidine-4-yl]butylamino}-6-(2-hydroxyethyl)amino-s-triazine

The product obtained in Example 5 was subjected to reaction with a solution of ethanolamine and sodium hydroxide. The crude reaction mixture was diluted with ethyl acetate and washed with water. The aqueous layer was extracted with ethyl acetate and the combined organic layers were concentrated. The residue was dissolved in ethyl acetate and was added cyclohexane. The brown oil was removed. The remaining solution was concentrated with the receipt of 13.7 g of crude product. The crude product was purified using flash chromatography on silica gel, elwira first mixture (2:1, V/V) ethyl acetate/hexane, and then with a mixture (8:1, V/V) ethyl acetate/methanol, resulting in a received 6.4 g of a yellow oil. This oil was dissolved in ethanol and was treated with decolorizing charcoal at 60°C for one hour. Solids were removed by filtration and the solvent evaporated, resulting in received of 6.5 g of a whitish solid, so pl. 67-80°C.

NMR analysis showed that this solid substance, mixture in addition to structural hydroxycyclohexanone and dihydroxyacetone-isomers, steppedin

A solution of 50.7 g (0.75 mol) of 50% aqueous hydrogen peroxide mixed with 25 ml of tert-butyl alcohol within two hours was added to a mixture of 25.8 g (0.15 mol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine, of 8.95 g (0.045 mol) of ferric chloride tetrahydrate(2) and 110 ml of tert-butyl alcohol at 50°C. Then the reaction mixture was stirred for six hours at 50°C and the reaction course was monitored by gas chromatography. Then were added to 17.7 g (0.26 mol) of 50% hydrogen peroxide and the reaction mixture was heated at 50°C for two hours to almost complete cessation of the reaction source nitrocellulose connection. The reaction mixture was filtered to remove solids and the filtrate was diluted with water. A solution of tert-butyl alcohol and water three times were extracted with methylene chloride and the aqueous layer was thoroughly extracted with ethyl acetate to obtain 7.4 g of the target compound. The combined organic layers once washed with saturated sodium chloride, dried with anhydrous magnesium sulfate and concentrated to obtain of 21.7 g of orange oil. This orange oil was purified using flash chromatography on silica gel, elwira with a mixture of heptane/ethyl acetate (3:2), which was obtained 12.4 g of the target is connected to the-propoxy)-2,2,6,6-tetramethylpiperidine-4-it, as it was shown by gas chromatography.

In Examples 6A and 6D illustrate the effect of addition of ligand in the method described in Example 6.

Example 6A

4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

The iron chloride tetrahydrate(2) (0,99 g, 5.0 mmol) was added to 400 ml of tert-butyl alcohol, heated to 40°C. the Mixture was stirred for 15 minutes to a solution of tert-butyl alcohol was added to 0.78 g (5.0 mmol) of 2,2’-dipyridyl. Then the solution was stirred for 5 minutes and added to 17.2 g (100 mmol) 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine. A solution of 49 g (to 0.72 mol) of 50% aqueous hydrogen peroxide mixed with 100 ml of tert-butyl alcohol within 10 hours was added to the reaction mixture at 40 to 45°C. Then was added 6 g (0,088 mol) of 50% aqueous hydrogen peroxide with heating the reaction mixture at 45°C for four hours until completion of the reaction source nitrocellulose connection. Analysis by gas chromatography showed that the reaction mixture contained 6% (by area) 1-(2-hydroxy-2-methyl-propoxy)-2,2,6,6-tetramethylpiperidine-4-it is compared with 22% (by area) of the compound of Example 6. Solids were removed by filtration and p is th and the mixture is thoroughly extracted with ethyl acetate. The extract was concentrated to obtain 24.2 g of light-brown crystalline solid, which has a similar retention time to that of an authentic sample of the target compound, as it was shown by gas chromatography. In an analogous experiment, the final product was recrystallized several times from heptane, resulting in received of 16.9 g (yield 69%) of target compound, so pl. 127-131°C.

Example 6B

4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

The solution 32,3 g (475 mmol) of 50% aqueous hydrogen peroxide mixed with 35 ml of tert-butyl alcohol were added for six hours at 45 to 50°C to the mixture obtained by successive addition 0,362 g (1.2 mmol) of ethylenediaminetetraacetic acid, 55 ml of tert-butyl alcohol and 17.2 g (100 mmol) 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine to a solution of 0.80 g (4 mmol) of ferric chloride(2), dissolved in 5 ml of water. Analysis by gas chromatography showed that after the addition of peroxide remained 15% of the original nitrocellulose connection. The reaction mixture was stirred for one hour at 45-50°C, and then for 72 hours at 25°C to complete the reaction. Analysis about who her target compound to 1 part of 1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-it.

Example 6C

4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

Repeating the procedure of Example 6B using oxide three-phenylphosphine instead of ethylenediaminetetraacetic acid.

Example 6D

4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

Repeating the procedure of Example 6B using the disodium salt of ethylenediaminetetraacetic acid instead of ethylenediaminetetraacetic acid.

Example 7

Bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]adipate

To a mixture of bis(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl]-adipate and iron chloride tetrahydrate in tert-butyl alcohol at 30-50°C was added aqueous hydrogen peroxide. The excess peroxide was subjected to decomposition by adding an aqueous solution of sodium sulfite. The organic layer was concentrated and the crude product was purified using flash chromatography on silica gel to obtain the target compounds.

Example 8

Bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]glutarate

To a mixture of bis(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl] glutarate and iron chloride tetrahydrate in tert-butyl spy aqueous solution of sodium sulfite. The organic layer was concentrated and the crude product was purified using flash chromatography on silica gel to obtain the target compounds.

Example 9

Bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]succinate

To a mixture of bis[1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl]-succinate and iron chloride tetrahydrate(2) in tert-butyl alcohol at 30-50°C was added aqueous hydrogen peroxide. The excess peroxide was subjected to decomposition by adding an aqueous solution of sodium sulfite. The organic layer was concentrated and the crude product was purified using flash chromatography on silica gel to obtain the target compounds.

Example 10

Bis[1-(2-hydroxy-2-venetucci)-2,2,6,6-tetramethylpiperidine-4-yl]sebacate

To a mixture of bis[1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl]-sebacate and iron chloride tetrahydrate in tert-butyl alcohol at 30-50°C was added aqueous hydrogen peroxide. The excess peroxide was subjected to decomposition by adding an aqueous solution of sodium sulfite. The organic layer was concentrated and the crude product was purified using flash chromatography on silica gel to obtain the target compounds.

Example 11

2,4-Bis{N-[1-(2-hydroxy-2-methyl is sid hydrogen was added in two portions over five hours to a mixture of 43.2 g (0,076 mol) of 2,4-bis[N-(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl)butylamino-6-chloro-s-triazine and 7.0 g (0.035 mol) of ferric chloride tetrahydrate(2) in 150 g of tert-butyl alcohol and 15 g of water. Then to the reaction mixture was added another portion of 50% aqueous hydrogen peroxide (3 g, 0,044 mol) by heating the reaction mixture at 40 to 45°C for 2.25 hours. The reaction mixture was diluted with 100 g of ethyl acetate. Then within one hour was added to 100 g of a solution of 20% aqueous sodium sulfite at 60°C for the decomposition of residual peroxide. The aqueous layer was extracted with ethyl acetate, and the combined organic layers were concentrated. The crude product was purified using flash chromatography on silica gel using 1:1 (V/V) hexa-on/ethyl acetate, resulting in received of 54.1 g of the target compound.

Example 12

2,4-Bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]butylamino}-6-(2-hydroxyethyl)amino-s-triazine

The target compound was obtained by reaction of the intermediate obtained as described in Example 11, with ethanolamine and sodium hydroxide. The aqueous layer was removed, and the remaining layer was extracted with cyclohexane. The solvent is evaporated under reduced pressure, and the crude product was purified using flash chromatography on silica gel using 1:2 (V/V) hexane/ethyl acetate, which was obtained 4.1 g of target compound in the form of NCH2); 3,59 Junior doctor (s, 4H, DOWN2).

Example 13

Reaction of the product of Example 11 N,N’-bis(3-aminopropyl)Ethylenediamine

The product obtained in Example 11 was subjected to reaction with N,N’-bis(3-aminopropyl)Ethylenediamine in a molar ratio of 3:1. The mixture of products contained N,N’,N’-Tris{2,4-bis[N-[1-(2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl)butylamino]-s-triazine-6-yl}-3,3’-ethylendiaminetetraacetic and N,N’,N’-Tris{2,4-bis[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl)butylamino]-s-triazine-6-yl}-3,3’-ethylendiaminetetraacetic.

Example 14

2,4-Bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]butylamino}-6-octylamine-s-triazine

The compound obtained in Example 11 was subjected to reaction with excess octylamine, resulting in the obtained target compound in the form of glassy whitish substance, so pl. 68-86°C.

Example 15

N,N’-Bis{4,6-bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]butylamino}-s-triazine-2-yl}-1,6-diaminohexane

The target compound was obtained by reaction of the compound obtained in Example 11, with hexamethylenediamine were.

Example 16A

The reaction of 4-hydroxy-1-oxyl-2,and to a mixture of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine and iron chloride tetrahydrate(2) in tert-butyl alcohol at 30 to 60°C. The excess peroxide was decomposed by adding an aqueous solution of sodium sulfite. The organic layer was concentrated and the crude product was purified using flash chromatography on silica gel to obtain sample 4-hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine.

Example 16B

1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-eletcrical

The target compound was obtained by reaction of the compound obtained in Example 16A, with methyl methacrylate.

Example 17

4 Allyloxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

A suspension of 8.4 g (0.21 mol) of 60% sodium hydride in mineral oil at 50°With portions was added to the solution 49,1 g (0.20 mol) of the compound obtained in Example 16A, in 500 ml of anhydrous diglyme. To the reaction mixture was added allylbromide (20,8 ml of 29.1 g, 0.24 mol) in a few hours and the mixture was stirred for 7 hours at 50°C. the Reaction mixture was cooled and extinguished 2 N. hydrochloric acid. After adding saturated sodium bicarbonate solution to neutralize the excess acid, the organic layer was concentrated to obtain and 47.5 g (yield 83%) of target compound, which is a VC who ridin

The target compound was obtained by reaction of the compound obtained in Example 16A, with epichlorohydrin.

Example 19

1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl-3-{[[[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yloxy]carbonyl]amino]methyl]-3,5,5-trimethylcyclohexylamine

The target compound was obtained by reaction of the compound obtained as described in Example 16A, 5-isocyanato-1-(isocyanatomethyl)-1,3 .3m-trimethylcyclohexane (=isophorone-diisocyanate).

Example 20

Bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]-1,6-hexadienal

The target compound was obtained by reaction of the compound obtained as described in Example 16A, hexamethylenediisocyanate.

Example 20A

Bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]toluene-2,4-dicarbamate

The target compound was obtained by reaction of the compound obtained as described in Example 16A, with toluene-2,4-diisocyanate.

Example 20B

1,3,5-Tris{[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yloxy]carbonylmethyl}-2,4,6-trioxo-s-triazine

Target sedinkin]-2,4,6-trioxo-s-triazine (DESMODUR® N-3390).

Example 21

1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl-acrylate

The target compound was obtained by reaction of the compound obtained as described in Example 16A with methyl acrylate.

Example 22

2,4,6-Tris{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]butylamino}-s-triazine

A solution of 40 g (0.35 mol) of 30% aqueous hydrogen peroxide in 1.25 hours was added to a mixture of 11.7 g (to 0.011 mol) of 2,4,6-Tris[N-(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl]butylamino}-s-triazine and 3.0 g (0.015 mol) of ferric chloride tetrahydrate(2) in 100 g of tert-butyl alcohol and 9 g of water. During the addition of peroxide, the reaction temperature was maintained at 60-65°C. To the reaction mixture were added in two equal portions (2 g, 0.29 mol) of 50% aqueous hydrogen peroxide, while maintaining a temperature of 60°C for 9.5 hours. After diluting the reaction mixture with ethyl acetate and cooling to room temperature, to the mixture was added 100 g of 20% aqueous solution of sodium sulfite. The reaction mixture was heated at 60°C for one hour to decompose excess peroxide. The aqueous layer was extracted with ethyl acetate and the combined organic layers were concentrated. Raw productwelcome which received the product, which is rubbed with a mixture (V/V, 1:1) cyclohexane/acetone to obtain 4.0 g of the target compound in the form of a white solid substance having a melting point 172-176°C.

Example 23A

The reaction of 1-oxyl-2,2,6,6-tetramethylpiperidine-4-one with tert-butyl alcohol

To a mixture of 1-oxyl-2,2,6,6-tetramethylpiperidine-4-it and ferric chloride(2) in tert-butyl alcohol at 30 to 60°C was added an aqueous solution of hydrogen peroxide. The excess peroxide was decomposed by adding an aqueous solution of sodium sulfite. The organic layer was concentrated and the residue was purified by flash chromatography to obtain the desired 1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-it.

Example 23C

4 Butylamino-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

A mixture of butylamine, compounds obtained as described in Example 23A, and a catalytic amount of 5% platinum-on-coal was hydrogenosomal in the Parr apparatus under a pressure of 3 atmospheres. The catalyst was removed by filtration and the solvent evaporated to obtain the target compounds.

Example 24

4 Trimethylsilyloxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

Chlortrimeton the Sano in Example 16A, 8.5 ml of triethylamine and 125 ml of anhydrous tetrahydrofuran. The reaction mixture was stirred for 2 hours at 60°C and then for 1 hour at room temperature. After evaporation of the solvent the residue was distributed between water and dichloromethane. The organic layer was dried with anhydrous magnesium sulfate and concentrated to obtain 14.6 g (yield 92%) of target compound as a yellow oil.

Example 25

4-Benzoyloxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

A solution of 50% aqueous hydrogen peroxide was slowly added to a mixture of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and iron chloride tetrahydrate(2) in tert-butyl alcohol at 30 to 60°C. Excess peroxide was removed by adding an aqueous solution of sodium sulfite. The organic layer was concentrated and the residue was purified using flash chromatography to obtain the target compounds.

Example 26

1-(2-Hydroxy-2-methylpropoxy)-4-[3-(trimethylsilyl)propoxy]-2,2,6,6-tetramethylpiperidine

The target compound was obtained by reaction of the compound obtained as described in Example 17, with trimethylsilanol and bieksa-chloroplatinate(IV) in isopropyl alcohol.

Example 26A

Example 27

Tetrakis{3-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-Tetra-methylpiperidin-4-yloxy]propyl}1,3,5,7-tetramethylcyclotetrasiloxane

The target compound was obtained by heating a mixture of 30.3 g (0,106 mol) of the compound obtained as described in Example 17, 6.3 ml (0,026 mol) of 1,3,5,7-tetramethylcyclotetrasiloxane and 1 ml of 2% solution of bisexualitat (IV) in isopropyl alcohol at 100°C for 4 hours. The reaction mixture was cooled and distributed between dichloromethane and water. The organic layer was filtered and concentrated under reduced pressure to get to 31.7 g (yield 98%) of target compound in the form of a viscous orange oil.

Example 28

Poly{[3-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yloxy]propyl]methyl}silane

Target soedineniya (IV) in isopropyl alcohol.

Example 29

Poly{[3-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yloxy]propyl]methyl}siloxane, terminated trimethylsiloxy

The target compound was obtained by heating a mixture of 29.6 g (0.104 g mol) of the compound obtained as described in Example 17, 6.8 ml (0,004 mol) poly(methylhydrosiloxane), terminated end trimethylsiloxy and having an average molecular weight of 1700, and 1 ml of 1% solution of bisexualitat (IV) in isopropyl alcohol at 100°C for 1 hour. The resulting polymer mass was partially dissolved in hot dichloromethane, and the suspension was extracted with hot water. The organic layer was filtered and concentrated with getting to 34.7 g of target compound in the form of a white kauchukopodobnoe solids.

Elemental analysis for C439,5H910N25,5O103Si27,5(n=25.5 V source connection): Calculated: C, 58,82; N, Of 10.21; N, Of 3.97; Found: C, 59,62; H, 10,11; N is 3.08.

Example 30

A mixture of bis[1-4-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-piperidine-4-yl]glutarate and bis[1-4-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]adipate

The mixture of compounds obtained as described in Example 16, a mixture of dimethyl al. The reaction mixture was extinguished dilute mineral acid, and the organic layer was washed with water and dried with anhydrous magnesium sulfate. Xylology the solution evaporated under reduced pressure and the obtained mixture of the target compounds.

Example 30A

A mixture of bis[1-4-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-piperidine-4-yl]adipate and bis[1-4-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]glutarate

A solution of 50% aqueous hydrogen peroxide was added dropwise to a mixture of ferric chloride(3), an aqueous solution of hydrochloric acid, water, t-butyl alcohol and a mixture of bis(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl)adipate and bis(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl)glutarate, derived from dibasic complex ester DBE-3 (DuPont®). The excess peroxide was decomposed by adding an aqueous solution of sodium sulfite. The reaction mixture was filtered and the solvents evaporated. The residue was purified using flash chromatography on silica gel, elwira with a mixture of hexane/ethyl acetate, resulting in the obtained target compound as a white solid, so pl. 131,5-133°C.

Example 31

The reaction of bis(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl)sebacate with neopentyl alcohol

Water pen is silt alcohol method described in Example 25.

