Substituted benzotriazole, stable compositions and coating system

 

(57) Abstract:

Substituted benzotriazole General formula A

represent an important class of commercial UV absorbers, which are widely used as stabilizers for a wide range of organic substrates from the adverse effects of actinic radiation, the compounds of formula A, where R1- remotemachine or branched alkyl containing from 1 to 24 carbon atoms; R2- remotemachine or branched alkyl containing from 1 to 24 carbon atoms, with the specified alkyl may be substituted by one or more hydroxy-group, or R2-CH2CH2COR5where R5-NH2or or6where R6is hydrogen, alkyl containing from 1 to 24 carbon atoms, or or6-(OCH2CH2)WOH, where W is 1 to 12, or R2-(CH2m-CO-X(Z)P-Y-R15where X and Y - O - Z - alkylen with the number of carbon atoms from 3 to 13, substituted hydroxyl group, R15- group-CO-C(R18)=CH2where R18is hydrogen or methyl, m = 0,1 or 2, and p = 1; R3- alkyl with C8-20, aryl C6-10or represents a radical of the formula B2,

where E is C2-C12-alkylene, C5-C12qi> On the basis of connections And get stabilized composition comprising the polymer is subjected to erosion due to adverse effects of actinic radiation, and coating system, consisting of upper and lower layers of a polymer containing an effective amount of the compound (A). UV Absorbers based on 2-(2-hydroxyphenyl)-2H-benzotriazole, substituted in position 5 benzo-ring sulfoxides or sulfonic group, have shown an increased absorption in colovaginal range (350 nm), which enables these compounds to be particularly effective in protecting polymer systems that are affected by the destruction caused by actinic radiation at a wavelength of 350 nm. 5 C. and 16 h.p. f-crystals, 4 PL.

The present invention relates to substituted benzotriazoles, namely 2-(2-hydroxyphenyl)-2H-benzotriazole, substituted in position 5 Pensacola sulfoxides or sulfonic part, and to stabilized compositions, and coating system containing such compounds.

2-(2-Hydroxyphenyl)-2H-benzotriazole represent a very important class of commercial UV absorbers, which are widely used as stabilizers for a wide range of PRS period in the history of commercial and technical interest in this class of compounds has a number of publications and patents, describing this General class of compounds. Only a few of these references relate to the substituted 2H-benzotriazoles any group containing sulfur.

Patent US 3218332A, 16.11.65 reveals 2H-benzotriazole, substituted in position 5 Pensacola lower alkylsulfonyl (i.e., alkylsulfonyl parts). This reference also describes benzotriazole substituted in the same position a sulfonamide, lower alkylsulfonamides or esters by arylsulfonate. This sulfonamidnuyu substitution is also described in patents US 3766205A, 16.10.73, and 3862087A, 21.01.75.

The proposed compounds and compositions differ from the compounds known in this field. None of these references disclose that the substitution derived 2H-benzotriazole in position 5 Pensacola a sulfoxide or higher alkylsulfonyl radical leads to a significant increase in absorption capacity in the UV region, as well as to the shift of the maximum absorbance values at about 20 nm towards longer wavelength as compared with benzotriazole without 5-thiazolidine. This increased spectral absorption ability in combination with the red shift of the maximum absorbance values towards higher Delany (almost seems) as for example, coating materials, plastics and fibers.

One of the purposes of the invention is to create a 2H-benzotriazoles substituted in 5-position,- SO - or-SO2- radical and characterized by high UV absorption in the long wavelength region as compared with the known benzotriazole.

Another objective of the present invention to provide stabilized compositions and coating systems containing an effective amount of 2H-benzotriazole substituted in 5-position,- SO - or-SO2- radical.

Another object of the invention is to create a 2H-benzotriazoles substituted in 5-position,- SO - or-SO2radicals containing reactive fragments, allowing you to enter them at the expense of chemical bonds in a variety of substrates with making them immobile relative to the substrate.

To achieve these goals according to the invention offers a substituted benzotriazole General formula A

< / BR>
where

R1means remotemachine or branched alkyl containing from 1 to 24 carbon atoms;

R2means remotemachine or branched alkyl containing from 1 to 24 carbon atoms, with the specified alkyl is 5 equal-NH2or6where R6means hydrogen, alkyl containing from 1 to 24 carbon atoms, unsubstituted or substituted by one or more hydroxy-group or OR6means a group -(OCH2CH2)wOH, where w is 1 to 12, or

R2means -(CH2)m-CO-X-(Z)p-Y-R15where X and Y denote-O-, Z - alkylen with the number of carbon atoms from 3 to 12, a substituted hydroxyl group, R15- group-CO-C(R18)=CH2where R18is hydrogen or methyl, m = 0, 1, or 2, and p=1;

R3means alkyl with the number of carbon atoms from 8 to 20, aryl with the number of carbon atoms from 6 to 10, or R3represents a radical of the formula B2< / BR>
< / BR>
where

E means C2-C12alkylene, C5-C12cycloalkyl or C8-C12alkylen, interrupted by cyclohexylphenol,

r = 0 or 1, and L is-SO - or-SO2-.

Preferred substituted benzotriazole the above formula A, where:

R1means remotemachine or branched alkyl with a number of carbon atoms from 1 to 24;

R2means remotemachine or branched alkyl with a number of carbon atoms from 1 to 24; or R2means a group of formula-CH2CH26means -(OCH2CH2)wOH, where w is 1 to 12, or

R2means -(CH2)m-CO-X-(Z)p-Y-R15where X and Y denote-O-, Z - alkylen with the number of carbon atoms from 3 to 12, a substituted hydroxyl group, R15means a group-CO-C(R18)=CH2where R18is hydrogen or methyl, m = 0, 1, or 2, and p=1;

R3means alkyl with the number of carbon atoms from 8 to 20, aryl and the number of carbon atoms from 6 to 10;

L is-SO - or-SO2-.