Example 32

The reaction of 1-oxyl-2,2,6,6-tetramethylpiperidine-4-it neopentylglycol

Aqueous hydrogen peroxide was added to a mixture of bis(1-oxyl-2,2,6,6-tetramethylpiperidine-4-it and ferric chloride(2) in neopentylglycol the method described in Example 25.

Example 33

The reaction of 4-octadecanoyloxy-1-oxyl-2,2,6,6-piperidine with tert-amyl alcohol

Aqueous hydrogen peroxide was added to a mixture of 4-octadecanoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferric chloride(2) in tert-amyl alcohol by the method described in Example 25.

Example 33A

The reaction of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine with 2-methyl-2-butanol

A solution of 34.5 g (0.20 mol) of 4-hydroxy-1-oxyl-2,2,6,6-Tetra-methylpiperidine in 50 ml of water and a solution of 22.5 g of 50% aqueous hydrogen peroxide was added at 90-95°C to a mixture containing only 1.88 g of iron sulfate heptahydrate(2), 2,05 g methanesulfonic acid, 20 ml of water and 450 ml of 2-methyl-2-butanol (t-amyl alcohol). The reaction was completed after 6 hours. The reaction mixture was filtered to remove solids and the filtrate was stirred with sodium sulfite and then with a basic sodium borohydride. The aqueous layer was removed and the organic layer receiving and 46.3 g of a yellow oil. Analysis using gas chromatography/mass spectroscopy showed that the product is a mixture of 3 main components, each of which has a molecular weight 259, which corresponds to the addition of t-amyl alcohol to the original nitrocellulose connection.

Example 33B

The transesterification reaction product of Example 33A by metalseadramon

Mix with 44.8 g (0,173 mol) of the reaction product obtained as described in Example 33A, of 47.1 g (0,158 mol) of methyltaurine, 0,223 g of lithium amide and toluene was heated under reflux. Methanol drove from the reaction mixture together with a certain amount of toluene. The reaction mixture was extinguished dilute acetic acid and then washed with water, diluted aqueous sodium bicarbonate solution and saturated sodium chloride solution. Toluene solution was dried with magnesium sulfate, filtered and concentrated to obtain a solid substance. After purification using flash chromatography on silica gel with elution by the mixture hexane/ethyl acetate received 70,0 whitish solid product, so pl. 38-43°C.

Example 34

4-Benzoyloxy-1-(2-hydroxycyclohexyl)-2,2,6,6-tetramethylpiperidine in chlorobenzene was added dropwise hydride presence of TBT. To facilitate the passage of the reaction mixture was heated. The crude reaction mixture was passed through silica gel with elution with heptane, and then with a mixture of heptane/ethyl acetate, resulting in the obtained target compound in the form of a mixture of CIS-/TRANS-isomers.

Example 35

4-Hydroxy-1-(2-hydroxycyclohexyl)-2,2,6,6-tetramethylpiperidine

The target compound was obtained by heating the compound obtained as described in Example 34, in a solution of potassium hydroxide in methanol.

Example 36

The reaction of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine with propylene glycol

Aqueous hydrogen peroxide was added to a mixture of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and iron chloride tetrahydrate(2) in propylene glycol by the method described in Example 25.

Example 37

The reaction of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine with triethyleneglycol

Aqueous hydrogen peroxide was added to a mixture of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and iron chloride tetrahydrate(2) triethyleneglycol the method described in Example 25.

Example 38

Bis[1-(2-hydroxyethoxy)-2,2,6,6-tetramethylpiperidine-4-yl]-sebacate

To a solution of the NML added anti-hydride. The crude reaction mixture was passed through silica gel, elwira heptane, and then with a mixture of heptane/ethyl acetate, resulting in a received target connection.

Example 39

The reaction of bis(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl)sebacate with isopropanol

Aqueous hydrogen peroxide was added to a mixture of bis(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl)sebacate and iron chloride tetrahydrate(2) in isopropanol as described in Example 25.

Example 40

The reaction of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine with 1,4-butanediol

Aqueous hydrogen peroxide was added to a mixture of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and iron chloride tetrahydrate(2) in 1,4-butanediol as described in Example 25.

Example 41

The reaction of 4-hexyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine with pinkola

Aqueous hydrogen peroxide was added to a mixture of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and iron chloride tetrahydrate(2) pinacol the method described in Example 25.

Example 42

The reaction of 1-oxyl-2,2,6,6-tetramethylpiperidine-4-she glycerin

Aqueous hydrogen peroxide was added to a mixture of 1-oxyl-2,2,6,6-tetramethylpiperidine-4-it and tccia 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine with 2-ethyl-1-hexanol

Aqueous hydrogen peroxide was added to a mixture of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and iron chloride tetrahydrate(2) 2-ethyl-1-hexanol the method described in Example 25.

Example 44

1-(2-Hydroxy-2-methylpropoxy)-4-hexadecanoate-2,2,6,6-tetramethylpiperidine

The mixture 12,11 g (49.4 mmol) of the compound obtained as described in Example 16A, 12,11 g (44,8 mmol) of methylhexadecanoic (methylvalerate), 0,76 g of lithium amide and toluene was heated under reflux. Methanol drove from the reaction mixture together with a certain amount of toluene. The reaction mixture was extinguished dilute acetic acid and then washed in water, methanol, diluted aqueous sodium bicarbonate solution and saturated sodium chloride solution. Toluene solution was dried with magnesium sulfate, filtered and concentrated to obtain a solid substance. After purification using flash chromatography on silica gel, elwira with a mixture of hexane/ethyl acetate, obtained 18 g of solid substance. After recrystallization from methanol was obtained 10.7 g of target compound in the form of a white solid substance, so pl. 60-64°C.

Example 44A

1-(2-Hydroxy-2-methylpropoxy)-4-eicosanoate-2,2,6,6-those who mol) of methylacetate, of 0.35 g of lithium amide and toluene was heated under reflux. The reaction mixture was extinguished dilute acetic acid and then washed with an aqueous solution of methanol, dilute aqueous solution of sodium bicarbonate and a saturated solution of sodium chloride. Toluene solution was dried with magnesium sulfate, filtered and concentrated to obtain solid, which was purified using flash chromatography on silica gel, elwira with a mixture of hexane/ethyl acetate, which was given to 9.9 g of the target compound in the form of a white solid substance, so pl. 69-73°C.

Example V

1-(2-Hydroxy-2-methylpropoxy)-4-(2-ethylhexyloxy)-2,2,6,6-tetramethylpiperidine

A mixture of 51.6 g (0,210 mol) of the compound obtained as described in Example 16A, 30,6 g (rate of 0.193 mol) of methyl 2-ethylhexanoate, 1.26 g of amide lithium and toluene was heated under reflux. Methanol drove from the reaction mixture together with a certain amount of toluene. The reaction mixture was extinguished dilute acetic acid and then washed with an aqueous solution of methanol, dilute aqueous solution of sodium bicarbonate and a saturated solution of sodium chloride. Toluene solution was dried with magnesium sulfate, filtered Irua with a mixture of hexane/ethyl-acetate, received of 51.0 g of target compound as pale yellow oil.

Example S

1-(2-Hydroxy-2-methylpropoxy)-4-dodecanoate-2,2,6,6-tetramethylpiperidine

The mixture 72,7 g (0,297 mol) of the compound obtained as described in Example 16A, 51.9 g (0,242 mol) of metallogenica (metallura), of 0.43 g of lithium amide and toluene was heated under reflux. Methanol drove from the reaction mixture together with a certain amount of toluene. The reaction mixture was extinguished dilute acetic acid and then washed with an aqueous solution of methanol, dilute aqueous solution of sodium bicarbonate and a saturated solution of sodium chloride. Toluene solution was dried with magnesium sulfate, filtered and concentrated to obtain a solid substance. After purification using flash chromatography on silica gel, elwira with a mixture of hexane/ethyl acetate, got 96,7 g of target compound in the form of a white solid substance, so pl. 46-48°C.

Example 45

The reaction of N,N’,N’,N’’-tetrakis[2,4-bis[N-(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl]butylamino]-s-triazine-6-yl}-3,3’-ethylenediaminetetramethylene with cyclohexanol

A mixture of N,N’,N’,N’’-tetrakis[2,4-bis[N-(1-oxyl-2,2,6,6-Tetra-methylpiperidin-4-yl]butylamine is Orada and iron chloride tetrahydrate(2) method, described in Example 4. There was obtained a white solid substance with so pl. 133-175°C.

Example 46

Reaction of 2,4,6-Tris[N-(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl]-butylamino}-s-triazine with cyclohexanol

A mixture of 2,4,6-Tris{N-(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl]-butylamino]-s-triazine and cyclohexanol were subjected to reaction with aqueous hydrogen peroxide and ferric chloride tetrahydrate(2) the method described in Example 4. There was obtained a light brown oil.

Example 47

Bis[1-(3-hydroxypropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]sebacate

To a solution of 3-bromo-1-propanol and excess bis(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl)sebacate in chlorobenzene was added dropwise hydride presence of TBT. To facilitate the passage of the reaction mixture was heated. The crude reaction mixture was passed through silica gel, elwira heptane, and then with a mixture of heptane/ethyl acetate, resulting in a received target connection.

Example 48

Bis[1-(12-hydroxy-1-dodecyloxy)-2,2,6,6-tetramethylpiperidine-4-yl]sebacate

To a solution of 12-bromo-1-dodecanol and excess bis(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl)sebacate in chlorobenzene was added dropwise hydride t through silica gel, elwira heptane, and then with a mixture of heptane/ethyl acetate resulting in a received target connection.

Example 49

Bis[1-(2-hydroxypropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]sebacate

To a solution of 1-bromo-2-propanol and excess bis(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl)sebacate in chlorobenzene was added dropwise hydride presence of TBT. To facilitate the passage of the reaction mixture was heated. The crude reaction mixture was passed through silica gel, elwira heptane, and then with a mixture of heptane/ethyl acetate, resulting in a received target connection.

Example 50

The reaction product of the compound of Example 11 N,N' bis(3-aminopropyl)Ethylenediamine

N,N’-Bis(3-aminopropyl)Ethylenediamine and the product obtained as described in Example 11 was subjected to the reaction in a molar ratio of 1:3:0: 1:3:5. The mixture of products contained N,N’,N’-Tris{2,4-bis[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-Tetra-methylpiperidin-4-yl]-butyl-amino]-s-triazine-6-yl}-3,3’-ethylene-diaminodiphenylamine, N,N’,N’’-Tris{2,4-bis[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]butylamino]-s-triazine-6-yl]-3,3'-ethylendiaminetetraacetic and N,N’,N’,N’’-tetrakis{2,4-bis[N-[1-(2-hydroxy-2-methylpropoxy)-2,P CLASS="ptx2">N,N’,N’,N’’-tetrakis{2,4-bis[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]butylamino]-s-triazine-6-yl}-3,3’-ethylendiaminetetraacetic

The target compound was obtained by adding aqueous hydrogen peroxide to a mixture of N,N’,N’,N’’-tetrakis{2,4-bis[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]butylamino]-s-triazine-6-yl}-3,3’-ethylenediaminetetramethylene, iron chloride(2) and tert-butyl alcohol by the method described in Example 7.

Example 51A

N,N’,N’’-Tris{2,4-bis[N-[1-(2-hydroxy-2-methyl-propoxy)-2,2,6,6-tetramethylpiperidine-4-yl]butylamino]-s-triazine-6-yl}-3,3’-ethylendiaminetetraacetic

The target compound was obtained by adding aqueous hydrogen peroxide to a mixture of N,N’,N’’-Tris{2,4-bis[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]butylamino]-s-triazine-6-yl}-3,3’-ethylenediaminetetramethylene, iron chloride(2) and tert-butyl alcohol by the method described in Example 7.

Example 51B report

N,N’,N’-Tris{2,4-bis[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]butylamino]-s-triazine-6-yl}-3,3’-ethylendiaminetetraacetic

The target compound was obtained by adding aqueous hydrogen peroxide to a mixture of N,N’,N’iminodipropylamine, iron chloride(2) and tert-butyl alcohol by the method described in Example 7.

Example 52

Reaction of the product of Example 11 N,N’-bis(3-aminopropyl)Ethylenediamine

N,N’-Bis(3-aminopropyl)Ethylenediamine and the product obtained as described in Example 11 was subjected to the reaction in a molar ratio of 1:4,0. The mixture of products contained N,N’,N’-Tris{2,4-bis[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]butylamino]-s-triazine-6-yl}-3,3’-ethylendiaminetetraacetic, N,N’,N’’-Tris{2,4-bis[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]butylamino]-s-triazine-6-yl]-3,3’-ethylendiaminetetraacetic and N,N’,N’,N’’-tetrakis-{2,4-bis[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]butylamino]-s-triazine-6-yl}-3,3’-ethylendiaminetetraacetic.

Example 53A

2-[N-[1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]butylamino}-4,6-dichloro-s-triazine

The compound obtained as described in Example 23C, were subjected to reaction with equimolar amounts of cyanuric chloride acid and sodium bicarbonate at 0°C, resulting in a received target connection.

Example V

N,N’-Bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]-1,6-gentiane, obtained as described in Example 23A, diamine, methanol and a catalytic amount of 5% platinum-on-charcoal grill.

Example S

N,N’-Bis{2-[N-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-piperidine-4-yl]butylamino]-4-chloro-s-triazine-6-yl)-N,N’-bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]-1,6-hexanediamine

The target compound was obtained by reaction of the two compounds obtained as described in Examples 53A and B, in a molar ratio of 2:1 in xylene at 60-80°C With sodium hydroxide, is used as the acid acceptor.

Example 53D

The oligomer of N-{2-[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]butylamino]-s-triazine-4-yl}-N,N’-bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]-1,6-hexanediamine, terminated 2,4-bis(dibutylamino)-s-triazine-6-yl

The compounds obtained as described in Examples V and S, was mixed in a molar ratio of 2:1 in a solution of xylene at 100-160°C With sodium hydroxide, is used as the acid acceptor. Then the reaction mixture was treated with 2,4-bis-(dibutylamino)-6-chloro-s-triazine in the same conditions, resulting in received oligomeric product having a low number (2, 4, 6, 8) povtorjajushchi.

Example 54

The oligomer of N-{2-[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-Tetra-methylpiperidin-4-yl]butylamino]-s-triazine-4-yl}-N,N’-bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]-1,6-hexanediamine, terminated 2,4-bis(dibutylamino)-s-triazine-6-yl

N,N’-Bis(2,2,6,6-tetramethylpiperidine-4-yl)-1,6-hexanediamine and N,N’-bis{2-[N-(2,2,6,6-tetramethylpiperidine-4-yl)-butylamino]-4-chloro-s-triazine-6-yl}-N,N’-bis(2,2,6,6-tetramethylpiperidine-4-yl)-1,6-hexanediamine was mixed in a molar ratio of 2:1 in xylene at 100-160°C With sodium hydroxide, used as acid acceptor. Then the reaction mixture was treated with 2,4-bis(dibutylamino)-6-chloro-s-triazine in a similar situation. The mixture of oligomers was heated with tert-butylhydroperoxide and a catalytic amount of molybdenum trioxide in an inert solvent, such as 1,2-dichloroethane, with the formation of N-ocelovych compounds. Then aqueous hydrogen peroxide was added to a mixture of N-ocelovych compounds and iron chloride tetrahydrate(2) in tert-butyl alcohol by the method described in Example 7. The final products were a mixture of oligomers described in Example 53D, although the relationship of the individual components may not be analogichnorazdache)-2,2,6,6-Tetra-methylpiperidin-4-yl]butylamino]-s-triazine-4-yl}-N,N’-bis[1-(2-hydroxy-2-methylpropoxy)-2.2,6,6-tetramethylpiperidine-4-yl]-1,6-hexanediamine, terminated 2-butylamino-4-{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]-butylamino-s-triazine-6-yl

The target compound was obtained by heating the mixture of compounds obtained as described in Examples 53A and B, in a molar ratio of 1.33:1.0 in xylene at 100-160°C in the presence of sodium hydroxide, is used as the acid acceptor. Then to the reaction mixture under the same conditions was added dibutyltin to complete the reaction. The resulting product was a mixture of oligomers that contain 1-4 repeating units, the structure of which is shown below.

Example 56

The oligomer of N-{2-[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-Tetra-methylpiperidin-4-yl]butylamino]-s-triazine-4-yl}-N,N’-bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]-1,6-hexanediamine, terminated 2-butylamino-4-{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]-butylamino-s-triazine-6-yl

The target compound was obtained by heating the mixture of compounds obtained in Examples V and S, in a molar ratio of 0.5:1 in xylene at 100-160°C in the presence of sodium hydroxide, is used as the acid acceptor. Then to the reaction mixture at tomarow, containing 1, 3, 5 and 7 repeating units, the structure of which is presented below.

Example 57

The oligomer of N-{2-[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-Tetra-methylpiperidin-4-yl]butylamino]-s-triazine-4-yl}-N,N’-bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]-1,6-hexanediamine, terminated 2-butylamino-4-{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]-butylamino-s-triazine-6-yl

N,N’-Bis(2,2,6,6-tetramethylpiperidine-4-yl)-1,6-hexanediamine and N,N’-bis{2-[N-(2,2,6,6-tetramethylpiperidine-4-yl)butylamino]-4-chloro-s-triazine-6-yl}-N,N’-bis(2,2,6,b-tetramethylpiperidine-4-yl)-1,6-hexanediamine was mixed in a molar ratio of 0.5:1 in xylene at 100-160°C With sodium hydroxide, used as acid acceptor. Then the reaction mixture was treated with 2,4-bis(dibutylamino)-6-chloro-s-triazine in a similar situation. The mixture of oligomers was heated with tert-butylhydroperoxide and a catalytic amount of molybdenum trioxide in an inert solvent, such as 1,2-dichloroethane with formation of the corresponding N-ocelovych compounds. Aqueous hydrogen peroxide was added to a mixture of N-ocelovych compounds and iron chloride tetrahydrate(2) in tert-butyl alcohol method,solutions of the individual components may not be similar to the relationship of the product of Example 56.

Example 58

The oligomer of N-{2-[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-Tetra-methylpiperidin-4-yl]butylamino]-s-triazine-4-yl}-N,N’-bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]-1,6-hexanediamine, terminated by acetyl

The compounds obtained in Examples V and S, was mixed in a molar ratio of 2:1 in a solution of xylene at 100-160°C in the presence of sodium hydroxide, is used as the acid acceptor. After completion of the reaction, the reaction mixture was concentrated under reduced pressure. Then to the reaction mixture at room temperature was added acetic anhydride, after which the mixture was heated at 130°C. the Crude mixture was cooled and neutralized with potassium carbonate. The reaction mixture was concentrated under reduced pressure. The resulting product was a mixture of oligomers, which included 2, 4 and 6 repeating units, as shown in the following structure.

Example 59

The oligomer of N-{2-[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-Tetra-methylpiperidin-4-yl]butylamino]-s-triazine-4-yl}-N,N’-bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]-1,6-hexanediamine, terminated by acetyl

Repeated Example 54 for ISI with the procedure described in Example 58. The final product was a mixture of oligomers described in Example 58, although the relationship of the components may not be identical to the components of the product obtained as described in Example 58.

Example 60

Poly[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]acrylic

The target compound was obtained by free radical polymerization of the compound obtained as described in Example 16B. The average molecular weight of the polymer was 1500-3000.E.

Example 61

Poly[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]acrylate

The target compound was obtained by free radical polymerization of the compound obtained as described in Example 21. The average molecular weight of the polymer was 1500-3000.E.

Example 62

1,4-Bis(4-hydroxy)-2,2,6,6-tetramethylpiperidine-1 yloxy)-2-butanol

To a solution of 1,4-dibromo-2-propanol and excess 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine in chlorobenzene was added dropwise hydride presence of TBT. To facilitate the passage of the reaction mixture was heated. The crude reaction mixture was passed through silica gel, e is="ptx2">1,3-bis(4-hydroxy)-2,2,6,6-tetramethylpiperidine-1 yloxy)-2-propanol

To a solution of 1,3-dibromo-2-propanol and excess 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine in chlorobenzene was added dropwise hydride presence of TBT. To facilitate the passage of the reaction mixture was heated. The crude reaction mixture was passed through silica gel, elwira heptane, and then with a mixture of heptane/ethyl acetate, and received the target connection.

Example 64

2-Hydroxy-2-methylpropan-1,3-diyl-bis-{[1(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl](1-hydroxy-2,2,6,6-tetramethylpiperidine-4-yl)sebacate

The target compound was isolated from the crude reaction product obtained as described in Example 2, using liquid chromatography high pressure.

Example 65

1,3-Bis(4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine-1 yloxy)-2-methyl-2-propanol

To a mixture of 4-octadecanoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and iron chloride tetrahydrate in tert-butyl alcohol at 30-50°C was added aqueous hydrogen peroxide. The excess peroxide was decomposed by adding an aqueous solution of sodium sulfite. The organic layer was concentrated to obtain a mixture, which is the first compound was isolated from the mixture using liquid chromatography high pressure.

Example 66

1,3-Bis(4-hydroxy-2,2,6,6-tetramethylpiperidine-1 yloxy)-2-methyl-2-propanol

The target compound was isolated from the crude reaction product obtained as described in Example 16A using liquid chromatography high pressure.

Example 67

1,3-bis(4-oxo-2,2,6,6-tetramethylpiperidine - 1 yloxy)-2-methyl-2-propanol

The target compound was isolated from the crude reaction product obtained as described in Example 23A, using liquid chromatography high pressure.

Example 68

1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-1-yl)hexanoate

The target compound was obtained by heating a mixture of methylhexanoate, compounds obtained as described in Example 16A, lithium amide and xylene at the temperature of reflux distilled, removing methanol by distillation.

Example 69

4-Benzoyloxy-1-(2-hydroxyethoxy)-2,2,6,6-tetramethylpiperidine

To a solution of 2-idechannel and 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine in chlorobenzene was added dropwise hydride presence of TBT. The crude reaction mixture was passed through silica gel, elwira heptane, and then with heptane/ethyl acetate piperidin

The target compound was obtained by heating a methanol solution of the compound obtained as described in Example 69, with potassium hydroxide.

Example 71

Poly[4-hydroxy-1-(2-hydroxyethoxy)-2,2,6,6-tetramethylpiperidine-4-yl]succinate]

The target compound was obtained by reaction of approximately equimolar amounts of dimethylsuccinic and compounds obtained in Example 70.

Example 72

Poly[4-hydroxy-1-(2-hydroxycyclohexyl)-2,2,6,6-tetramethylpiperidine-4-yl]succinate]

The target compound was obtained by reaction of approximately equimolar amounts of dimethylsuccinic and compounds obtained as described in Example 35.

Example 73

1-(2-Hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine

A mixture of methyltaurine, compounds obtained as described in Example 16A, and a catalytic amount of lithium amide were heated under reflux in xylene. From the reaction mixture drove methanol. The reaction extinguished diluted acid. The organic layer was concentrated and the crude product was purified using flash chromatography on silica gel to obtain the desired compound in the form of b-2,2,6,6-tetramethylpiperidine-1 yloxy)-2-octadecanoyloxy-2-methylpropan

The target compound was obtained by reaction of the compound obtained as described in Example 16A with the excessive number of methyltaurine and a catalytic amount of lithium amide in xylene.

Example 74

4-Hydroxy-1-(2-hydroxy-1-venetucci)-2,2,6,6-tetramethylpiperidine

The target compound was obtained by heating a methanol solution of the compound obtained as described in Example 10, with potassium hydroxide.

Example 75

Poly[4-hydroxy-1-(2-hydroxy-1-venetucci)-2,2,6,6-Tetra-methylpiperidin-4-yl]succinate]

The target compound was obtained by reaction of approximately equimolar amounts of dimethylsuccinic and compounds obtained as described in Example 74.

Example 76

Stabilization of thermoplastic olefins

Molded samples for testing were obtained by injection molding the pellets of thermoplastic olefin (TPO), containing pigments, postit, phenolic antioxidant or a hydroxylamine, a metal stearate, the absorbers of ultraviolet radiation or stabilizers based on sterically zatrudnienia amines or a mixture of a UV absorber and stabilizer based on sterically constrained Amin.

KOMMERCHESKIY available TPO by mixing cooled in a water bath and granulated components in 1’single screw extruder Superior/MPM with a universal screw (DL/dia.=24:1) at 400°F (200°C). The obtained pellets were molded into 2’×2’plates, of a thickness of 60 mils (0,006 inch=0,1524 mm) at about 375°F (190°C) on the machine for injection moulding BOY 30M.

Pigmented TPO composition consisting of polypropylene mixed with a rubber modifier, where specified rubber modifier represents the in situ reacted copolymer or a mixed product containing copolymers of propylene and ethylene with a third component, such as ethylidenenorbornene, or without, stabilized with the use of the main stabilizing system consisting of N,N-dialkylhydroxylamines or sterically constrained phenolic antioxidant, whether or not containing organophosphorus compound.

All concentrations of additives and pigments in the final composition is expressed in mass percent by weight of the polymer.

Before extrusion and molding components were subjected to dry mixing in a drum dryer.

Plate for testing were removed from the metal mold and subjected to processing in weatherometer Atlas Ci65 Xenon Arc Weather-Ometer at a temperature of black panel 70°C to 0.55 W/m2at 340 nanometers and 50% relative humidity, with alternating cycles of light/dark is kilo intervals by measuring color spectrophotometer Applied Color Systems according to the type of reflection in accordance with ASTM D 2244-79. The obtained data represented values of Delta E, L*, a* and b*. Measurement of gloss was carried out on the device for measuring the turbidity/gloss BYK-Gardner at an angle of 60° according to ASTM D 523.

Test by UV-irradiation

Of test specimens subjected to UV irradiation, was found exceptional resistance to photodegradation when they stabilization svetosobirayushchim systems containing a combination of 2-(2-hydroxy-3,5-di-tert-amylphenol)-2H-benzotriazole (TINUVIN® 328, Ciba), compound of Example 73 and N,N’,N’,N’’-tetrakis[(4,6-bis(butyl-1,2,2,6,6-pentamethylpiperidin-4-yl)-amino-s-triazine-2-yl]-1,10-diamino-4,7-dosagecan (CHIMAS-SORB® 119, Ciba). The control sample consisted of songs stabilizers commonly used in industry for imparting resistance to UV-irradiation. All samples contained pigment, pigment Red 177 and talc.

Plate test described above, contained the following components (all concentrations are given in wt.% by weight of the polymer).

The polymer substrate was a commercially available polyolefin mixture POLYTROPE® TRR 518-01 supplied by A. Schulman Inc. Akron, Ohio).

The set of dyes represented 0,025% Red 3B - Red pigment 177, S. 1#65300.

Each petroline plate additionally contain:

0.1% of IRGANOX® B225 (mixture 50:50 IRGANOX® 1010 Ciba (neopentecostal-tetrakis(4-hydroxy-3,5-di-tert-butylhydrazine) and IRGAFOS® 168, Ciba [Tris(2,4-di-tert-butylphenyl)postit];

0.2% of TINUVIN® 770, Ciba [bis(2,2,6,6-tetramethylpiperidine-4-yl)sebacate];

0.2% of CHIMASSORB 944, Ciba [a polycondensation product of 4,4’-hexamethylene-bis(amino-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-tert-octylamine-s-triazine].

Each of the two plates for testing (NOR-1 and NOR-2) contained 0.05% of N,N-dialkylhydroxylamines;

NOR-1 was additionally contain:

0,2% CHIMASSORB® 119; and

0.2% of TINUVIN® 123 Ciba, [bis(1-octyloxy-2,2,6,6-tetramethylpiperidine-4-yl)sebacate];

NOR-2 additionally contained:

0,2% CHIMASSORB® 119; and

0,2% of the compound of Example 73.

The results of the test by UV-irradiation are presented in table.2.

The compound of Example 73, present in NOR-2-containing plates for testing, contributed, in particular, significantly better gloss retention compared to less effective control system and, in fact, was also more effective than the related compound sterically constrained amine (TINUVIN®123), present in NOR-1-containing plates for testing. The stability of their unsaturated triple component, such as a mixture of EPDM (ethylene propylene diene polymer with a co monomer), are particularly suitable for the stabilization of more effective systems of light stabilizers of the present invention described above.

In all cases, these light stabilizing compositions were encountered much more resistance to photodestruction than unstabilized samples were quickly destroyed under the action of UV radiation in the conditions described above.

Example 77

Painted TPO

Molded samples for testing were obtained by injection molding the pellets of thermoplastic olefin (TPO), containing compounds of the present invention, pigments and other adjuvants as described in Example 76.

Permanent tracks were painted one-component dyeing systems and tested for interaction "TPO-dye". Before staining the samples were first washed according to the method GM998-4801 and dried for 15 minutes at 200°F (94°C). Then applied the adhesion promoter with the receipt of a film (dry) thickness of 0.2 to 0.4 mil. The samples were dried for five minutes, then applied a primer coating 1K in the form of a film thickness of 1.2-1.4 m is the thickness (dry film) 1.2 to 1.5 mils, then dried in a stream of hot air for 10 minutes and subjected to heat treatment in an oven at 250°F (121°C) for 30 minutes.

The adhesion of the dye was measured by testing for adhesion in aggressive environments (patented test method conducted Technical Finishing, Inc.) and tested for abrasion on the device Taber. Painted panels, which retained more than 80% of the paint coating was seen as tested. After the test for adhesion in a hostile environment samples with loss of color, less than 5% were considered to have passed the test.

To assess the interaction between TPO/dye were carried out following samples were tested:

Composition And contained 0.2% of CHIMASSORB® 944, AND 0.2% TINUVIN® 328, 500 ml. e sterate calcium and 750 ml. D. N,N-dialkylhydroxylamines in TVET reactor type.

The composition also contained 0.2% of bis(2,2,6,6-tetramethylpiperidine-4-yl)sebacate (TINUVIN® 770, PKand=9,1).

Compositions b and C contained 0.2% of CHIMASSORB® 944, AND 0.2% TINUVIN® 328, 500 ml. e sterate calcium and 750 ml. D. N,N-dialkylhydroxylamines in TVET, suitable for reactors.

The composition also contained 0.2% of bis(1-octyloxy-2,2,6,6-tetramethylpiperidine-4-yl)sebacate (TINUVIN® 123, PKametripitline (the Compound of Example 73, PKand=4,0).

The data in the table showed that, although the composition is not tested for abrasion to Taber and tested for adhesive strength, however, and composition, and the composition passed the test for adhesion of the dye. The estimation of pKa values showed that the lower the pKa value (less than basic) for connection sterically constrained Amin, the less loss of color, registerware in the test for adhesion in agressivnyh environments. The compound of Example 73 of the present invention containing a hydroxyl group, had the lowest pKa value and the smallest loss of color and gave even better results than structurally similar to the well-known compound, which did not contain a hydroxyl group.

Example 78

The stabilization of the products that are molded from polypropylene

Molded samples for testing were obtained by injection molding of polypropylene granules containing pigments, postit, phenolic antioxidant or a hydroxylamine, a metal stearate, sinks ultraviolento radiation or stabilizers based on sterically constrained amine or a mixture of UV absorbers and stabilizer based on sterically constrained Anta, stabilizers, auxiliary additives and commercially available polypropylene by mixing cooled in a water bath and granulated components in 1’single screw extruder Superior/MPM with a universal screw (DL/dia.=24:1) at 475°F (250°C). The obtained pellets were molded into 2’×2’plates with a thickness of 60 mils (0,006 inch=0,1524) at about 475°F (250°C) on the machine for injection moulding BOY 30M.

Pigmented polypropylene composition consisting of homopolymer polypropylene or a copolymer of polypropylene stabilized with the use of the main stabilizing system consisting of N,N-dialkylhydroxylamines or sterically constrained phenolic antioxidant with organophosphorus compound, or without it.

All concentrations of additives and pigments in the final composition is expressed in mass percent by weight of the polymer.

Before extrusion and molding these components were subjected to dry mixing in a drum dryer.

Plate for testing were removed from the metal mold and subjected to processing in weatherometer (Atlas Ci65 Xenon Arc Weather-Ometer) at a temperature of black panel 70°C to 0.55 W/m2at 340 nanometers and relative humidity the samples was conducted at approximately 625 kilo intervals by measuring color spectrophotometer Applied Color Systems according to the type of reflection in accordance with ASTM D 2244-79. The obtained data represented values of Delta E, L*, a* and b*. Measurement of gloss was carried out on the device for measuring the turbidity/gloss BYK-Gardner at an angle of 60° according to ASTM D 523.

Test by UV-irradiation

Of test specimens subjected to UV irradiation, was found exceptional resistance to photodegradation after their stabilization svetosobirayushchim systems containing a combination of TINUVIN 328, the compounds of Examples 73 and CGL 2020. CGL 2020 is an oligomer of N-{[2-(N-2,2,6,6-tetramethylpiperidine-4-yl)butylamino-s-triazine-4-yl}-N,N’-{[bis-(2,2,6,6-tetramethylpiperidine-4-yl)-1.6-hexanediamine, terminated 2,4-bis-(dibutylamino)-s-triazine-6-yl. The control sample consisted of songs stabilizers commonly used in industry to stabilize to UV radiation. All samples contained pigment Red 177.

- All songs are based, stable 0.05% dialkylhydroxylamines in the final polymer composition.

Polymer substrate is commercially available polypropylene homopolymer - Profax 6501 (a commercial vendor Montell Polyolefins).

- Set dyes represents 0.25% of the Red 3B - pigment Red 177, C. 1#65300.

and tert-amylphenol)-2H-benzotriazole.

- NOR-2 represents bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)succinate.

Each composition contains 0.1% sterate calcium.

The samples represent 2’×2’plates with a thickness of 60 mils, sparmannia by injection molding.

UV-irradiation was carried out under conditions of SAE J 1960 - external conditions for the testing of automotive coatings.

All concentrations of additives and pigments in the final composition is expressed in mass percent by weight of the polymer.

The composition containing the target compound of Example 73, was found, in particular, significantly better gloss retention compared to less effective control system, even at a lower total concentration. Resistance to color change under the action of UV radiation was also higher. The target compound of Example 73 was also more effective in maintaining appearance compared to other solid compound N-O-R HALS (NOR 2) with similar molecular structure at equal concentrations.