Particularly preferred substituted benzotriazole formula A, in which:

R1means branched alkyl with a number of carbon atoms from 4 to 8;

R2means remotemachine or branched alkyl with a number of carbon atoms from 1 to 8, substituted by one or more hydroxyl group; or R2means a group of formula-CH2CH2COR5where R5means-NH2or6where R6means hydrogen or alkyl with the number of carbon atoms from 1 to 24, unsubstituted or substituted by one or more hydroxy-group or OR6means -(OCH2CH2)wOH, where w is 1 to 12, or

R2means -(CH2)m-CO-X-(Z)p-Y-R15where X and Y denote-O-, Z 18)=CH2where R18is methyl, m = 2 and p=1; and

R3means phenyl or alkyl with the number of carbon atoms from 8 to 12, and L represents-SO - or-SO2-.

The most preferred substituted benzotriazole formula A, representing a compound selected from the group including:

(a) 5-n-dodecylamino-2-(2-hydroxy-3,5-di-tert. -butylphenyl)-2H-benzotriazole;

(b) 5-n-bezelservices-2-(2-hydroxy-3,5-di-tert. -butylphenyl)-2H-benzotriazole;

(C) 5-n-bezelservices-2-(2-hydroxy-3,5-di-tert. -butylphenyl)-2H-benzotriazole;

(g) 5,5'-sulfonyl-bis[2-(2-hydroxy-3,5-di-tert. -butylphenyl)-2H-benzotriazol];

(d) 5-benzazolyl-2-[2-hydroxy-3-tert.-butyl-5-(--octyloxyphenyl)phenyl]-2H-benzotriazole;

(e) 5-benzazolyl-2-[2-hydroxy-3-tert. -butyl-5-( 3-hydroxypropyl)phenyl]-2H-benzotriazole;

(W) 3-(5-benzazolyl-2H-benzotriazol-2-yl)-5-tert. -butyl-4 - hydroxyvitamin acid;

(C) 3-(5-benzazolyl-2H-benzotriazol-2-yl)-5-tert. -butyl-4 - hydroxyvitamin acid;

(I) an isomeric mixture of 3-[3-(5-benzolsulfonat-2H-benzotriazol-2-yl)-5-tert. -butyl-4 - hydroxyhydrocinnamate] -2-hydroxypropylmethacrylate and 2-[3-(5-benzazolyl-2H-benzotriazol-2-yl)-5-tert. -butyl-4 - hydroxyperoxy(ethylenoxy)carbonylethyl]phenyl}-2H-benzotriazole.

When any one of R1-R6denotes alkyl, such groups mean, for example, methyl, ethyl, isopropyl, n-butyl, isobutyl, sec.-butyl, tert.-butyl, tert. -amyl, 2-ethylhexyl, tert.-octyl, lauryl, tert.-dodecyl, tridecyl, n-hexadecyl, n-octadecyl and eicosyl.

When R3denotes aryl C6-C10such groups include, for example, phenyl, naphthyl or phenyl substituted by alkyl, for example, tolyl and xylyl.

When R6denotes alkyl, substituted by one or more groups-OH, part-OR6may mean -(OCH2CH2)wOH, where w is 1 to 12.

As C3-C12alkylene, substituted hydroxyl group, Z represents 2-hydroxytyramine, 2-hydroxyhexanoate and especially 2-hydroxytrimethylene.

When E denotes, for example, alkylene, values are, for example, ethylene, tetramethylene, hexamethylene, 2-methyl-1,4-tetramethylene, hexamethylene, octamethylene, decamethrin and dodecamethyl. When E denotes cycloalkyl, values are, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclododecyl. When E denotes alkylene, interrupted or terminated cyclohexylphenol, values are reprimed proposed compounds contain free carboxyl portion, in the case when R2denotes-CH2CH2COOR6where R6means hydrogen, alkali metal salts or amines of the above acids are also intended as part of the present invention, and they allow such UV absorbers to be used in aqueous systems due to the increased water solubility of such compounds.

The present invention also relates to stable compositions that contain (a) an organic substance, the polymer being destroyed due to the adverse effects of actinic radiation, and (b) an effective stabilizing amount of substituted benzotriazole General formula A as A UV absorber.

Preferably, the organic substance is a synthetic polymer. Such polymers are especially those containing aromatic part, for example polystyrene, graft copolymers of styrene, for example a copolymer of Acrylonitrile, butadiene and styrene (ABS), polyphenyleneoxides, polyphenylensulfide, polyurethanes, polyisocyanates, aromatic polyesters, aromatic polyamides, polyureas, polyimides, polyamideimides, polysulfones, polyethersulfone, polyetherketone, alkyd resin, amino resin.

Stabilized composition as substituted benzotriazole contains, most preferably, 5-benzazolyl-2-(2-hydroxy-3,5-di-tert. -butylphenyl)-2H-benzotriazole.

Preferred compositions that as a UV absorber contain the following substituted benzotriazole: 5-benzazolyl-2-(2-hydroxy-3,5-di-tert. -butylphenyl)-2H-benzotriazole, 5-benzazolyl-2-[2-hydroxy-3-tert. -butyl-5 -(-octyloxyphenyl)phenyl] -2H-benzotriazole, 5-benzazolyl-2-{ 2-hydroxy-3-tert. -butyl-5-[2 -(-hydroxycut(ethylenoxy)-carbonylethyl] phenyl} -2H-benzotriazole, - hydroxypoly(ethylenoxy)-3-(5-benzosulfonazole-2-yl)-5 - tert.-butyl-4-hydroxyhydrocinnamate or poly(ethyleneoxy)bis[3-(5 - benzosulfonazole-2-yl)-5-tert. -butyl-4-hydroxyhydrocinnamate].