In all cases, light-resistant composition was found much greater resistance to photodestruction than unstabilized samples that bilopillya fiber

Samples of the fibers were obtained by extrusion of polypropylene, suitable for the manufacture of fibers, with the compounds of the present invention, auxiliary additives and pigments. Typical compositions contain compounds of the present invention in amounts of from 0.05 to 2.0%, a metal stearate such as calcium stearate in an amount of from 0.05 to 0.5%, the pigments in an amount of from 0 to 5%, UV absorbers in the amount of from 0.05 to 2.0%, phosphites in an amount of from 0 to 0.1%, phenolic antioxidants in an amount of from 0 to 1.25%, N,N-dialkylhydroxylamines in the amount of from 0 to 0.1%, and optionally other steric amines employed in amounts of from 0 to 2.0%. All concentrations of additives and pigments in the final composition is expressed in mass percent by weight of the polymer.

Concentrates of pigments were obtained from pure pigment and polypropylene (PROFAX®, Hercules) by mixing the two components in the mixer with large shear forces in relation to 25% pigment and 75% of the polymer, with subsequent pressing of the mixture of polymer/pigment in the mold Wabash Compression (Model # 30-1515-TS) and receipt of a thin plate, which was then divided into small pieces for dispersion in polypropylene at low concentrations. Alternatively, the oxygen is of the fiber at low concentrations.

The compositions containing postit, phenolic antioxidant, dialkylhydroxylamines, calcium stearate, UV absorber, sterically hindered amine, were subjected to dry mixing in a drum drying and extrusion 1’-single screw extruder Superior/MPM with a universal screw (DL/dia.=24:1) at 475°F (246°C), cooled in a water bath and granulated. From the obtained pellet by spinning at 475°F (246°C) extruder for forming fibers (HILLS Research Fiber Extruder, Model # REM-3P-24) with Villeroy 41 hole, having a Delta configuration, produced fiber. Spun harness stretched at a rate of pulling of 3:2:1 with a final denier 615/41.

Of the fibre samples for laboratory knitting machine Lawson-Hemphill Fiber Analysis Knitter knitting socks that are cut into strips of appropriate length and processed in weatherometer (Atlas Ci65 Xenon Arc Weather-Ometer) at a temperature of black panel 70°C to 0.55 W/m2at 340 nm and at a relative humidity of 50% (Society of Automotiv Engineers - SAE J 1885 Test Procedure).

Samples of the fibers were tested by measuring color spectrophotometer Applied Color Systems according to the type of reflection in accordance with ASTM D 2244-79. Identical, but other samples of fibers were evaluated on the complete destruction and registration of the Wali good stabilization against adverse effects of UV radiation.

Example 80

Other socks made of polypropylene fibers obtained as described in Example 79, were placed in a pressure oven Blue M at 120°C. the Destruction was determined by the criteria specified in Example 79. Thus, the longer the time of complete destruction, the more effective stabilizing system.

Socks containing compounds of the present invention, showed a good thermal stabilization.

Example 81

Film-forming polyethylene was subjected to dry blending from about 10 wt.% subjects additives, such as the compound of Example 51, and then was subjected to molding in the melt at 200°With obtaining granules "masterbatches". Fully molded pellets "masterbatches" were subjected to dry blending with polyethylene resin to obtain the desired final concentration of the stabilizer. Typical compositions contain compounds of the present invention in amounts of from 0.05 to 2.0%, a metal stearate such as calcium stearate, in amounts of from 0.05 to 0.5%, postit in the amount of from 0 to 0.1%, phenolic antioxidant in an amount of from 0 to 1.25%, N,N-dialkylhydroxylamines in the amount of from 0 to 0.1%, and optionally other sterically hindered amine in an amount of from 0 to 2.0%. Then from the 00°C in the apparatus for fabricating films DOLCI.

The film obtained by extrusion injection blow, worked in weatherometer (Atlas Ci65 Xenon Arc Weather-Ometer) in accordance with ASTM G26 at a temperature of black panel 63°C, 0.35 watts/m2at 340 nm without a series of spraying. The film periodically tested to any change in elongation using an Instron dynamometer 112. In this test, the destruction was determined by monitoring the loss of % elongation in the film. The longer the time for which there is the loss of this elongation, the more effective the system stabilizers.

Film containing a mixture of compounds of the present invention, showed a good svetozarauladocy.

Example 82

Film-forming polyethylene was subjected to dry blending with 10 wt.% subjects additives, such as the compound of Example 51, and then was subjected to molding in the melt at 200°with the formation of granules full of uterine composition. Granules "masterbatches" were subjected to dry blending with polyethylene resin to obtain the final concentration of the stabilizer. This full resin composition was obtained a film thickness of 150 microns by blowing at 200°C in the apparatus for fabricating films DOLCI.

The resulting films were placed in a greenhouse at hall N-methyldithiocarbamate, VAPAM every six months and SESMETRIN every month). Data were registrirovali by monitoring the percent residual elongation. A negative test result was defined as the time elapsed up to 50% loss of the initial elongation.

Films containing compounds of the present invention, had good resistance to pesticides.

Example 83

Granules masterbatches, obtained as described in Example 81, mixed in dry form with a plastic resin to obtain the final concentration of the stabilizer. Full resin composition was obtained a film thickness of 150 microns by blowing at 200°C in the apparatus for fabricating films DOLCI.

The films obtained were applied to the soil to simulate conditions that are created when using agricultural mulch. Treatment consisted of exposure of this film methylbromide a fumigant for three days at 60 g/m3. The parameters were recorded by monitoring the time of occurrence of physical fragility.

Films containing compounds of the present invention, had good resistance to fumigants.

Example 84

Samples of films for greenhouses received, as described in Prietella. Typical compositions contain from 0.05 to 2 wt.% sterically obstructed amines of the present invention, 0.05 to 0.5% of metal stearate such as calcium oxide, and 0.05 to 0.5% of metal oxide such as zinc oxide or magnesium oxide.

Efficacy was evaluated as described in Example 82. Films containing compounds of the present invention, had good sitosterolaemia.

Example 85

Polypropylene fibers were obtained as described in Example 79. In addition to the compounds of the present invention in this composition were also included selected halogenated flame retardants (fire retardants). These flame retardants represented Tris(3-bromo-2,2-bis(methyl bromide)propyl)phosphate, decabromodiphenyl oxide, ethylene bis-(tetrabromophthalimide) or ethylene-bis-(dibromo-norbornenedicarboxylic).

In accordance with the criteria for svetozarauladocy described in Example 79, socks knitted from polypropylene fibers containing compounds of the present invention, had good sitosterolaemia.

Example 86

Polypropylene is suitable for molding grade) was mixed in dry form with test additives and then molded in the melt to obtain granules. In addition to the compounds nasali a Tris(3-bromo-2,2-bis(methyl bromide)propyl)phosphate, decabromodiphenyl oxide, ethylene bis-(tetrabromophthalimide) or ethylene-bis(dibromomalonamide). Then granulated full polymer composition was subjected to injection molding to molding and received test samples using a mold for injection molding a laboratory model Boy 50M.

Plate for testing were removed from the metal mold and subjected to processing in weatherometer Atlas Ci65 Xenon Arc Weather-Ometer, with alternating cycles of light/dark and spraying water in accordance with the test method according to ASTM G26. Samples were periodically tested at certain intervals of time to change the mechanical properties in tension. In this test, the degradation was determined by monitoring the ability to stretch. The longer the time for which there is a loss of this ability to stretch, the more effective the system stabilizers.

The test samples containing a mixture of compounds of the present invention, showed a good svetozarauladocy.

Example 87

Molded test samples was obtained by injection molding the pellets of thermoplastic olefin (TPO), as described in Example 76. In addition to the compounds of the present invention, these samples tacit, decabromodiphenyl oxide, ethylene bis(Tetra-bromophthalimide) or ethylene-bis(dibromomalonamide).

Test samples containing sterically difficult amines of the present invention, showed a good svetasmilygirl activity.

Example 88

Film-forming polyethylene was formed and received the film by blowing at 200°C, as described in Example 82, the apparatus for obtaining films DOLCI. In addition to the compounds of the present invention, this composition also contained the selected flame retardants. These flame retardants represented Tris(3-bromo-2,2-bis-(methyl bromide)propyl)phosphate, decabromodiphenyl oxide, ethylene bis(tetrabromophthalimide) or ethylene-bis(dibromomalonamide).

When testing on svetasmilygirl activity as described in Example 82, the film containing the compounds of the present invention, showed a good stabilization.

Example 89

Molded test samples was obtained by injection molding the pellets of thermoplastic olefin (TPO), as described in Example 77.

Samples for testing were stained with one-component systems of dyes and tested for the interaction TPO-dye". Before staining the leaching of these samples were coated with adhesion promoter, and then primer coating and optionally a non-pigmented coating. A typical film thickness of various coatings was 0.1 to 0.3 mil for the adhesion promoter, 0.6 to 0.8 mil for primer coating and 1,2-1,5 million for non-pigmented coatings. After staining, the samples were dried in an oven for 30 min at 120°C.

The samples were tested for interaction TPO-dye" as follows. In the initial test, the adhesion of the transparent cellophane adhesive tape was used to cover 3 mm, the surface marked with a dash of paint; or in the test for water resistance, the painted plate was left for 240 hours at 38°C in an atmosphere having a relative humidity of 98%. Assessment bubbles was performed by visual inspection according to ASTM D 714.

In accordance with the criteria defined above, the samples containing the compounds of the present invention, had good properties in respect of interaction "TPO-dye".

Example 90

Thermoplastic elastomers

Polymeric materials of the General class known as thermoplastic elastomers and examples of which are copolymers of styrene and butadiene or isoprene and/or copolymer of these is rowany from the melt to obtain granules. Typical compositions contain compounds of the present invention in amounts of from 0.05 to 2.0%; metal stearate such as calcium stearate, in amounts of from 0.05 to 0.5%; pigments in an amount of from 0 to 5%, UV absorbers in the amount of from 0.05 to 2.0%; phosphites in an amount of from 0 to 0.1%; phenolic antioxidants in an amount of from 0 to 1.25%; N,N-dialkylhydroxylamines in the amount of from 0.0 to 0.1%, and optionally other stabilizers based on sterically obstructed amines in amounts of from 0.0 to 2.0%.

Then this granulated full polymer composition was molded into the desired product in such a way as extrusion injection blow or extrusion from the melt with obtaining film, injection molding to obtain a molded product, the molded thermoplastics with obtaining molded products, extrusion getting sheath wire and cable, or rotational molding with obtaining hollow products.

Materials containing compounds of the present invention have a stability against the destructive effect of UV radiation and high temperatures.

Example 91

The product obtained as described in Example 90 which additionally contain selected organic pigments and compounds of the present high temperatures.

Example 92

The product obtained as described in Example 90 which additionally contain sterically hindered phenolic antioxidant selected from the group consisting of neopentylglycol(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 1,3,5-trimethyl-2,4,6-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,2-bis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)hydrazine, [bis(monoethyl-3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate] calcium; 1,3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate and 1,3,5-Tris-(3-hydroxy-4-tert-butyl-2,6-dimethylbenzyl)isocyanurate; and compounds of the present invention, also had a stability against the destructive action of photochemically active radiation and high temperatures.

Example 93

The product obtained as described in Example 90 which additionally contain phosphorus stabilizer selected from the group comprising Tris(2,4-di-tert-butylphenyl)hospit; bis(2,4-di-tert-butyl-6-were)ethylphosphate; 2,2’,2’-nitrilo[triethyl-Tris(3,3’,5,5’-Tetra-tert-butyl-1,1’-biphenyl-2,2’-diyl)postit], Tetra-KIS(2,4-dibutyltin)-4,4’-biphenylenediisocyanate, Tris(nonyl-phenyl)hospit; bis(2,4-di-tert-butylphenyl-tert-butylphenylphosphine, and compounds of the present invention, also had a stability against the destructive action of photochemically active radiation and high temperatures.

Example 94

The product obtained as described in Example 90, which, in addition, contained benzofurazanyl stabilizer, which is 5,7-decret-butyl-3-(3,4-dimetilfenil)-2H-benzofuran-2-it, as well as compounds of the present invention, also had a stability against the destructive effect of UV radiation and high temperatures.

Example 95

The product obtained as described in Example 90 which additionally contain a stabilizer based dialkylhydroxylamines, which is N,N-dialkylhydroxylamines obtained by direct oxidation of N,N-di(hydrogenated tallow)amine and compounds of the present invention, also had a stability against the destructive action of photochemically active radiation and high temperatures.

Example 96

The product obtained as described in Example 90 which additionally contain other stabilizers based on sterically obstructed amines selected from the group comprising bis(2,2,6,6-tetramethylpiperidine-4-yl)sebacate, the polycondensation product -(1,2,2,6,6-pentamethylpiperidin-4-yl)amino)-s-triazine-2-yl]-1,10-diamino-4,7-dosagecan, the polycondensation product of 4,4’-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-tert-octylamine-s-triazine; the polycondensation product of 4,4’-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-morpholino-s-triazine; (2,2,6,6-tetramethylpiperidine-4-yl)octadecanoate, 3-dodecyl-1-(1-acetyl-2,2,6,6-tetramethylpiperidine-4-yl)pyrrolidin-2,5-dione; 1,3,5-Tris{N-cyclohexyl-N-[2-(2,2,6,6-tetramethylpiperidine-3-one-4-yl)-ethyl]amino)-s-triazine; poly[methyl-3-(2,2,6,6-tetramethylpiperidine-4-yloxy)propyl]siloxane, a polycondensation product of 2,4-dichloro-6-(2,2,6,6-tetramethylpiperidine-4-yl)butylamino)-s-triazine and 2,2’-ethyl n-bis{[2,4-(2,2,6,6-tetramethylpiperidine-4-yl)butylamino-s-triazine-6-yl]aminodimethylaniline} and compounds of the present invention, also had a stability against the destructive action of photochemically active radiation and high temperatures.

Example 97

The product obtained as described in Example 90 which additionally contain other N-hydrocarbonization steric employed amines selected from the group comprising bis(1-octyloxy-2,2,6,6-tetramethylpiperidine-4-yl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidine-4-yl)adipate, bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)adipate; bis is decanoate, and compounds of the present invention, also had a stability against the destructive action of photochemically active radiation and high temperatures.

Example 98

The product obtained as described in Example 90 which additionally contain o-hydroxyphenyl-2H-benzotriazoles, hydroxystilbamidine or o-hydroxyphenyl-s-trisonomy UV absorber selected from the group comprising 2-(2-hydroxy-3,5-di-cumylphenol)-2H-benzotriazole; 2-(2-hydroxy-5-were)-2H-benzotriazole; 5-chloro-(2-hydroxy-3,5-decret-butylphenyl)-2H-benzotriazole; 2-(2-hydroxy-3,5-decret-amylphenol)-2H-benzotriazole; 2-(2-hydroxy-3-cumylphenol-5-tert-octylphenyl)-2H-benzotriazole; 2,4-decret-butylphenyl-3,5-decret-butyl-4-hydroxybenzoate; 2-hydroxy-4-n-octyloxybenzophenone and 2,4-bis(2,4-dimetilfenil)-6-(2-hydroxy-4-octyloxyphenyl)-s-train, and compounds of the present invention, also had a stability against the destructive effect of UV radiation and high temperatures.

Example 99

Subjects stabilizers based on difficulty amine was introduced in a two-component polyester urethane coating based on commercially available complex polyether (polyol) (DESMOPHEN® 670-80) and was commercially doctorserial of 0.015 wt.% dilaurate dibutylamine by mass of all solid polymer.

Each composition for coating was applied on a transparent glass slide measuring approximately 4’×6’ in the form of a film thickness of 2 mils (0.002 inch) in the triple duplicate.

These glass plates in the triple duplicates were processed as follows:

Plate 1 - heat treatment for 30 minutes at 180°F (82°C). the curing at room temperature; and daily inspection.

Plate 2 - air drying (drying at ambient temperature); curing at room temperature; and daily inspection.

Plate 3 - air drying for one day; keeping in an oven at 120°F (49°C); daily inspection and subsequent curing at 120°F (49°C).

Starting from time 0, all plates were visually evaluated on their appearance, while there is some haze inside the coverage and appearance of any effusion on the coating surface was observed. The results of the four-day observations are presented below.

These data showed that the compound of the present invention having a hydroxy-group, present on the group attached at the 1-position is sterically constrained Amin, obespechenie using the most structurally similar known compounds, in which there is no specified hydroxy-group.

Experiments have shown that if the compounds of the present invention are soluble and compatible in this particular transparent coating, it is possible to tell with confidence that they will be compatible and soluble in other polymer systems.

Example 100

Approximately 50 ml of the same stable two-component clear coatings described in Example 99, was placed in the gel in a sealed vessel with a capacity of 4 ounces (118 cm3). After curing these cured coating was visually evaluated on the transparency. The appearance of opacity and Berezoutski indicates incompatibility between the stabilizer based on sterically constrained amine, and a composition for coating. Utverjdenie floor in the vessel:

These data showed that the compound of the present invention having a hydroxy-group, present on the group attached at the 1-position is sterically constrained amine, provides excellent solubility and compatibility for polyester urethane coating, which cannot be achieved using the most structurally similar known is methylpropoxy)-4-[9-(methoxycarbonyl)-nonanoate]-2,2,6,6-tetramethylpiperidine

The target compound was obtained by reaction of the compound obtained as described in Example 16A with one or more equivalents of dimethylcarbonate and with a catalytic amount of lithium amide in xylene.

Example 102

1-(2-Hydroxy-2-methylpropoxy)-4-[5-(methoxycarbonyl)-pentanoate]-2,2,6,6-tetramethylpiperidine

The target compound was obtained as described in Example 101, except that instead of dimethylcarbamate used equivalente number of dimethyladipate.

Example 103

1-(2-Hydroxy-2-methylpropoxy)-4-[3-(methoxycarbonyl)-propionyloxy]-2,2,6,6-tetramethylpiperidine

The target compound was obtained as described in Example 101, except that instead of dimethylcarbamate used equivalente number of dimethylsuccinic.

Example 104

1-(2-Hydroxy-2-methylpropoxy)-4-[4-(methoxycarbonyl)-butyryloxy]-2,2,6,6-tetramethylpiperidine

The target compound was obtained as described in Example 101, except that instead of dimethylcarbamate used equivalente number of dimethylglutaric.

Example A

A mixture of 1-(2-Hydroxy-2-methylpropoxy)-4-[5-(methoxycarbonyl)-pentanoate]-2,2,6, the ina

Repeated Sample 101, except that instead of dimethylcarbamate used the equivalent number of complex dibasic ester DBE-2 (DuPont®).

Example V

A mixture of 1-(2-hydroxy-2-methylpropoxy)-4-[5-(methoxycarbonyl)-pentanoate]-2,2,6,6-tetramethylpiperidine and 1-(2-hydroxy-2-methylpropoxy)-4-[4-(methoxycarbonyl)butyryloxy]-2,2,6,6-tetramethylpiperidine

Repeated Sample 101, except that instead of dimethylcarbamate used the equivalent number of complex dibasic ester DBE-3 (DuPont®).

Example 105

The condensation products of 4-hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine with hexamethylenediisocyanate, terminated with methoxy group

The target compound was obtained by reaction of approximately equimolar amounts of the compound obtained as described in Example 16A, hexamethylenediisocyanate followed by reaction with an excess of methanol.

Example 106

The condensation products of 4-hydroxy-1-(2-hydroxyethoxy)-2,2,6,6-tetramethylpiperidine with hexamethylenediisocyanate, terminated with methoxy group

The target compound was obtained by reaction of approximately equimole what eakley with an excess of methanol.

Example 107

The condensation products of 4-hydroxy-1-(2-hydroxy-1-venetucci)-2,2,6,6-tetramethylpiperidine with hexamethylenediisocyanate, terminated with methoxy group

The target compound was obtained by reaction of approximately equimolar amounts of the compound obtained as described in Example 74, hexamethylenediisocyanate followed by reaction with an excess of methanol.

Example 108

Stabilization of two-component acrylic urethane clear coating

Subjects stabilizers based on difficulty amine was introduced in a two-component polyester urethane coating described in Example 99. This system catalyzed 0.02 wt.% dilaurate dibutylamine by mass of all solid polymer. The stabilizer was added in an appropriate amount to acrylic paleologou part two-component coating, which is then combined with the isocyanate component before application.

Steel panels 3’×4’, which by electrodeposition was applied primer coating was then covered with a pale blue metal primer coating, after which it was senesino stable depigmentation), then inflicted stable non-pigmented coating with obtaining a dry film thickness of 2.0 mils (50 microns). The coating was air dried and kept for two weeks. Then the panels were treated in weatherometer Xenon Arc Weather-Ometer under the following conditions:

Standard conditions - 180 cycles: 40 minutes only to light; 20 minutes on the light front spraying; 60 minutes only to light; 60 minutes in the dark with the rear jet condensation.

Lamp filters: quartz inside/borosilicate's outside.

Exposure: 0.45 watts per square meter.

The gloss on gloss with the reflection of light at an angle 20° (20°-Shine) was measured before exposure and after 500-hour intervals during exposure. Desirable is more time saving Shine.

These data showed that replacement compounds of the present invention provide value save 20°-Shine, comparable with values NOR-compounds at equivalent molar concentrations.

Example 109

Stabilization of two-component acrylic urethane clear coating

Transparent coating obtained as described in Example 108, caused by the centrifuge holds is about 25 microns. Initial optical film thickness of each disk was measured using interferometer Cassa. Then the disks were processed in weatherometer Xenon Arc Weather-Ometer under the following conditions:

Standard conditions - 180 cycles: 40 minutes only to light; 20 minutes on the light front spraying; 60 minutes only to light; 60 minutes in the dark with the rear jet condensation.

Lamp filters: quartz inside/quartz outside.

Exposure: 0.45 watts per square meter.

The optical film thickness periodically measured every 250 hours, and for each composition was determined by loss of film coating. Loss of film coating, due to atmospheric effects and measured through 3972 and 5561 hours, are presented in the table below. It is desirable to lower the value of the loss of film coating.

These data showed that replacement compounds of the present invention give the values of resistance to erosion, comparable with the values of the most structurally close NOR-compounds at equivalent molar concentrations.

Example 110

Coatings for plastic substrates

The main application of the minority istericheskogo many low-molecular directionspanel light stabilizers migrate into the plastic substrate during drying and curing. As a result of this significant part of sitosterolemia can move from the upper surface to the substrate, and therefore the protection of this upper surface may be ineffective.

The degree of migration of stabilizers based on sterically obstructed amines during application and curing of the coating is determined by comparing the concentration of sterically constrained amine in dry non-pigmented coating on a plastic substrate, with the same non-pigmented coating deposited on an opaque substrate, such as glass or steel.

Subjects stabilizers based on sterically obstructed amines were injected into the elastic thermosetting acrylic/melamine clear coating, suitable for use on automotive plastic substrates. Sterically hindered amine was injected in the amount of 1.5 wt.% by mass of all solid polymer.

Each composition for coating was applied by automatic spray on the substrate RIM for car (molded by casting under pressure) and TPO (thermoplastic polyolefin). Both substrates were fabricated in the form of plates size 4’×12’. Each floor of Nana heat treatment at 250°F (121°C) for 20 minutes.

Samples of triple duplicate for each utverzhdenii composition for coating was separated from each of the substrates, and crushed in cryogenic conditions to obtain fine powder. A known amount of each sample was extracted with boiling toluene during the night. Present sterically hindered amine quantitatively analyzed by diluting to a known volume and analyzed using HPLC - or ZH-chromatography. Then, for each of the test compounds stabilizer constructed calibration curves. This method determined the content of the sterically constrained amine for each extracted coverage.

When comparing compounds sterically obstructed amines of the present invention, substituted on the N-atom by a group-O-E -, HE, with the corresponding NOR-compounds that do not contain hydroxyl groups, it was found that the compounds sterically obstructed amines of the present invention have a higher save percentage in non-pigmented coating on a plastic substrate, which indicates that the stabilizers based on sterically obstructed amines of the present invention is much less than migrate into the plastic substyle substrates.

Example 111

Stabilization of water-soluble wood lacquer

All of the coatings are an important and growing importance of the water-soluble coating, widely used in various purposes, including primer coating for automobiles, industrial coatings and films used in the trade. These coatings can be pigmented or transparent. There is also a tendency to use more solid compositions, which mainly depend on light stabilizers that ensure the preservation of the properties of this composition when exposed to the external environment, and to use lower levels of alcohol. This requires a higher solubility of the stabilizer in said cosolvent (mostly water) or, in fact, the solubility in water.

Subjects stabilizers were introduced in the water-soluble dispersion by pre-dissolving in a mixture of co-solvents. Water-soluble dispersion is a commercially available acrylic/urethane hydride resin. This mixture of co-solvents is a 1:1-mixture of TEXANOL® (2,2,4-trimethyl-1,3-pentandiol, Texaco) and ARCOSOLVE®TPM (methyl ether of tripropyleneglycol, AtlanticRichfield).

0.45 g ispytuemomu composition:

Jr. d

FLEXTHANE®630 (Air Products) 100,0

The foaming agent VF 0,1

Water 10,0

NOL®/ARCOSOLVE®/hindered amine 10,5

UV absorber (TINUVIN® 1130, Ciba) 1,2

BYK 346 0,5

MICHEMLUBE® 162 2,0

Each coating was applied by brush on 6’×6’ section of cedar and pine boards. The weight of the coating controlval by weight of the coating and brush before and after application, and watched to coatings applied to each section were the same.

Section boards coated with the coatings were left for drying at ambient temperature for two weeks and then evaluated their appearance, gloss and color L*, a* and b* on a scale of hunter. These sections were placed on stands at an angle of 45° in South Florida for six months, and then they were returned and evaluated their appearance, gloss, discoloration and any other signs of degradation or delamination.

Compounds sterically obstructed amines of the present invention, substituted N-atom by a group-O-E-HE-has ensured a higher degree of stabilization of these sections, such as their appearance, gloss retention, resistance to color change and stratification than in meeting pigmented primer coating OEM for cars

Primer coating, pigmented mixture of red pigment 177 and mica, stabilized 1 wt.% stabilizer based on sterically constrained amine by weight of all solids primer coating (pigment plus resin). This primer coating was applied by atomization onto steel panels measuring 4’×12’ thin layer with a dry film thickness of 1 mil (25 microns), and then top inflicted commercially available transparent coating with a high content of solid substances of a kind used for vehicles. Panel coating was dried in an oven at 250°F (121°C) for 30 minutes. Then these panels were treated in weatherometer under the following conditions:

Standard conditions - 180 cycles: 40 minutes only to light; 20 minutes on the light front spraying; 60 minutes only to light; 60 minutes in the dark with the rear jet condensation.

Lamp filters: quartz inside/borosilicate's outside.

Exposure: 0.55 watts per square meter.

20° luster, flawless appearance, body color saturation on the hunter L*, a*, b* and E) were measured before testing and after 3000 hours of testing.

Compounds sterically obstructed amines of the present invention, showing their appearance, save Shine, resistance to color change and stratification than the corresponding NOR-compounds that do not have a hydroxyl group.

Example 113

Use the molded ABS

Thermoplastic materials consisting of mixtures of copolymers obtained by copolymerization of styrene monomer with Acrylonitrile copolymerization of styrene monomer with butadiene, and commonly called ABS, mixed in dry form with the compounds of the present invention and formed from the melt to obtain granules. Typical compositions contain compounds of the present invention in amounts of from 0.05% to 2.0% of a metal stearate such as calcium stearate in an amount of from 0.05% to 0.5%, and the pigments in an amount of from 0% to 5%, UV absorbers in the amount of from 0.05% to 2.0%, phosphites in the amount of from 0.0% to 0.1%, phenolic antioxidants in an amount from 0.0% to 1.25%, N,N-dialkylhydroxylamines in number from 0.0% to 0.1%, and optionally other steric amines employed in amounts of from 0.0% up to 2.0%.

Then from this granulated full resin composition was obtained the desired product by appropriate processing, such as extrusion with getting plates, films, profiles, and tubes; formovani what lay in molded products; or rotational molding with obtaining hollow products.

Materials containing compounds of the present invention have a resistance to the destructive action of UV radiation and high temperatures.

Example 114

The values of the PKand

To determine the values PKandwater-insoluble materials standard organic compounds with known values PKandin water were subjected to anhydrous titration. Curve was built according to the capacity of polyneuropathy (PPN) from known values of water PKandfor the reference compounds. Determined DNF of the test material and extrapolated to obtain the corresponding values of the PKandfor the test material. These reference compounds are 2,2,6,6-tetramethylpiperidine; 4-hydroxy-2,2,6,6-tetramethylpiperidine; 1-hydroxyethyl-4-hydroxy-2,2,6,6-tetramethylpiperidine; triacetonamine and N-methylaniline.

Reference materials, which by their structure, at least perifericheskie are related test compounds of the present invention, and which are soluble in both water and in a mixture (1:1) acetonitrile:chloroform, were used for postro m 0.1 N. the solution perchloro acid/dioxane). Approximately 0.5 milliequivalents test material was weighed in a vessel for titration. For dissolution of the sample was added 30 ml of acetonitrile. Before titration was added 30 ml of chloroform. Then titration was performed and determined DNF. Electrolyte for standard electrode was 2-(aminomethylpyridine). To achieve equilibrium after filling the electrolyte electrode was left in the solvent system for two hours. All samples were taken in duplicates.

The values of the PKandpresented in table.3.

As can be seen from each of the above pairs of related compounds, where the individual compounds differ from each other only by the substitution piperidino ring in the 1-position by a group-O-R or a group-O-E-HE, the compounds of the present invention containing the group-O-E-HE-have significantly lower the pKa value, which indicates that the compounds of the present invention are respectively lower basicity than the well-known N-OR-connection.

Evaluation of the results obtained in Example 77, has shown that this lower basicity and a lower pKa value can be interpreted as the best indicator connected to the input voltage to the loss of color in painted thermoplastic polyolefins (TPO).

Example 115

Inhibition burning

Polypropylene, suitable for production of fibers, mixed in dry form with test additives and then molded in melt at 234°C (450°F) with the formation of granules. All compositions also contained system stabilizers used for forming from the melt. Then granulated full polymer composition was subjected to spinning to obtain fibers with 246°C (475°F) using a laboratory extruder model of Hills for spinning fibers. Spun the wiring 41 of the fiber was stretched in the ratio of 1:3:2 with a final denier 615/41.

Then from these fibers knitted socks for experimental knitting machine Lawson-Hemphill. Ten duplicates of each sample were tested by the method of vertical combustion NFPA701-1996. For related socks time (in seconds) after the termination of the flash of flame and until complete attenuation was defined as the time after ignition". On the effectiveness of the injected flame retardant indicated the observed low value of time of burning after ignition in comparison with the control sample containing no flame retardant. It was also registered during burning drops of material and loss of mA is Renov.

Example 116

Inhibition of combustion thick plates of polypropylene

Polypropylene, suitable for molding, mixed in dry form with test additives and then molded from the melt with the formation of granules. In addition to the compounds of the present invention, the composition also included halogenated flame retardants. Typical compositions contain a compound of the present invention and flame retardants, such as Tris(3-bromo-2,2-bis(methyl bromide)propyl)phosphate (FMC PB370); bis(2,3-dibromo-propyl ether) of bisphenol a (RE); decabromodiphenyl oxide (DBDPO); ethylene-bis-tetrabromophthalimide (SATEX W-93); ethylene-bis-dibromomalonamide (SATEX BN-451). Other songs in addition to the brominated flame retardants may also contain Sb2O3. Other compositions may contain flame retardants based on phosphorus, such as diphosphate Ethylenediamine (EDAP). Then granulated full polymer composition was molded under the pressure of obtaining samples for testing using a Wabash press.

Plate for testing tested under vertical combustion UL-94. The test was subjected to at least three duplicate. For the test sample was the average time in seconds to complete the Declaration of the observed time of burning. Compounds of the present invention containing only or halogenated phosphate flame retardant, promote inhibition of burning.

Example 117

Inhibition of combustion thick plates of polypropylene

Polypropylene, suitable for molding, obtained by injection molding the pellets of thermoplastic olefin (TPO), containing compounds of the present invention. TPO compositions can also contain pigments, phenolic antioxidants, postit or hydroxylamine, a metal stearate, the absorbers of UV radiation (UVA) or stabilizers based on sterically obstructed amines (HALS), or a mixture of UV absorbers and stabilizers based on sterically obstructed amines.

In addition to the compounds of the present invention, the composition also included halogenated flame retardants. Typical compositions contain a compound of the present invention and flame retardants, such as Tris(3-bromo-2,2-bis(methyl bromide)propyl)-phosphate (FMC PB370); bis(2,3-dibromopropyl ether) of bisphenol a (RE); decabromodiphenyl oxide (DBDPO); ethylene-bis-tetrabromophthalimide (SATEX W-93); ethylene-bis-dibromomalonamide (SATEX BN-451). Other songs, in addition to the brominated flame retardants, may also contain Sb

Plate for testing tested under vertical combustion UL-94. The test was subjected to at least three duplicate. For the test sample was the average time in seconds to complete attenuation of the flame after the first and second bursts of flame. Compounds of the present invention containing only or halogenated phosphate flame retardant, promote inhibition of burning.

Example 118

Sitosterol the molded ABS with the use of flame retardants

ABS, suitable for molding, mixed in dry form with test additives and then molded from the melt with the formation of granules. In addition to the compounds of the present invention, the composition also included selected flame retardants. Such flame retardants was Tris[3-bromo-2,2-bis(methyl bromide)propyl]phosphate; decabromodiphenyl oxide; ethylene-bis(tetrabromophthalimide) and ethylene-bis(dibromomalonamide). Then granulated full polymer composition was subjected to injection molding the molding on a lab machine for injection moulding model BOY 50M with obtaining samples for testing. Other songs, in addition to bromi skilled flame retardants may also contain antimony trioxide (Sb2O3<>P CLASS="ptx2">Plate for testing were removed from the metal mold and subjected to processing in weatherometer (Atlas Ci65 Xenon Arc Weather-Ometer), with alternating cycles of light/dark and spraying water in accordance with the test procedure according to ASTM G26. Samples were periodically tested at certain intervals of time on the mechanical properties of tensile and color change. The longer the time for which there is a loss of these properties, and change the color, measured as E, the more effective the system stabilizers.