Compositions of particular interest include those which contain (a) an organic substance subject to erosion caused by the adverse effects of actinic radiation, which is a coating system consisting of the lower layer of polymer, which comprises inorganic and/or organic pigment, and the top light layer of polymer, and (b) an effective stabilizing amount of the lower layer of the polymer, or in both layers of the polymer.

Layers of polymer coating systems as substituted benzotriazole preferably contain: 5-benzazolyl-2-(2-hydroxy-3,5-di-tert.-butylphenyl)-2H-benzotriazole, 5-benzazolyl-2-[2-hydroxy-3-tert.-butyl-5 -(- octyloxyphenyl)phenyl]-2H-benzotriazole, 5-benzazolyl-2-{2-hydroxy-3-tert. -butyl-5-[2 -(- hydroxycut(ethylenoxy)-carbonylethyl]phenyl} -2H-benzotriazole, - hydroxypoly(ethylenoxy)-3-(5-benzosulfonazole-2-yl)-5 - tert.-butyl-4-hydroxyhydrocinnamate or poly(ethyleneoxy)bis[3-(5 - benzosulfonazole-2-yl)-5-tert.-butyl-4-hydroxyhydrocinnamate].

Most preferably the coating system contains 5-benzazolyl-2-{2-hydroxy-3-tert.-butyl-5-[2 -(- hydroxycut(ethylenoxy)-carbonylethyl] phenyl}-2H-benzotriazole.

Coating system preferably may further comprise a UV absorber selected from the group consisting of benzophenone, benzotriazole derived cyanacrylate acid, hydroxyaryl-S-triazines, organic Nickel compounds and oxanilide located either in the upper or in the lower layer of the polymer, or both polymer layers.

Preferred UV absorbers are choosing inyl)-2H-benzotriazole, 2-[2-hydroxy-3-tert.-butyl-5 -(- hydroxycut(ethyleneoxy)carbonyl) ethylphenyl]-2H-benzotriazole, 2-[2-hydroxy-3-tert. -butyl-5-(2 - octyloxyphenyl)phenyl] -2H-benzotriazole, 4,4'-distractionmanila, 2,2'-dioctyl-5,5'-di-tert. -butylacrylate, 2,2'-didodecyl-5,5'-di-tert. -butylacrylate, 2-ethoxy-2'-atrocinerea, 2,6-bis(2,4-dimetilfenil)-4-(2-hydroxy - 4-octyloxyphenyl)-S-triazine, 2,6-bis(2,4-dimetilfenil)-4-(2,4 - dihydroxyphenyl)-S-triazine, 2,4-bis(2,4-dihydroxyphenyl)-6-(4 - chlorophenyl)-S-triazine, 2,6-bis(2,4-dimetilfenil)-4-[2-hydroxy-4-(2 - hydroxy-3-dodecyloxyethoxy)phenyl] -S-triazine and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone.

Coating system of interest, preferably additionally contains an effective stabilizing amount of a phenolic antioxidant or in the upper or in the lower layer of the polymer, or both polymer layers, or optionally contains a derivative of difficult amine, or further comprises fosfatnyi or pospolity stabilizer either at the top or bottom, or both layers.

Of particular interest coating system in which organic matter is enamel with a high content of solids used for industrial p is incobrasa finishes under the tree.

When the proposed compounds also contain reactive functional group, such compounds can be chemically bonded or condensation reaction or a radical reaction accession to the polymer substrate. This results in non-migrating, sublimirovannogo stabilizer, UV-absorber. Such reactive functional groups include hydroxy, amino, amido, carboxyl and ethylene unsaturated part.

Thus, the invention also relates to the methacrylate copolymer obtained additive polymerization isomeric mixture of 3-[3-(5-benzazolyl-2H-benzotriazol-2-yl)-5-tert. -butyl-4 - hydroxyhydrocinnamate]-2-hydroxypropylmethacrylate and 2-[3-(5-benzazolyl-2H-benzotriazol-2-yl)-5-tert. -butyl-4 - hydroxyhydrocinnamate] -3-hydroxypropylmethacrylate, and stabilized compositions containing organic polymer substance is subjected to erosion due to adverse actinic radiation, and an effective stabilizing amount of the above methacrylate copolymer.

Various organic substances usable in the present invention, described in more detail below together with the various with ichino favorable.

The proposed compounds are usually obtained by reacting 5-Alojamientos 2H-benzotriazole with aliphatic or aromatic mercaptans in the presence of an aprotic solvent, such as N,N-dimethylformamide, dimethylsulfoxide, etc. at temperatures between 30 and 200oC in the presence of an acid acceptor, such as an oxide, carbonate or hydroxide of alkali or alkaline earth metal. When using dithiol get bis connection. The reaction can be performed in non-polar hydrocarbon solvents, such as xylene or mesitylene, using the aforementioned polar solvents as a co-solvent or in a hydrocarbon solvent under conditions of phase transfer.

Alternative methods of obtaining the proposed connection is to attach 5-mercaptoimidazole 2H-benzotriazole through one or more unsaturated double bonds in the molecule.

As shown in example 12, using 5-Alojamientos 2H-benzotriazole with alkoxycarbonylmethyl the mercaptan is not allocated the expected connection tiefer. Instead, it is the reverse Michael reaction, and the selected product is bioedilizia oxidation using a conventional oxidizing agent, such as hydrogen peroxide, m-chloroperoxybenzoic acid and so on.

Generally stabilized polymers include:

1. The polymers of monoolefins and diolefins, for example polyethylene (which can be structured), polypropylene (PP), polyisobutylene, polybutene-1, polymethylpentene-1, polyisoprene or polybutadiene, and also polymers of cycloolefins, such as cyclopentene or norbornene.

2. Mixtures of the polymers mentioned in part 1), for example mixtures of polypropylene with polyisobutylene.

3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene/propylene, propylene/butene-1, propylene/isobutene, ethylene/butene-1, propylene/butadiene, isobutylene/isoprene, ethylene/alkylacrylate, ethylene/alkyl methacrylates, ethylene/vinyl acetate (EVA) or ethylene/acrylic acid, and their salts (ionomers) and ternary copolymers of ethylene with propylene and a diene (EPDM), for example hexadiene, Dicyclopentadiene or ethylidenenorbornene.

4. Polystyrenes, poly -(- methylsterol).

5. Copolymers of styrene or methylstyrene with denami or acrylic derivatives, for example styrene/butadiene, styrene/Acrylonitrile, styrene/Erie impact styrene copolymers and another polymer, for example, a polyacrylate, a diene polymer or ternary copolymer of ethylene/propylene/diene and copolymers of styrene, for example styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.

6. Graft copolymers of styrene, for example styrene on polybutadiene, styrene and Acrylonitrile on polybutadiene, styrene and alkylacrylate or methacrylates on polybutadiene, styrene and Acrylonitrile on ternary copolymers of ethylene/propylene/diene, styrene and Acrylonitrile on polyacrylates or polymethacrylates, styrene and Acrylonitrile in the copolymers of acrylate/butadiene, as well as mixtures thereof with the copolymers listed in part 5), for example the copolymer mixtures known as polymers of acrylonitrilebutadienestyrene (ABS), a ternary copolymer of methyl methacrylate, butadiene and styrene (MBS), thermoplastic copolymer of Acrylonitrile, styrene and acrylic ester (ASA) or thermoplastic (Quaternary) a copolymer of Acrylonitrile, ethylene, propylene and styrene (AES).

7. Halogen-containing polymers such as polychloroprene, chlorinated rubbers (PC), chlorinated or sulfochlorinated polyethylene, epichlorhydrine Homo - and copolymers, polymers of the ID, polyvinylidene fluoride, and copolymers such as vinyl chloride/vinylidenechloride, vinyl chloride/vinyl acetate, visitengland/vinyl acetate, or copolymers of winifrida/vinyl ether.

8. Polymers that are derived from ,- unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates, polyacrylamide and polyacrylonitrile.

9. The copolymers of the monomers mentioned in part 8), with each other or with other unsaturated monomers, such as copolymers of Acrylonitrile/butadiene, Acrylonitrile/acelacelleto, Acrylonitrile/alkoxyalkanols or Acrylonitrile/vinylchloride, or ternary copolymers of Acrylonitrile/akryliteline/butadiene.

10. Polymers which are derived from unsaturated alcohols and amines or their acyl or their acetals, for example polyvinyl alcohol, polyvinyl acetate, polivinilbutiral, polyvinylether, polyvinylacetate, polyvinyl butyral, polyarylate or polyallylamine.

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

12. Polyacetal, such as Polyoxymethylene and those polyoxymethylenes mixture of oxides Polyphenylene with polystyrene.

14. Polyurethanes which are derived from polyethers, polyesters or polybutadienes with terminal hydroxyl groups on one side or aliphatic or aromatic polyisocyanates on the other side, as well as their predecessors (polyisocyanates, polyols or prepolymers).

15. Polyamides and copolyamids, which are derived from diamines and dicarboxylic acids and/or aminocarbonyl acids or the corresponding lactams, for example Polyamid-4, polyamide-6, polyamide-6/6, nylon-6/10, polyamide-11, polyamide-12, poly-2,4,4-trimethylhexamethylenediamine, poly-p-phenyleneterephthalamide or poly-m-phenylenedimaleimide, as well as their copolymers with polyethers, e.g. with polyethylene glycol, polypropyleneglycol or polytetramethylene.

16. Polyureas, polyimides and polyamideimides.

17. Polyesters obtained from dicarboxylic acids and diols and/or from hydroxycarbonic acids or the corresponding lactones, for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylcyclohexane, poly[2,2-(4-hydroxyphenyl)-propane]terephthalate and polyhydroxybenzenes and block sobolifera-polyesters derived from polyethers having polyetherketone.

20. Crosslinked polymers which are derived from aldehydes on the one hand and phenols, ureas and melamine, on the other hand, for example, phenol/formaldehyde resins and melamine/formaldehyde resins.

21. Drying and non-drying alkyd resins.

22. Unsaturated polyesters which are derived from spoliation of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications with low Flammability.

23. Thermoset polyacrylates obtained from substituted complex acrylic esters, such as epoxyacrylate, urethaneacrylate or acrylate polyesters.

24. Alkyd resins, polyesters or polyacrylates in a mixture with melamine resins, urea resins, polyisocyanates or epoxy resins as crosslinking agents.

25. Crosslinked epoxy resin that is obtained from polyepoxides, for example from bis-glycidyloxy ethers or from cycloaliphatic diepoxides.

26. Natural polymers such as cellulose, rubber, gelatin and derivatives thereof which are chemically modified in a polymer-homologous of Speleology, such as methylcellulose.

27. Mixtures of the polymers mentioned above, for example PP/EPDM, polyamide-6/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP(polybutylenterephthalate)/ABS.

28. Naturally occurring and synthetic organic substances which are pure Monomeric compounds or mixtures of such compounds, for example mineral oils, animal and vegetable fats, oils and waxes, or oils, fats and waxes based on synthetic esters (e.g. phthalates, adipinate, phosphates or trimellitates), and also mixtures of synthetic esters with mineral oils in any mass ratios, and these substances can be used as plasticizers for polymeric or textile sizing, as well as aqueous emulsions of such substances.