The test samples containing a mixture of compounds of the present invention, showed a good ability to stretch and minimal color change during curing under conditions of rapid destruction under the influence of atmospheric effects.

Example 119

Sitosterol in forming PSWAP using flame retardants

Polystyrene, high impact resistance, suitable for molding, mixed in dry form with test additives and then molded from the melt with the formation of granules. In addition to the compounds of the present invention, the composition also included selected flame retardants. Such flame retardants was Tris[3-bromo-2,2-bis(brough rboxylic). Then granulated full polymer composition was subjected to injection molding the molding on a lab machine for injection moulding model BOY 50M with obtaining samples for testing. Other songs, in addition to the brominated flame retardants, may also contain antimony trioxide (Sb2O3). Other compositions may contain flame retardants based on phosphorus, such as diphosphate Ethylenediamine (EDAP).

Plate for testing were removed from the metal mold and subjected to processing in weatherometer (Atlas Ci65 Xenon Arc Weather-Ometer), with alternating cycles of light/dark and spraying water in accordance with the test procedure according to ASTM G26. Samples were periodically tested at certain intervals of time on the mechanical properties of tensile and color change. The longer the time for which there is a loss of these properties, and change the color, measured as E, the more effective the system stabilizers.

The test samples containing a mixture of compounds of the present invention, showed a good ability to stretch and minimal color change during curing under conditions of rapid destruction under the influence of atmospheric effects.

Example 120

The enamel of thermosetting acrylic polymer with a high solids content (50 wt%), catalyzed 0.8 wt.% dodecylbenzenesulfonic acid by weight of film-forming polymer, stabilized by adding various compounds of the present invention. Composition for enamel obtained from thermosetting acrylic polymer with a high content of solids (Acryloid AT-400 from Rohm & Haas, contained hydroxyethylmethacrylate, methyl methacrylate, styrene, butyl acrylate and butylmethacrylate and melamine curing agent.

Then pieces of steel plate size 4’×12’ (9,16 cm × 30.48 cm), coated with a primer coating based on polyester/epoxy resin, was coated Tio3-pigmented primer coating obtained on the basis of a binder containing 70% of monomers such as hydroxyethylacrylate, styrene, Acrylonitrile, butyl acrylate and acrylic acid, and 30% melamine resin and an acid catalyst, then applied a clear top coat enamel. Primer coating thickness of about 0.8 mil (0,0203 mm) was applied on the plate by comminution and air-dried for three minutes. Then on the plate by comminution inflicted transparent pokrywy is obrabotke at 121°C for 30 minutes.

Before coating on the primer coating in the coating enamel-based thermosetting acrylic resin was added to the test stabilizers in a concentration of 1 wt.%.

After storage for three weeks in a room with air conditioning (at a relative humidity of 23°C/50%) plate coating was exposed for 2000 hours weathering in weatherometer (Xenon Arc Weather-Ometer) in accordance with SAE J 1920. In this apparatus, the samples were subjected to weathering in repeating cycles within 180 minutes. The stabilization effect was measured on conservation 20°-luster after keeping in atmospheric conditions.

Plate, stable compounds of the present invention, showed a good preservation of the 20°-luster after their withstand extreme weather conditions.

Example 121

The samples obtained as described in Example 120, also assessed on the Knoop hardness (ASTM D-1474-68), where we used the samples subjected to hot and superhot heat treatment, flawless appearance (DOI); the office of the hunter; 20°gloss (ASTM D-523-80); and cracking by visual observation.

The samples stabilized by the compounds in the absence of a strong cracking after processing.

Example 122

In the composition of the enamel of thermosetting acrylic resin, obtained as described in Example 120, consisted of 3 wt.% benzotriazole UV absorber and 1.5 wt.% the test compounds sterically constrained amine of the present invention. The enamel was coated on top of the white ground or on top of a silver metal primer coating. Hot heat treatment was carried out at the normal temperature of the heat treatment 121°C or at a temperature low temperature heat treatment 82°C, used in the repair of cars.

Panels coated was placed in the apparatus for creating atmospheric conditions (Xenon Arc) and was determined 20° Shine and flawless appearance (DOI).

The samples stabilized with the compounds of the present invention, differed longer save 20°-Shine and the best DOI.

Example 123

Received two pieces of enamel from thermosetting acrylic resin containing 3 wt.% benzotriazole UV absorber and 1 wt.% the test compounds sterically constrained amine of the present invention.

The enamel of thermosetting acrylic resin contained binder, comprising 70% of Muminova resin and acid catalyst, such as p-toluensulfonate acid, dinonylnaphthalenesulfonic acid, dodecylbenzensulfonate or acid phosphate, phenyl acid.

Then pieces of steel plate size 4’×12’ (9,16 cm × 30.48 cm), coated with a primer coating based on polyester/epoxy resin, was coated with a primer coating, and then the transparent coating enamel. Primer coating thickness of about 0.8 mil (0,0203 mm) was applied on the plate by comminution and air-dried for three minutes. Then on the plate by comminution inflicted transparent enamel coating thickness of about 2.0 mils. After a 15-minute air drying plates coated was subjected to hot to heat treatment at 121°C for 30 minutes.

Panels coated was placed in the apparatus for creating atmospheric conditions (Xenon Arc) and was determined 20° Shine and flawless appearance (DOI).

The samples stabilized with the compounds of the present invention, has a higher saving 20°-Shine and the best DOI.

Example 124

In this example, used white, not containing oil, alkylamino floor for roll materials based on polyester/melamine. Full lacor the m floor, as a result, we got the tape, where the dry film thickness was 0.6-0.8 mil. These panels were subjected to heat treatment at 220°C for approximately 90 seconds, and then removed from the furnace and immediately immersed in water. These panels are coated was placed in weatherometer (Xenon Arc), and then the sun at an angle of 45° in South Florida and was determined 20°-luster.

The samples stabilized with the compounds of the present invention, differed best saving 20°-luster.

Example 125

In the composition of the enamel of thermosetting acrylic resin, obtained as described in Example 124 and containing 0.8 wt.% dodecylbenzenesulfonic acid, consisted of various concentrations benzotriazole or s-triazine UV absorbers and compound sterically constrained amine of the present invention. The enamel was coated over the silver metal primer coating by the method described in Example 124, and held hot heat treated for 30 minutes at normal temperature heat treatment 121°C.

Panels coated was placed in weatherometer (Xenon Arc) and determined the time to 50% loss 20°-luster.

The samples stabilized with the compounds of the present invention and OMIM up to 50% loss 20°-luster.

Example 126

Received enamel of thermosetting acrylic resin containing binder, consisting of 70% of monomers such as hydroxyethylacrylate, styrene, Acrylonitrile, butyl acrylate and acrylic acid, and 30% of a melamine resin and an acid catalyst such as p-toluensulfonate acid, dinonylnaphthalenesulfonic acid or dodecylbenzenesulfonic acid. As the substrate used commercially available panel Uniprime size 9,16 cm × 30,48 see These panels were plated silver metal with a primer coating, and then a transparent coating enamel. This primer coating stabilized with 1% benzotriazole UV absorber and 1% of the tested compounds sterically constrained amine of the present invention (by weight of solid polymer) and caused by atomization of the panel with the formation of a film thickness of about 0.6-0.8 mil and then dried in the air for three minutes. Then by comminution inflicted transparent coating containing the above-mentioned stabilizers and having a thickness of 1.7 to 2.0 mils, and after 10 minutes of air drying the plate with the coating was subjected to heat treatment for 30 minutes at 121°C. Panel floor room is stabilized by the compounds of the present invention and a UV absorber, had superb save 20°to Shine.

Example 127

Enamel based on water-soluble acrylic melamine had the following composition:

The solid part of the polymer

Sintaksis VSW 6483

(acrylic dispersion from Hoechst) 30

Sintaksis VSW 6484 (50% acrylic

resin in butyldiglycol, Hoechst) 42

Marinal MF 915 (70% melamine

resin in Isobutanol) 25

Marinal MF 927(melamine resin) 3

100

Water-soluble primer coating/clear enamel coating was obtained by applying (spraying) of a commercially available water-soluble silver metal primer coating (from BASF) with a thickness of 0.6-0.8 mil on aluminum panel coated with epoxy primer coating. This material was kept in for five minutes at 80°C, and then were covered with a transparent water-soluble enamel thickness of 1.6-1.8 mil. This system was subjected to heat treatment at 80°C for 10 minutes and then at 140°C for 30 minutes. Before applying a clear coating the dye was added to the test compounds of the present invention and light stabilizers, dissolved in a minimal amount of acetate Basov. Then determined the preservation of the integrity of appearance (DOI) panels.

The samples stabilized with the compounds of the present invention, differed best conservation DOI.

Example 128

Stabilization of varnish based on Tung oil and phenol

For testing commercially available lacquer from Tung oil and phenol (supplied McCloskey) were used panel size 1.27 cm × 20.32 cm × 30.48 cm, made of thuja and having a thin radial sections. One half of each panel was covered with two layers of unstabilized varnish. The other half of the panel was covered with two layers of equal amount of lacquer containing 5 wt.% (by weight of solid resin) of the test stabilizers. After aging for two weeks at ambient temperatures wooden panels were placed on eight months in atmospheric conditions at an angle of 45°S. Then measured 60°-the glow of each half of the panel in its upper, middle and lower parts, and the data were averaged in accordance with ASTM D 523. Due to the lack of homogeneity of woody substrates gloss retention of the same varnish varies slightly for each specific panel. Thus, application of unstabilized it is the absence of the test compounds of the present invention.

Panel, stabilized by the compounds of the present invention, was found excellent gloss retention after prolonged exposure.

Example 129

Stabilization of varnish on the basis of aromatic urethane

A sample of commercially available lacquer on the basis of aromatic urethane (Flecto-Varathane #90) was tested by the method described in Example 128. After keeping in atmospheric conditions at an angle of 45°S for five months was determined parameters save 60°-Shine for unstabilized and stabilized portions of the panels.

Panel, stabilized by the compounds of the present invention, was found excellent gloss retention.

Example 130

Stabilization of two white shiny enamel on the basis of polyester and urethane

White polyester composition had the following composition:

Component Part I

Desmophen 670-90 (polietilenglikol, Mobay) 132,4

Titanium dioxide 198,6

Cellosolve 98,9

Sand mill

Desmophen 670-90 94,98

Additive for imparting fluidity 0,28

Tertiary amine 0,015

Cellosolve 332,6

Component II

Panel, stabilized by the compounds of the present invention, was found excellent gloss retention.

Example 131

Stabilization of acrylic alkyd enamel repair paint

Commercially available pigments for acrylic alkyd enamels containing newsplease aluminum pigment and light blue pigment, stabilized benzotriazole UV absorber and the test compound sterically constrained amine of the present invention, and then were applied to Bonderite panels is th temperature for curing and kept under atmospheric conditions at an angle of 45°S for eight months. Then measured 20° Shine exposed panels.

Panel, stabilized by the compounds of the present invention, was found excellent gloss retention.

Example 132

Stabilization alkyd enamel oil-based

Alkyd enamel oil-based, pigmentirovannuyu newsplease aluminum pigment and light blue pigment, stabilized benzotriazole UV absorber and the test compound sterically constrained amine of the present invention, and then put the panel from cold-rolled steel, which were pre-coated with epoxy primer coating. After keeping at room temperature for two weeks, the panel was placed on 840 hours in weatherometer (Xenon Arc) to create accelerated weather. Before and after exposure was determined value 20°-Shine panels.

Panel, stabilized by the compounds of the present invention, it was discovered the wonderful preservation of luster.

Example 133

Composition for coatings applied by the electroplating method

A typical composition is applied by electro-deposition, obtained by adding to the flask dipyridamolee catalyst type dimethylbenzylamine in xylene and the temperature was maintained for two hours at 143°C. Then measured the epoxy mass (weight epoxy resin containing one epoxy group, EM), and was added prior crosslinking agent containing 2,4-colorvision, trimethylolpropane blocked by alcohol, after which the temperature was lowered to 100°C. Then the remaining epoxypropyl blocked two different secondary amines, namely dicaterino Diethylenetriamine and methylethanolamine in phenylalaline. The temperature was maintained at 110°C for one hour and added the stapling hexamethylenediisocyanate blocked by alcohol. The temperature was maintained at about 100°C for 30 minutes, and the polymer mixture was added to deionized water, surfactant and lactic acid, resulting in the obtained polymer emulsion.

This polymer emulsion was added steric difficulty amine compound of the present invention, as well as epoxy resin, carbon soot, catalyst oxide dibutylamine, titanium dioxide, silicate of lead, water and UV absorber. After dispersion using a sand mill to obtain a fine powder mixture was introduced into a bath of water for deposition on use is for E-coating thickness 23-30 μm and utverjdali for 20 minutes at a temperature 176-201°C. On top of this coating was applied pigmented polymer layer thickness 20-51 μm using acrylic composition for coating in an organic solvent, pigments and UV absorber. Then the panel with the coating was subjected to heat treatment at 121-129°C for curing pigmented layer.

Then these panels were placed on four months in ambient conditions. Panel containing compounds based on sterically constrained amine of the present invention, in particular, with the use of UV absorber was found superior resistance to delamination of the E-layer from the metal substrate.

Example 134

Compositions for wear-resistant coatings

Isopropanolamine a solution of 50% (by weight) of 1,6-hexandiol, 10% 3-methacryloxypropyltrimethoxysilane and 40% kolloidales silicon dioxide (in the form of a 34% aqueous dispersion) was subjected to vacuum evaporation to remove volatile substances and combined with the connection sterically constrained amine of the present invention, benzotriazole UV absorber and 2,4,6-trimethylbenzoyl-diphenylphosphinyl photoinitiation. These compositions did not gelation during storage.

The above composition was applied waliou at 43°with the linear speed of 610 cm/min These compositions were utverjdali obtaining colorless and optically transparent coating on top of the polycarbonate substrate.

These coatings subjected to the test for abrasion on the device Taber (ASTM D 1044), had to wear.

The samples were also subjected to a test for accelerated aging using weatherometer (Atlas Ci65 Xenon Arc Weather-Ometer). The results showed that the coatings containing compounds are sterically constrained amine of the present invention, have excellent resistance to yellowing and clouding.

Example 135

The coating on the polycarbonate

Two-component coating based on polyester and urethane stabilized by adding compounds sterically constrained amine of the present invention. Polyester polyol containing solid substances (Desmophen 670-80, Bayer) were made with polymer-based isocyanate (Desmodue N-3390, Bayer). The catalyzed coating of 0.015 wt.%. Catalyst - dilaurate dibutylamine.

Plate of a polycarbonate plastic substrate (Hepo) size 4’×6’ covered by a transparent coating with a thickness of approximately 1.5 mils. The coating was applied on the substrate by comminution and sateau weeks at room temperature, each plate is cut into strips measuring 2’×3’ with five duplicates for each composition. Each strip was placed in a vessel with a capacity of 8 ounces with 2 ml of distilled water and tightly closed. All samples were placed in an oven at 54°C. the adhesion Test when applying stroke was carried out for one week, at least two samples duplicates as long as the samples did not peel 5% loss of adhesion) or after 40 days.

Samples containing compounds sterically constrained amine of the present invention, had excellent resistance to delamination.

Example 136

Chromogenic photographic layers was obtained by manual application of a gelatin emulsion containing silver bromide, yellow krasnobryzhyy component and an additive, polyethylene coated paper.

The composition of this layer are given in table.4, where quantities are given in mg/m

These layers were dried for 7 days in a ventilated room. The dried samples Paladino exhibited white light with the stages of exposure to 0.3 logE. These samples showed the way R for color negative photo paper Agfa-Gevaert in accordance with manufacturers ' recommendations.

After exposure and processing was measured by the decrease of the density yellow pigment the s light energy was 60 kJ/cm2. UV filter consisted of emulsion deposited on a transparent polyester substrate so that the layer contained 1 g/m2Tinu-vin B976®. The temperature was 43°C and relative humidity of 50%. Determined the loss of density from the density in the blue range, equal to 1. When this is desired is a low D value (see table.5).

These results showed that the additive of the present invention improves the resistance to light yellow photographic layers.

Example 137

Chromogenic photographic layers was obtained by manual application of a gelatin emulsion containing silver bromide, yellow krasnobryzhyy component and an additive, polyethylene coated paper.

The composition of this layer are given in table.6, where the amounts are given in mg/m:

These layers were dried for 7 days in a ventilated room.

The dried samples Paladino exhibited white light with the stages of exposure to 0.3 logE. These samples showed the way R for color negative photo paper Agfa-Gevaert in accordance with manufacturers ' recommendations.

After exposure and processing was measured by the decrease of the density of the yellow dye in the and, starting from the density in the blue range, equal to 1. When this is desired is a low D value (see table.7).

These results showed that the additive of the present invention improves the resistance to light yellow photographic layers.

In Examples 136 and 137 were used components are listed in the end of the description.

X is a compound of Example 30.

Y is a compound of Example 73.

Z is a compound of Example 16A.

Example 138

Stabilization of thermoplastic polyolefins

Molded samples for testing were obtained and tested as described in Example 76 except that the sample NOR-2 instead of N,N-dialkylhydroxylamines stabilizer used amine oxide, Genox EP. Composition of light stabilizers containing a mixture of components specified in Example 76, the amine oxide and compounds of the present invention, had good ability to stabilize against adverse effects of UV radiation.