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

30. Polysiloxane, such as soft, hydrophilic polysiloxane described, for example, in patent US 4259467A, 31.03.81, and solid polyorganosiloxanes described, for example, in patent US 4355147A, 19.10.82.

31. Polietilene in combination with the saturated akrout urethane acrylates, polyester acrylates, vinyl or acrylic considered unsaturated groups and melamine acrylate. Polietilene derived from polyamines and ketones in the presence of an acid catalyst.

32. Radiation curable compositions containing ethylenevinylacetate monomers or oligomers and polyunsaturated aliphatic oligomer.

33. Aproximadamente resin, such as resistant to light epoxy resin, crosslinked with epoxy-functional collaboration esterified highly rigid melamine resins, for example LSE-4103 (Monsanto).

In General, compounds of the present invention are used in quantities of from about 0.01 to 5% by weight of the stabilized composition, although it may vary depending on the particular substrate and destination. The preferred range is from about 0.5 to 2%, and especially from 0.1 to 1% by mass.

The stabilizers of the present invention can be easily introduced into the organic polymers by traditional methods at any convenient stage prior to the manufacture of molded products from them. For example, the stabilizer may be mixed with the polymer in the form of a dry powder or suspension and lizirovania polymer compositions of the invention may optionally contain from about 0.01 to 5%, preferably about 0,025-2%, and especially about 0.1-1% by weight of various conventional additives, such as substances 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-cyclopentyl-4-METHYLPHENOL,

2-(-methylcyclohexyl)-4,6-dimethylphenol,

2,6-dioctadecyl-4-METHYLPHENOL,

2,4,6-tricyclohexyltin,

2,6-di-tert.-butyl-4-methoxymethanol.

1.2. Alkylated hydrochinone, for example

2,6-di-tert.-butyl-4-methoxyphenol,

2,5-di-tert.-butyl-hydroquinone,

2,5-di-tert.-amyl-hydroximino,

2,6-diphenyl-4-octadecylphenol.

1.3. Gidroksilirovanii thiodiphenylamine ethers, for example

2.2 thio-bis(6-tert.-butyl-4-METHYLPHENOL),

2.2 thio-bis(4-octyphenol),

4.4 thio-bis(6-tert.-butyl-3-METHYLPHENOL),

4.4 thio-bis(6-tert.-butyl-2-METHYLPHENOL).

1.4. Alkalinebattery, for example

2,2'-methylene-bis(6-tert.-butyl-4-METHYLPHENOL),

2,2'-methylene-bis(6-tert.-butyl-4-ethylphenol),

2,2'-methylene-bis[4-methyl-6 -(- methylcyclohexa is tilen-bis[6 -(- methylbenzyl)-4-Nonylphenol],

2,2'-methylene-bis[6 -(,- dimethylbenzyl)-4-Nonylphenol],

2,2'-methylene-bis(4,6-di-tert.-the butylphenol),

2,2'-ethyliden-bis(4,6-di-tert.-the butylphenol),

2,2'-ethyliden-bis(6-tert.-butyl-4-isobutylphenyl),

4,4'-methylene bis(2,6-di-tert.-the butylphenol),

4,4'-methylene-bis(6-tert.butyl-2-METHYLPHENOL),

1,1-bis(5-tert.-butyl-4-hydroxy-2-were)butane,

2,6-di(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-were)-3-n - dodecylmercaptan,

ethylene glycol bis[3,3-bis(3'-tert.-butyl-4'-hydroxyphenyl) butyrate],

di(3-tert.-butyl-4-hydroxy-5-were)Dicyclopentadiene,

di-[2-(3'-tert. -butyl-2'-hydroxy-5'-methylbenzyl)-6-tert. -butyl - 4-were]terephthalate.

1.5 Connection benzyl, for example

1,3,5-three(3,5-di-tert.-butyl-4-hydroxybenzyl)-2,4,6 - trimethylbenzyl,

di(3,5-di-tert.-butyl-4-hydroxybenzyl)sulfide,

complex isooctyl ester of 3,5-di-tert.-butyl-4-hydroxymethylcytosine acid,

bis(4-tert.-butyl-3-hydroxy-2,6-dimethylbenzyl)determinethat,

1,3,5-Tris(3,5-di-tert.-butyl-4-hydroxybenzyl)isocyanurate,

complex dioctadecyl ester of 3,5-di-tert. -butyl-4-hydroxybenzyl the Noah acid.

1.6 Aceraminophen, for example

anilide 4-hydroxylamino acid,

anilide 4-hydroxystearate acid,

2,4-biochimique-6-(3,5-di-tert.-butyl-4-hydroxyanisole)-S-triazine,

octyl-(N-3,5-di-tert.-butyl-4-hydroxyphenyl)carbamate.

1.7 esters - (3,5-di-tert.-butyl-4-hydroxyphenyl)-propionic acid with monatomic or polyatomic alcohols such as methanol, octadecanol, 1,6-hexanediol, neopentylglycol, thiodiethanol, diethylene glycol, triethylene glycol, pentaerythritol, Tris-hydroxyethylstarch, diamid dihydroxyisoflavone acid.

1.8 esters - (5-tert.-butyl-4-hydroxyphenyl)-propionic acid with monatomic or polyatomic alcohols such as methanol, octadecanol, 1,6-hexanediol, neopentylglycol, thiodiethanol, diethylene glycol, triethylene glycol, pentaerythritol, Tris-hydroxyethylstarch, diamid dihydroxyisoflavone acid.

1.9 Amides - (3,5-di-tert.-butyl-4-hydroxyphenyl)-propionic acid, for example

N,N'-di(3,5-di-tert.butyl-4-hydroxyphenylpropionic) hexamethylenediamine were,

N,N'-di(3,5-di-tert.butyl-4-hydroxyphenylpropionic) trimethylenediamine,

N,N'-di(3,5-di-tert.butyl-4-hydroxyphenylpropionic the naphtylamine, 4,4'-di-tert.-octyl-diphenylamine, the product of the interaction of N-phenylaniline and 2,4,4-trimethylpentene, the interaction product of diphenylamine and 2,4,4-triphenylmethane, the product of the interaction of N-phenyl-1-naphtylamine and 2,4,4-triphenylmethane.

2. UV absorbers and light stabilizers

2.1 2-(2'-hydroxyphenyl)-benzotriazole, for example

5'-methyl, 3', 5-di-tert. -butyl-, 5'-tert.-butyl-, 5'-(1,1,3,3-TETRAMETHYLBUTYL)-, 5-chloro-3', 5'-di-tert.-butyl-, 5-chloro-3'-tert.-butyl-5'-methyl-, 3'-sec.-butyl-5'-tert.-butyl-, 4'-actoxy-3',5'-di-tert.-amyl-, 3',5'-bis-( , dimethylbenzyl)-, 3'-tert.-butyl-5'-(2 -- hydroxycut(ethylenoxy)-carbonylethyl)-, 3'-dodecyl-5'-methyl-5'-methyl-, 3'-tert.-butyl-5'-(2 - octyloxyphenyl)ethyl - and modelirovanie 5'-methyl-derivatives.

2.2 2-hydroxybenzophenone, for example

4-hydroxy-, 4-methoxy-, 4-actoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4,2'-4'-trihydroxy - and 2'-hydroxy-4,4'-dimethoxy-derivative.

2.3 esters of optionally substituted benzoic acids, for example fenilsalitsilat, 4-tert. -butylanisole, antifederalist, dibenzoylresorcinol, bis-(4-tert. -butylbenzoyl)-resorcinol, benzoylation, complex 2,4-di-tert.-BUTYLPEROXY ester of 3,5-di-tert.-butyl-4 - hydroxybenzoic acid and complex hexadienyl ether or complex isooctyl ester, cyano, - diphenylacetone acid, methyl ester - carbomethoxyamino acid, methyl ester or complex butyl ether - cyano -- methyl-p-methoxycatechol acid, methyl ester, carbomethoxy-p-methoxycatechol acid, N- (carbomethoxy-- lanvins)-2-methylindolin.

2.5 Connection of Nickel, for example

Nickel complexes of 2,2'-thio-bis-[4-(1,1,3,3-TETRAMETHYLBUTYL)-phenol], such as 1:1 or 1:2 complex, optionally with additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldimethylamine, dibutyldithiocarbamate Nickel, Nickel complex salt monoalkyl esters of 4-hydroxy-3,5-di-tert.-butylbenzylphthalate acid, such as complex methyl, ethyl or butyl ester, Nickel complexes of ketoximes, such as 2-hydroxy-4-methylphenylpolysiloxane, Nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazol, optionally with additional ligands.

2.6 Spatial employed amines, for example

bis(2,2,6,6-tetramethylpiperidine)sebacina, bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacina, di(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5-di-tert.-butyl-4 - hydroxybenzyl)-n-butylmalonate, the polycondensation product of 1-(2-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and amber cyclocreatine, Tris(2,2,6,6-tetramethylpiperidine)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).

2.7 the Diamide of oxalic acid, for example

4,4'-distractionware, 2,2'-dioctyloxy-5,5'-di-tert. -butylanisole, 2,2'-didodecyl-5,5'-di-tert. -butylanisole, 2-ethoxy-2'-ethyl-oxanilide, N, N'-bis(3-dimethylaminopropyl)oxanilide, 2-ethoxy-5-tert.-butyl-2'-ethoxyaniline and its mixture with 2'-ethoxy-2-ethyl-5,4'-di-tert.-butylacetamide and mixture of ortho - and para-methoxy-as well as with ortho - and paradoxi-dvuhkamernyi oxanilide.

2.8 Hydroxyphenyl-S-triazine, for example

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

2,6-bis(2,4-dimetilfenil(-4-(2,4-hydroxyphenyl)-S-triazine,

2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-S-triazine,

2,4-bis[2-hydroxy-4-(2-hydroxyethyl)phenyl]-6-(4-chlorophenyl)-S-triazine,

2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6- (2,4-dimetilfenil)-S-triazine,

2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl] -6-(4-bromophenyl)- S-triazine,

2,4-bis[2-hydroxy-4-(2-acetoacetate)phenyl] -6-(4-chlorophenyl)- S-triazine,

2,4-bis-(2,4-dihydroxyphenyl)-6-(2,4-dimetilfenil)-S-triazine.

3. Deactivators, N,N'-bis(3,5-di-tert.-4 - hydroxyphenylpropionic)hydrazine, 3-salicylamide-1,2,4-triazole, dihydrazide bis-benzylideneamino acid.

4. The phosphites and phosphonites, for example

triphenylphosphite, diphenylacetate, diphenylmethylphosphine, three(nonylphenyl)FOSFA, trilaurylamine, trioctadecyl, distearyldimethylammonium, Tris(2,4-di-tert. -butylphenyl)FOSFA, diisodecylphthalate, di(2,4-di-tert.-butylphenyl)- pentaerythrityl, traceability, tetrakis(2,4-di - tert.-butylphenyl)-4,4'-difeniloliropana.

5. Compounds which destroy peroxide, for example esters-thiodipropionic acid, such as complex lauric, stearyl, ministerului or tridecylamine esters, mercaptobenzimidazole or zinc salt of 2-mercaptobenzimidazole, dibutyldithiocarbamate zinc, dictatorially, pentaerythritol tetrakis ( - dodecylmercaptan)propionate.