Example 139

Painted thermoplastic polyolefins

Molded samples for testing were obtained and tested as op is used, the amine oxide, Genox EP. Composition of light stabilizers containing a mixture of components specified in Example 77, the amine oxide and compounds of the present invention, had good adesa dye compared with the composition containing the closely related known compound, in which no hydroxyl group.

Example 140

Stabilization of polypropylene fiber

Samples of the fibers were obtained and tested as described in Example 79, except that in the sample NOR-2 instead of N,N-dialkylhydroxylamines stabilizer used amine oxide, Genox EP. Composition of light stabilizers containing a mixture of components specified in Example 79, the amine oxide and compounds of the present invention, had good ability to stabilize against adverse effects of UV exposure.

Example 141

Stabilization of the powder clear coating based on glycidylmethacrylate

One of the major new coating technologies that can be used to meet the increasingly stringent requirements in respect of pollutant VOC solvents in okruzaushuyu environment, is the use of powder coatings. This item is for the application of the top finishes on cars, for coating on gardening tools and for the protection caps of the car wheels. For optimal introduction and stability during storage stabilizers used in powder coating, should be firm with a moderate melting temperature (~100°C), non-volatile and thermally stable under normal temperature heat treatment, powder coating (140-180°C).

In this test before the introduction of stabilizers based on sterically constrained amine to prepare a mixture of commercially available polymer-based GMA powder coatings, UV absorber and additions to make takuseshi by co-extrusion at 145°C. Then the test light stabilizers based on sterically constrained amine was injected in portions of this mixture together with commercially available 1,12-dodecanol acid, a crosslinking polymer. The final mixture was extrudible at 100°C, after which the extrudate was crushed on ultra centrifugal mill and cyclone separator for powder and then sieved. These powders were applied by electrostatic deposition on the ground floor with the formation of a film thickness of 60 microns. This coating was utverjdali for 30 minutes at 160°C.

Panel, stabilized by the compounds of the present invention, was found excellent gloss retention.

Example 142

Stabilization urethane alkyd polymer, a modified oil additive, for use on wood

The test light stabilizers based on sterically constrained amine was introduced into commercially available soluble in the solvent urethane alkyd resin McWhorter 43-4355. All compositions have also introduced 2-hydroxybenzotriazole UV absorber. Light stabilizers based on sterically constrained amine were added at equivalent levels of piperidine. After mixing on a Board of white pine was applied by brush transparent coating. Each Board was divided into 8 sections, separated from each other by grooves depth 1/8’, which was flooded by forming a transparent varnish, after which the top surface and the sides were covered with white chlorinated paint composition. Stable coating was applied to the boards in the triple duplicate three coatings so that on each Board were present control composition for comparison. Wood samples were left for 1 nedenini, stable compounds of the present invention, was found excellent color retention, resistance to cracking and visually observed the preservation of light.

Example 143

Pre-molded film of the applied layers on plastic surfaces

The present invention also relates to protective and decorative films, which were pre-formed and then deposited on the substrate by transfer of dry paint. These films consisted of one decorative layer, which was applied to a sheet substrate, and then put the layers on the adhesive thermoformed sheet-based. Then this sheet substrate was separated from the opposite side of the film, revealing the decorative layer. Then layered film/sheet-based subjected to molding by heating with obtaining three-dimensional form. In addition, these films can also be composed of multiple layers, where, for example, thermoplastic moulded transparent coating applied to a sheet substrate, and then utverjdayut with the formation of the optically transparent film. After that, open front surface, apply a clear finish and utverjdayut, resulting get painted plant layers on thermoformed sheet based, as explained above. The sheet substrate is removed as described above, after which the composite transparent coating/pigmented coating/base" put hot processing, as described above.

The polymer resin used for the above purposes, shall be thermoplastic and can be a fluoropolymer/acrylic blend.

1. 1-alkoxy-substituted sterically hindered amine, where alkoxygroup substituted one, two or three hydroxy groups, as shown in formulas (1) to(28), or its derivative having the formula (29) or (30)

where G1and G2independently represent alkyl with 1-4 carbon atoms or G1and G2taken together, represent pentamethylene;

E represents a straight or branched alkylene with 1-18 carbon atoms; cycloalkyl with 5-18 carbon atoms; cycloalkenyl with 5-18 carbon atoms; straight the alkyl groups with 1-4 carbon atoms;

b = 1, 2, or 3 with the proviso that b cannot exceed the number of carbon atoms in E or L, and if b = 2 or 3, each hydroxyl group is linked to other carbon atoms, F or L; and two sterically difficult amine group, usually, but not always, linked to other carbon atoms of L;

in each of formulas (1) to(15)

m = 0 or 1;

R1represents hydrogen, hydroxyl or hydroxymethyl;

R2represents hydrogen, alkyl with 1-12 carbon atoms or alkenyl with 2-12 carbon atoms;

n = 1-4;

if n = 1, R3represents alkyl with 1-18 carbon atoms, alkoxycarbonylmethyl with 4-18 carbon atoms, alkenyl with 2-18 carbon atoms, glycidyl, 2,3-dihydroxypropyl, 2-hydroxy or 2-(hydroxymethyl)substituted alkyl with 3 to 12 carbon atoms, where the specified alkyl interrupted by an oxygen atom acyl radical of aliphatic or unsaturated aliphatic carboxylic or carbamino acid containing 2-18 carbon atoms, acyl radicals of cycloaliphatic carboxylic or carbamino acid containing 7-12 carbon atoms, or acyl radical of an aromatic acid containing 7 to 15 carbon atoms;

if n = 2, R3p is efficiency dicarboxylic or dicarbamate acid, containing 2-18 carbon atoms, a divalent acyl radical cycloaliphatic dicarboxylic or dicarbamate acid containing 7-12 carbon atoms, or a divalent acyl radical of an aromatic dicarboxylic acid containing 8 to 15 carbon atoms;

if n = 3, R3represents a trivalent acyl radical of aliphatic or unsaturated aliphatic tricarboxylic acid containing 6 to 18 carbon atoms, or a trivalent acyl radical of an aromatic tricarboxylic acid containing 9 to 15 carbon atoms;

if n = 4, R3represents a tetravalent acyl radical of aliphatic, unsaturated aliphatic or cycloaliphatic tricarboxylic acid or tricarballylic acid containing 6-18 carbon atoms, or a tetravalent acyl radical of an aromatic tricarboxylic acid or tricarballylic acid containing 9 to 18 carbon atoms; or R3represents a tetravalent acyl radical of Tris(allylcarbamate acid), a derivative of cyanuric acid containing 12 to 24 carbon atoms;

p = 1-3, R4represents hydrogen, alkyl with 1-18 carbon atoms or acyl with 2 to 6 carbon atoms;

if R =TES aliphatic carboxylic or carbamino acid, containing 2-18 carbon atoms, acyl radicals of cycloaliphatic carboxylic or carbamino acid containing 7 to 12 carbon atoms, an acyl radical of an aromatic carboxylic acid containing 7 to 15 carbon atoms, or R4and R5taken together, represent -(CH2)5CO-, phthaloyl or divalent acyl radical of maleic acid;

if p = 2, R5is alkylene with 2-12 carbon atoms, a divalent acyl radical of aliphatic or unsaturated aliphatic dicarboxylic or dicarbamate acid containing 2-18 carbon atoms, a divalent acyl radical cycloaliphatic dicarboxylic or dicarbamate acid containing 7-12 carbon atoms, or a divalent acyl radical of an aromatic dicarboxylic acid containing 8 to 15 carbon atoms;

if p = 3, R5represents a trivalent acyl radical of aliphatic or unsaturated aliphatic tricarboxylic acid containing 6 to 18 carbon atoms, or a trivalent acyl radical of an aromatic tricarboxylic acid containing 9 to 15 carbon atoms;

if n = 1, R6represents alkoxy with 1-18 carbon atoms, alkenylacyl with 2-18 at what about the R6is alkylenedioxy with 2-18 carbon atoms, alkenylamine with 2-18 carbon atoms, -NH-alkylene-NH - with 2-18 carbon atoms, or-N(alkyl)-alkylene-N(alkyl)- with 2-18 carbon atoms, or R6is 4-methyl-1,3-phenylendiamine,

if n = 3, R6represents a trivalent alkoxyalkyl saturated or unsaturated aliphatic triol containing 3-18 carbon atoms;

if n = 4, R6represents a tetravalent alkoxyalkyl saturated or unsaturated aliphatic tetraol containing 4-18 carbon atoms;

R7and R8independently represent chlorine; alkoxy with 1-18 carbon atoms; -O-T1; the amino group, substituted 2-hydroxyethyl; -NH(alkyl with 1-18 carbon atoms; -N(alkyl)T1where the alkyl group has 1-18 carbon atoms; or-N(alkyl)2with 2-36 carbon atoms;

R9represents a divalent oxygen atom, or R9represents a divalent nitrogen atom substituted by hydrogen, alkyl with 1-12 carbon atoms, or T1

R10represents hydrogen or methyl;

q = 2-8;

R11and R12independently represent hydrogen or a group of T2,

cycloalkenyl with 5-8 carbon atoms; alkenyl with 2-12 carbon atoms; glycidyl; allyloxy; straight or branched hydroxyalkyl with 1-4 carbon atoms; or silyl or silyloxy, three times independently substituted by hydrogen, by phenyl, by alkyl with 1-4 carbon atoms or alkoxy with 1-4 carbon atoms;

R14represents hydrogen or silyl, three times independently substituted by hydrogen, by phenyl, by alkyl with 1-4 carbon atoms or alkoxy with 1-4 carbon atoms;

d = 0 or 1;

h = 0-4;

k = 0-5;

x = 3-6;

y = 1-10;

z is an integer such that the compound has a molecular weight of from 1000 to 4000 A. e;

R15is morpholino, piperidino, 1-piperazinyl, alkylamino with 1-8 carbon atoms, especially branched, alkylamino with 3-8 carbon atoms, such as tert-octylamine, -N(alkyl)T1where alkyl with 1-8 carbon atoms substituted T1; or-N(alkyl)2from 2-16 carbon atoms;

R16represents hydrogen, acyl with 2 to 4 carbon atoms; carbarnoyl, substituted by alkyl with 1-4 ATO is R15provided that two Deputy R15can be various;

R17is chlorine, amino substituted by alkyl with 1-8 carbon atoms or a substituted T1; -N(alkyl)T1where alkyl has 1-8 carbon atoms; -N(alkyl)2from 2-16 carbon atoms; or a group of T3;

R18represents hydrogen; acyl with 2 to 4 carbon atoms; carbarnoyl, substituted by alkyl with 1-4 carbon atoms; s is triazinyl, double-substituted-N(alkyl)2from 2-16 carbon atoms; or s-triazinyl, double-substituted-N(alkyl)T1with 1-8 carbon atoms;

L represents a straight or branched alkylene with 1-18 carbon atoms; cycloalkyl with 5-8 carbon atoms;

cycloalkenyl with 5-8 carbon atoms; albaniles with 3-18 carbon atoms; straight or branched alkylene with 1-4 carbon atoms substituted by phenyl or by phenyl substituted by one or two alkilani with 1-4 carbon atoms;

in formulas (16)-(26) R1, R2, R7, R8, R9, R10, R13, R14, d, h, k, m, q and T1have the same meaning as in formulas(1)-(15);

R19represents hydrogen; alkyl with 1-18 carbon atoms; alkenyl with 2-18 carbon atoms; glycide lcil is interrupted by oxygen; acyl radical of aliphatic or unsaturated aliphatic carboxylic or carbamino acid containing 2-18 carbon atoms; acyl radicals of cycloaliphatic carboxylic or carbamino acid containing 7 to 12 carbon atoms; or an acyl radical of an aromatic acid containing 7 to 15 carbon atoms;

R20is alkylene with 2-18 carbon atoms; divalent acyl radical of aliphatic or unsaturated aliphatic dicarboxylic or dicarbamate acid containing 2-18 carbon atoms; divalent acyl radical cycloaliphatic dicarboxylic or dicarbamate acid containing 7 to 12 carbon atoms; or a divalent acyl radical of an aromatic dicarboxylic acid containing 8 to 15 carbon atoms;

R21represents hydrogen, alkyl with 1-18 carbon atoms or acyl with 2 to 6 carbon atoms;

R22represents hydrogen; alkyl with 1-18 carbon atoms; acyl radical of aliphatic or unsaturated aliphatic carboxylic or carbamino acid containing. 2-18 carbon atoms; acyl radicals of cycloaliphatic carboxylic or carbamino acid containing 7 to 12 carbon atoms; acyl radical aroma is ut -(CH2)5CO-, phthaloyl or divalent acyl radical of maleic acid;

R23represents hydrogen, alkyl with 1-4 carbon atoms or acyl with 2 to 6 carbon atoms;

R24is alkylene with 2-18 carbon atoms; divalent acyl radical of aliphatic or unsaturated aliphatic dicarboxylic or dicarbamate acid containing 2-18 carbon atoms; divalent acyl radical cycloaliphatic dicarboxylic or dicarbamate acid containing 7 to 12 carbon atoms; or a divalent acyl radical of an aromatic dicarboxylic acid containing 8 to 15 carbon atoms;

R25represents alkoxy with 1-18 carbon atoms; alkenylacyl with 2-18 carbon atoms; -NH-alkyl with 1-18 carbon atoms or-N(alkyl)2with 2-36 carbon atoms;

R26is alkylenedioxy with 2-18 carbon atoms; alkenylamine with 2-18 carbon atoms; -NH-alkylene-NH - with 2-18 carbon atoms or-N(alkyl)-alkylene-N(alkyl)- with 3-18 carbon atoms;

in formulas (29) and (30) G is centered on the carbon biradical, derived from primary, secondary or tertiary alcohol G-OH, where z is defined above, and G represents a straight or does is Yes; albaniles with 3-18 carbon atoms; straight or branched alkylene with 1-4 carbon atoms substituted by phenyl or by phenyl substituted by one or two alkilani with 1-4 carbon atoms, provided that in the formula (29), the following radicals are sterically obstructed amines can be focused on the type of "head to head" or "head to tail";

T4represents hydrogen or T4is

R27represents a straight or branched alkylene with 1-18 carbon atoms, cycloalkyl or cycloalkenyl with 5-8 carbon atoms, phenylene or-NH-alkylene-NH - with 2-18 carbon atoms, including 5-amino-1-aminomethyl-1,3 .3m-trimethylcyclohexane and-NH-xylylene-NH-;

R28represents alkyl with 1-4 carbon atoms;

or

R29represents straight or branched alkyl or-NH-alkyl with 1-18 carbon atoms or-NH-cycloalkyl with 5-8 carbon atoms,

and, in addition, provided that in the formulae (1) and (2) if b = 1, then E is not the stands, ethyl, 2-propylene or 2-methyl-2-propylene, as well as in the formula (2), if for every G1and G2represents methyl, the group-E-(OH)bis not 1-phenyl-2-hydroxyethyl.