6. Hydroxylamine, for example

N, N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylsebacate, N,N-drawingdocument, N,N-detraditionalisation, N,N-dihexadecyl, N, N-dictatorially, N-hexadecyl-N-octadecyltriethoxysilane, N-hexadecyl-N-octadecylamino the measures

N-benzyl-phenylnitrone, N-ethyl-metallitron, N-octyl -- reptilian, N-lauryl-undecillion, N-tetradecyl-tridecylamine, N-hexadecyl -- pentadecane, N-octadecyl -- heptadecane, N-hexadecyl -- heptadecane, N-octadecyl -- pentadecane, N-heptadecyl -- heptadecane, N-octadecyl -- hexadecahedron, Nitron, obtained from N,N-dialkylhydroxylamines derived from hydrogenated tallow amine.

8. Polyamide stabilizers, for example

copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.

9. The main joint stabilizers, for example melamine, polyvinylpyrrolidon, dicyandiamide, treelistener, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and salts of alkaline earth metals of higher fatty acids, for example Ca stearate, Zn-stearate, Mg stearate, Na-ricinoleate and K palmitate, pyrocatechol antimony or pyrocatechol zinc.

10. The nucleating, for example

4-tert. -butylbenzoic acid, adipic acid, diphenyloxy acid.

11. Napolnyali and reinforcing fillers, for example calcium carbonate, silicates, glass fiber, the ASB is other additives, for example plasticizers, lubricants, emulsifiers, pigments, optical brighteners, agents that increase fire resistant, antistatic agents, speciatly and riosynergies substances, such as delayintolerant or distearyldimethylammonium.

Phenolic antioxidant of interest, selected from the group consisting of n-octadecyl-3,5-di-tert.-butyl-4-hydroxyhydrocinnamate, pointattributes(3,5-di-tert.-butyl-4-hydroxy - hydrocinnamate), 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-dioxoanthracene(3-methyl-5-tert. -butyl-4-hydroxyhydrocinnamate), 2,6-di-tert. butyl-p-cresol, 2,2'-ethylidene(4,6-di-tert. -butylphenol), 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)Mesita, hexamethylenebis(3,5-di-tert. butyl-4-hydroxyhydrocinnamate), 1-(3,5-di-tert. -butyl-4-hydroxyanisole)-3,5-di(octylthio)-S-triazine, insiststhat), ethylenebis[3,3-di(3-tert. -butyl-4-hydroxyphenyl)butyrate], octyl-3,5-di-tert.-butyl-4-hydroxybenzylideneamino, bis(3,5-di-tert. -butyl-4-hydroxyhydrocinnamate)hydrazine and N, N'-bis[2-(3,5-di-tert. butyl-4-hydroxyhydrocinnamate)ethyl]oksamida.

The most preferred phenolic antioxidant is pointattributes(3,5-di-tert. -butyl-4-hydroxyhydrocinnamate), n-octadecyl-3,5-di-tert. -butyl-4-hydroxyhydrocinnamate, 1,3,5-trimethyl-2,4,6-Tris(3,5-di-tert. -butyl-4-hydroxybenzyl)benzene, 1,3,5-Tris(3,5-di-tert.-butyl-4-hydroxybenzyl)isocyanurate, 2,6-di-tert.butyl-p-cresol or 2,2 ethylidene(4,6-di-tert.the butylphenol).

The connection is difficult Amin, special interest, which are selected from the group consisting of bis(2,2,6,6-tetramethylpiperidine-4-yl)sebacina, bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacina, di(1,2,2,6,6-pentamethylpiperidin-4-yl) (3,5-di-tert. -butyl-4-hydroxybenzyl)-n-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-triaza-Spiro[4.5]decane-2,4-diol, 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] generateterrain), the 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-butanetetracarboxylic, polycondensation product of 2,4-dichloro-6-morpholino-S-triazine and 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine), N, N', N",N"'-tetrakis[(4,6-bis(butyl-2,2,6,6-tetramethylpiperidine-4-yl) amino-S-triazine-2-yl] -1,10-diamino-4,7-desiderano, 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(2,2,6,6-tetramethylpiperidine-4-yl-carboxylate), 4,4'-ethylenebis(2,2,6,6-tetramethylpiperidine-3-one), N-2,2,6,6-tetramethylpiperidine-4-yl-n-dodecylamine, N-1,2,2,6,6-pentamethylpiperidin-4-yl-n-dodecylamine, N-1-acetyl-2,2,6,6-tetramethylpiperidine-4-yl-n-dodecylamine, 1-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-diazaspiro[4.5] decane-2,4-dione, di-(1-octyloxy-2,2,6,6-tetramethylpiperidine-4-yl-bipiperidine, 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] } and 2,4,6-Tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl) -n-butylamino]-S-triazine.

The most preferred compound of difficult amine used in the coating system is bis(2,2,6,6-tetramethylpiperidine-4-yl)sebacina, bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacina, di(1,2,2,6,6-pentamethylpiperidin-4-yl) (3,5-di-tert.-butyl-4-hydroxybenzo-n-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 and 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine), N,N',N",N"'-tetrakis[(4,6-bis(butyl-2,2,6,6-tetramethylpiperidine-4-yl)amino-S-triazine-2-l]-1,10-diamino-4,7 - dosagecan, di-(1-octyloxy-2,2,6,6-tetramethylpiperidine-4-yl)sebacina, 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[tryout the present invention. Examples 1-13, 17, 19, 21, 23 and 25 illustrate the obtaining of initial products to obtain the compounds of the present invention.