if b = 1, then E-HE and L-OH are respectively centered on the carbon radical formed preferably from 2-methyl-2-propanol, 2-propanol, 2,2-dimethyl-1-propanol, 2-methyl-2-butanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-nonanol, 1-decanol, 1-dodecanol, 1-octadecanol, 2-butanol, 2-pentanol, 2-ethyl-1-hexanol, cyclohexanol, cyclooctanol, allyl alcohol, ventilago alcohol or 1-phenyl-1-ethanol, most preferably E-HE and L-OH are formed from 2-methyl-2-propanol or cyclohexanol;

if b = 2, then E-HE and L-OH are respectively centered on the carbon radical or biradical, preferably formed from 1,2-ethanediol, 1,2-propane diol, 1,3-propane diol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propane diol, 1,2-cyclohexanediol, 1,3-cyclohexanediol or 1,4-cyclohexanediol;

if b = 3, then E-HE and L-OH are respectively centered on the carbon radical or biradical formed from glycerol, 1,1,1-Tris(hydroxymethyl)methane, 2-ethyl-2-(hydroxymethyl)-1,3-propane diol, 1,2,4-butanetriol or 1,2,6-hexanetriol;

in formulas (29) and (30), -G-O formed from ethanol, ventilago alcohol, cyclohexanol and hydroxymethyl, a R2represents hydrogen; or m = 1, R1is hydroxy or hydroxymethyl, a R2represents hydrogen, methyl or ethyl;

in the formula (5) R2represents hydrogen or dodecyl;

in the formula (6) n = 1-3, and, if n = 1, R3represents allyl, glycidyl, acryloyl, methacryloyl, octadecanoyl, hexadecanoyl, deletion, methoxycarbonylpropionyl, ethoxycarbonylbutyl, methoxycarbonylmethyl or methoxycarbonylamino; or if n = 2, R3is succinyl, glutaryl, adipoyl, sebacoyl, 1,6-hexadecanol, CIS - or TRANS-5-carbarnoyl-1-(carbamoylmethyl)-1,3 .3m-trimethylcyclohexane or toluene-2,4-decarbamoyl; or, if n = 3, R3is 1,3,5-Tris(6-carbamoylmethyl)-2,4,6-trioxo-8-triazine;

in the formula (7) p = 1 or 2, and if p = 1, R4represents hydrogen, a R5is butyl; or R4and R5taken together, represent a divalent acyl radical of maleic acid; or if p = 2, R4is hydrogen or acetyl, a R5is the 1.6-hexanediol;

in the formula (8) n = 1 or 2, and if n = 1, R6is ethoxy, 6-methyl-1-heptyloxy, ethylamino, butylamino or octylamine; or, if n = 2, then the diamino;

in the formula (9) R7and R8independently represent chlorine, octylamine, tert-octylamine or amino group, substituted T1and ethyl, bootrom or dodecyl; a R9represents a divalent nitrogen atom substituted by ethyl, bootrom or dodecyl;

in the formula (10) q = 2, 4 or 6, R7represents chlorine, octylamine, octadecylamine or amino group, substituted T1and ethyl, bootrom or dodecyl; a R10represents hydrogen;

in the formula (11) n = 3, p = 2, R2is ethyl, butyl or dodecyl; and one of R11or R12is T2and the other represents hydrogen;

in the formula (12) k = 3, R9represents a divalent oxygen atom or a divalent nitrogen atom substituted by ethyl, bootrom or dodecyl, R13represents hydrogen or methyl, and if d = 0, then x = 5 or 6, and if d = 1, then x = 3 or 4;

in the formula (13) d = 0 or 1; h = 0-2; k = 0 or 3; y = 1 to 8; R9represents a divalent oxygen atom or a divalent nitrogen atom substituted by ethyl, bootrom or dodecyl; R13represents hydrogen, methyl, ethyl, methoxy or ethoxy; a R14is hydrogen or trimethylsilyl;

in the formula (14) R9is douglasa mass of the compound is 1500-3000.E.;

in the formula (15) q = 6 and y = 1-7, R15represents tert-octylamine; morpholino; amino, substituted T1and bootrom, which may also be denoted as T1-butylamino; R16represents hydrogen; acetyl; ethylcarbitol; 2,4-bis(dibutylamino)-s-triazine; 2,4-bis(diethylamino)-s-triazinyl; s-triazinyl, double-substituted T1-butylamino; or s-triazinyl, once replaced diethylamino or dibutylamino and once replaced with T1-butylamino; R17is dibutylamino; diethylamino; T1-butylamino or R17is T3where R18represents acetyl or ethylcarbitol;

in the formula (17) m = 0, R1represents hydrogen or hydroxymethyl, a R2represents hydrogen; or m = 1, R1represents hydroxy or hydroxymethyl and R2represents hydrogen or methyl;

in the formula (19) R2represents hydrogen or dodecyl;

in the formula (20) R19represents hydrogen, allyl, acryloyl, methacryloyl, octadecanoyl or hexadecanoyl;

in the formula (21) R20is succinyl, glutaryl, adipoyl, sebacoyl, 1,6-hexadecanoyl or CIS - or TRANS-5-carbarnoyl-1-(carbamoylmethyl)-1,3 .3m-trimethylcyclohexane;

22taken together, represent a divalent acyl radical of maleic acid;

in the formula (23) R23is hydrogen or acetyl, a R24represents ethylene or hexamethylene;

in the formula (24) R25is ethoxy, 6-methyl-1-heptyloxy, ethylamino, butylamino or octylamine;

in the formula (25) R26represents 1,2-ethyoxy, 1,4-butanedione, ethylendiamine or hexamethylenediamine;

in the formula (26) R7and R8independently represent chlorine, octylamine, tert-octylamine, octadecylamine, T1-ethylamino, T1-butylamino or T1-dodecylamino, a R9represents a divalent nitrogen atom substituted by ethyl, bootrom or dodecyl;

in the formula (27) q = 2, 4 or 6, R7represents chlorine, octylamine, octadecylamine, T1-ethylamino, T1-butylamino or T1-dodecylamino, a R10represents hydrogen;

in the formula (28) d = 0 or 1; h = 0-2; k = 0 or 3, R9represents a divalent oxygen atom or a divalent nitrogen atom substituted by ethyl, bootrom or dodecyl, R13represents hydrogen, methyl, ethyl, methoxy or ethoxy, a R14is hydrogen or trimethylsilyl;

B1-aminomethyl-1,3 .3m-trimethylcyclohexane; z is an integer such that the molecular weight of the compound is 1500-3000.E.; R28represents methyl or ethyl, a G is ethylene, 1,2-cyclohexanediyl, 1,3-cyclohexanediyl, 1,4-cyclohexanediyl,

-CH(C2H5)CH2- or-CH2C(CH3)2-;

in the formula (30) R29is pentadecyl, heptadecyl, butylamino or cyclohexylamino.

3. Connection on p. 1, where in formula (6), if n = 1, R3is acryloyl, methacryloyl, glycidyl, octadecanoyl, hexadecanoyl, methoxycarbonylpropionyl, ethoxycarbonylbutyl, methoxycarbonylmethyl or methoxycarbonylamino; or if n = 2, R3is succinyl, glutaryl, adipoyl, sebacoyl, 1,6-hexadecanol, CIS - or TRANS-5-carbarnoyl-1-(carbamoylmethyl)-1,3 .3m-trimethylcyclohexane or toluene-2,4-decarbamoyl; or if n = 3, R3is 1,3,5-Tris(6-carbamoylmethyl)-2,4,6-trioxo-s-triazine;

in the formula (7) p = 1 or 2, and if p = 1, R4represents hydrogen, a R5represents hydrogen or butyl; and if p = 2, R4represents hydrogen, a R5is the 1.6-hexanediol;

in the formula (9) R7represents chlorine, octylamine or T1

in the formula (10) q = 6, R7is T1-butylamino, a R10represents hydrogen;

in the formula (11) n = 3, p = 2, and one of R11or R12is T2and the other represents hydrogen;

in the formula (12) k = 3, R9represents a divalent oxygen atom, R13represents hydrogen or methyl, and d = 0, x = 5 or 6, and if d = 1, then x = 3 or 4;

in the formula (13) d = 0 or 1, h = 0-2, k = 0 or 3, y = 1-8, R9represents a divalent oxygen atom, R13represents hydrogen, methyl, ethyl, methoxy or ethoxy, a R14is hydrogen or trimethylsilyl;

in the formula (15) q = 6, y = 1-7, R15is T1-butylamino; R16represents hydrogen, acetyl, ethylcarbitol, 2,4-bis(dibutylamino)-s-triazinyl, 2,4-bis(diethylamino)-s-triazinyl, s-triazinyl, double-substituted T1-butylamino, or s-triazinyl, once replaced diethylamino or dibutylamino and once T1-butylamino; R17is dibutylamino, diethylamino, T1-butylamino; or R17is T3where R18represents acetyl or ethylcarbitol;

in the formula (20) R19represents hydrogen, octadecanoyl or Gil;

in the formula (23) R23represents hydrogen, a R24is hexamethylene;

in the formula (26) R7represents chlorine, octylamine or T1-butylamino, R8represents chlorine or T1-butylamino, a R9represents a divalent nitrogen atom substituted by bootrom;

in the formula (27) q = 6, R7is T1-butylamino, a R9represents a divalent nitrogen atom substituted by bootrom;

in the formula (29) R27is ethylene, trimethylene, tetramethylene or octamethylene; z is an integer such that the molecular weight of the compound is 1500-2000 g/mol; a R28is methyl;

in the formula (30) R29is pentadecyl or heptadecyl.

4. Connection on p. 1, where G1and G2, each of which represents methyl, F-IT, L-OH and-G-O - in the compounds of formulas (1) to(30), formed from 2-methyl-2-propanol or cyclohexanol.

5. Connection on p. 1, where in formula (6), if n = 1, R3is acryloyl, methacryloyl, glycidyl, octadecanoyl, hexadecanoyl, methoxycarbonylpropionyl or ethoxycarbonylbutyl; or if n = 2, R3is succinyl, glutaryl, adipoyl or sebacoyl;

5is hexamethylene;

in the formula (9), where R7represents chlorine, octylamine or T1-butylamino, R8is T1-butylamino, a R9represents a divalent nitrogen atom substituted by bootrom;

in the formula (10) where q = 6, R7is T1-butylamino, and R10represents hydrogen;

in the formula (11), where n = 3, p = 2 and one of R11or R12is T2and the other represents hydrogen;

in the formula (12), where d = 1, k = 3, x = 3 or 4, R9represents a divalent oxygen atom, a R13is methyl;

in the formula (13), where k = 3, y = 4 to 8, R9represents a divalent oxygen atom, R13represents hydrogen or methyl, d, and h = 0, R14represents hydrogen; or d = 1 and h = 0, and R14is trimethylsilyl;

in the formula (14) m = 0, R9represents a divalent oxygen atom; R10represents hydrogen or methyl, a z is an integer such that the molecular weight of the compound is 1500-3000.E.;

in the formula (15), where q = 6, y is 1-7, R15is T1-butylamino; R16represents hydrogen, acetyl, ethylcarbitol, 2,4-bis(dibutylamino)-s-Tr is l, once replaced diethylamino or dibutylamino and once T1-butylamino; R17is dibutylamino, diethylamino or T3where R18represents acetyl or ethylcarbitol;

in the formula (20) R19represents hydrogen, octadecanoyl or hexadecanoyl;

in the formula (21) R20is succinyl, glutaryl, adipoyl or sebacoyl;

in the formula (30), R29is heptadecyl.

6. Connection on p. 1, which is

(a) bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl)]sebacate;

(b) a mixture of bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]glutarate and bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl)]adipate;

(c) 1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine;

(d) bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl)]adipate;

(e) bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl)]glutarate;

(f) bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl)]succinate;

(d) a mixture of bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]glutarate and bis[1-(2-hydroxy-2-methylprop is hydroxy)-2-octadecanoyloxy-2-methylpropan;

(i) 1-(2-hydroxy-2-methylpropoxy)-4-[9-(methoxycarbonyl)-nonanoate]-2,2,6,6-tetramethylpiperidine;

(j) 1-(2-hydroxy-2-methylpropoxy)-4-[5-(methoxycarbonyl)-pentanoate]-2,2,6,6-tetramethylpiperidine;

(k) 1-(2-hydroxy-2-methylpropoxy)-4-[3-(methoxycarbonyl)-propionyloxy]-2,2,6,6-tetramethylpiperidine;

(l) 1-(2-hydroxy-2-methylpropoxy)-4-[4-(methoxycarbonyl)-butyryloxy]-2,2,6,6-tetramethylpiperidine;

(m) the condensation products of 4-hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine with hexamethylenediisocyanate-terminated methoxy group;

(n) the condensation products of 4-hydroxy-1-(2-hydroxyethoxy)-2,2,6,6-tetramethylpiperidine and hexamethylenediisocyanate-terminated methoxy group;

(a) the condensation products of 4-hydroxy-1-(2-hydroxyphenoxy)-2,2,6,6-tetramethylpiperidine with hexamethylenediisocyanate-terminated methoxy group;

(R) 1-(2-hydroxy-2-methylpropoxy)-4-hexadecanoate-2,2,6,6-tetramethylpiperidine;

(q) 1-(4-hexadecanoate-2,2,6,6-tetramethylpiperidine-1 yloxy)-2-hexadecanoyl-2-methylpropan;

(r) 1-(2-hydroxy-2-methylpropoxy)-4-[5-(methoxycarbonyl)-pentanoate]-2,2,6,6-tetramethylpiperidine, 1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yloxy]carbonylmethyl}-2,4,6-trioxo-s-triazine;

(t) the reaction product 4-hydroxy-1-oxyl-2,2,6,6-tetramethyl-piperidine with 2-methyl-2-butanol;

(u) the reaction product of transesterification of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine with 2-methyl-2-butanol and metalseadramon or

(v) a mixture of 1-(2-hydroxy-2-methylpropoxy)-4-[5-methoxy-carbonyl)pentanoate]-2,2,6,6-tetramethylpiperidine and 1-(2-hydroxy-2-methylpropoxy)-4-[4-methoxycarbonyl)butyryloxy]-2,2,6,6-tetramethylpiperidine.

7. Composition that includes (a) an organic polymer or registriruemiy material exposed to the adverse effects of heat, oxygen and light, and (b) an effective stabilizing amount of one or more compounds selected from the compounds of formulas (1) to(30) under item 1.

8. The composition according to p. 7, where component (a) is a thermoplastic organic polymer binder for coatings, color-forming photographic material or ink for printing.

9. The composition according to p. 7, which further contains a component selected from solvents, pigments, dyes, plasticizers, antioxidants, thixotropic agents, leveling tools, additional light stabilizers, passivation metal, metal oxides, fosfororganicheskimi.

10. The composition according to p. 9 containing the absorber of UV radiation, selected from compounds of the class of 2-(hydroxyphenyl)-2H-benzotriazole, 4-hydroxybenzoate, 2-hydroxybenzophenones, oxalanilide, 2-hydroxyphenyl-s-triazines or mixtures thereof.

11. The composition according to p. 7, containing from 0.01 to 10 wt.% the stabilizer component (b) based on the weight of component (a).

12. Method of stabilizing an organic polymer or the recording material to protect them from damage, arising under the action of light, oxygen and/or heat, providing added to the specified material or application of this material at least one compound of the formulas (1) to(30) under item 1.

13. The stabilizer is an organic polymer or the recording material to protect them from damage, arising under the action of light, oxygen and/or heat, representing a compound of formula (1) to(30) under item 1.

14. The method of obtaining the compounds of formula IV

where G1and G2independently represent alkyl with 1-4 carbon atoms or G1and G2taken together, represent pentamethylene;

T represents a divalent organic radical, necessary for the ski difficult amine, replaced with G1and G2;

E is (b+1)-valent alkalinity radical with 2-18 carbon atoms; alkenylamine radical with 3-19 carbon atoms; cycloalkenyl radical with 5-12 carbon atoms; cycloalkanones radical with 5-12 carbon atoms or alkalinity radical with 2 to 4 carbon atoms substituted by phenyl or by phenyl substituted by one or two alkilani with 1-4 carbon atoms; and

b = 1, 2, or 3, provided that b cannot exceed the number of saturated carbon atoms in E, and if b = 2 or 3, each hydroxyl group is linked to another carbon atom in E;

moreover, this method involves the reaction of N-oxyl - constrained amine of formula (V)

with the alcohol of formula VI

in the presence of peroxide or organic hydroperoxide and a catalytic amount of a metal salt or metal-ligand complex.

15. The method according to p. 12, where the compound of formula IV corresponds to the formulas (1) to(28) under item 1.

16. The method according to p. 12, where each of G1and G2is stands, and T represents 2-hydroxy-1,3-PROPANEDIOL or 2-oxo-1,3-propandiol.

17. The method according to p. 12, where the compound E-(OH)bformula VI in the case where b = 1 is the-propandiol, 1,2-butanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propandiol, 2,5-dimethyl-2,5-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol or 1,4-cyclohexanediol, and if b = 3, then the specified compound is 1,1,1-Tris(hydroxymethyl)ethane, 2-ethyl-2-(hydroxymethyl)-1,3-propandiol, 1,2,4-butanetriol or 1,2,6-hexanetriol.

18. The method according to p. 12, where the specified peroxide is hydrogen peroxide or a product of the merger of urea and hydrogen peroxide.

19. The method according to p. 12, where the specified metal is a transition metal selected from metals of groups IVA, VA, VIIA, VIIIA and IB of the Periodic table of elements, and in particular, iron(II), iron(III), copper(I) copper(II), cobalt(II), cobalt(III), manganese(II) manganese(III), vanadium(II), vanadium(III), cerium(III) or titanium(III).

20. The method according to p. 19, where the counterion for the transition metal is chloride, sulfate, acetylacetonate, acetate, citrate, oxalate, nitrate, perchlorate, cyanide, hydroxide, phosphate, pyrophosphate or oxide and may contain an organic ligand selected from 2,2’-dipyridyl, 2,2’:6,2’-terpyridine, 1,10-phenanthroline, ethylenediaminetetraacetic acid, disodium salt ethylenediaminetetraacetic acid, pyridine, pikolinos acid, 2-pyrazinecarboxamide acid, aromatic 2,3-butandiol or triphenylphosphine oxide.

21. The method according to p. 12, where the compound of formula VI is used as a solvent in the ratio of 5-100 mol per 1 mole of nitroxyl group in formula V, where the amount of peroxide or organic hydroperoxide is 1-20 mol per 1 mole of nitroxyl group in formula V; where the amount of metal salt or metal-ligand complex is 0.001 to 0.5 molar equivalents per 1 mole of nitroxyl group in formula V, where acid is not used or is used in a quantity amounting to up to 1 molar equivalent per 1 mole of nitroxyl group in the formula V, and where the method is carried out at a temperature of from 20 to 100°C.

22. The composition according to p. 9, which is a polyolefin composition comprising as an additional component of halogenated flame retardant.

23. The composition according to p. 22, where the specified halogenated flame retardant selected from Tris(3-bromo-2,2-bis(methyl bromide)propyl)phosphate, decabromodiphenylethane, ethylene-bis-tetrabromophthalimide and ethylene-bis(dibromo-norbornenedicarboxylic).

Priority items:

25.02.1999 on PP.1-9, 22;

20.05.1999 on PP.14, 16-21;

25.02.2000 on PP.10-13, 15 and 23.



 

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< / BR>
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< / BR>
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