Example 1

5-n-Dodecylthio-2-(2-hydroxy-3,5-di-tert.-butylphenyl)-2H-benzotriazol

In a three-liter triggerlevel flask equipped with a mixer, a thermometer, a hole for the nitrogen inlet and distillation device, load of 57.8 g (1 mol) of 5-chloro-(2-hydroxy-3,5-di-tert. -butylphenyl)-2H-benzotriazole supplied by the company CIBA-GEIGY Corp. in 327, 216,8 g (1.05 mol) of n-dodecylmercaptan and 600 ml of N,N-dimethylformamide (DMF). Then add 73,9 g (0.54 mol) of potassium carbonate and 2 g of potassium iodide and the mixture is heated for 20 hours at a temperature of 150oC in nitrogen atmosphere. The water liberated in the reaction is distilled off in the form of an azeotropic mixture up until the temperature in the head part will reach 132oC. After 20 hours at a temperature of 150oC source 2H-benzotriazol completely consumed. When a partial vacuum at a temperature of 80-100oC most of the DMF Argonauts. To the resulting oil is added at a temperature of 80oC 1 l of toluene and 500 ml of water. The aqueous phase is away. The toluene solution is washed twice with more than 500 ml of water containing 1 ml of acetic acid. Organic racoome whole toluene, except about 100 ml of distilled off at a temperature of 70oC. the Residue is diluted at a temperature of 60oC 2 l of isopropanol and add seed crystals of the product. The product gradually crystallized, after which the mixture is slowly cooled to a temperature of 10oC. the Product is filtered and washed with 300 ml of isopropanol to obtain 490,4 g (93.6% of theoretical) specified in the title compound, melting point 62-64oC.

Example 2

5-Phenylthio-2-(2-hydroxy-3,5-di-tert.-butylphenyl)-2H-benzotriazol

In a two-liter triggerlevel flask equipped with a mixer, a thermometer, a distillation device and a supply of nitrogen, download 268,4 g (0.75 mol) of 5-chloro-2-(2-hydroxy-3,5-di-tert. -butylphenyl)-2H-benzotriazole, 93,7 g (0,825 mol) of thiophenol and 400 ml of N,N-dimethylformamide (DMF). The reactor Tegaserod and filled three times with nitrogen in order to establish an inert atmosphere. To the suspension is added to 66.0 g(0,825 mol) of 50% aqueous sodium hydroxide solution and the mixture is heated to a temperature of distillation. At this point the water is distilled off in the form of an azeotropic mixture up until the temperature in the head part will reach 132oC, and the reaction temperature 150oC. After 18 hours not found any astemperature 80oC. Then, to the residue is added 500 ml of toluene and 200 ml of water. After slow stirring for several minutes at a temperature of 80oC the lower aqueous phase is distilled. Add 200 ml of water are repeated twice, the second time using 1 ml of acetic acid. Residual water azeotrope is distilled off to obtain a light solution. Approximately 300 ml of toluene is removed under partial vacuum at a temperature of 90oC, and to concentrate add 800 ml of isopropanol, which leads to rapid crystallization. The reaction mixture is cooled to a temperature of 20oC and filtered. Light yellow crystals are washed with 250 ml of isopropanol and dried to obtain 317 g (97,9% of theoretical) specified in the title compound, melting point 132 - 134oC.

An alternative is specified in the title compound is synthesized as follows.

In a 250 ml round bottom flask, equipped with magnetic stirrer, intake of nitrogen and condensate load 3.0 g (0,0084 mol) 5-chloro-2-(2-hydroxy-3,5-di-tert.-butylphenyl)-2H-benzotriazole, 1.1 g (at 0.020 mol) of powdered potassium hydroxide, 1.6 ml (0,016 mol) of thiophenol, is 0.135 g (0.49 mol) of 18-crown-6-, and 9 ml of mesitylene. The mixture is heated under reflux and parametrisations acid. The layers are separated and the organic layer was washed 1 time with water and 1 times with saline, and then dried in the presence of anhydrous magnesium sulfate. Analysis of the crude mixture by NMR (CDCl3) shows that the conversion to the target compound indicated in the title, is about 15%.

Example 3-13

< / BR>
According to the method of examples 1 and 2 similarly obtain the following compounds listed in table. 1, usually with outputs in excess of 90%.

Example 14

5-Benzosulfimide-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H - benzotriazol

A solution of 10.8 g (0,025 mol) 5-phenylthio-2-(2-hydroxy-3,5-di - tert.-butylphenyl)-2H-benzotriazole obtained in example 2 in 80 ml of methylene chloride cooled to a temperature of 3 to 5oC. for 30 minutes, add a solution of 5.1 g (0,025 mol) m-chloroperoxybenzoic acid (MCPBA) to 85% in 80 ml of methylene chloride at a temperature of 3 to 5oC. the Reaction mixture is stirred for 2 hours at a temperature of 0 to 5oC with deposition of m-chlorbenzol acid. It is shown that the original substance is absent. After removal of solvent the residue is dissolved in 200 ml of toluene, m-chlorbenzol acid is removed by filtration and subsequent washing, 10% aqueous solution of the carbonate natrium. The amorphous residue is dissolved in 60 ml of petroleum ether and crystallized. Filtering and washing the crystals with cold petroleum ether allow to obtain 9.8 g (87,6% yield) specified in the connection header in the form of a solid, melting at 152 - 154oC.

Example 15

5-Benzazolyl-2-(2-hydroxy-3,5-di-tert. -butylphenyl)-2H - benzotriazol

10,8 (0,025 mol) 5-phenylthio-2-(2-hydroxy-3,5-di-tert. butylphenyl)-2H-benzotriazole obtained in example 2, is dissolved in 80 ml of methylene chloride and cooled to a temperature of 10oC. a Solution of 11.2 g (by 0.055 mol) m-chloroperoxybenzoic acid 85% in 100 ml of methylene chloride added at a temperature of 10 - 15oC for 20 minutes. Then the reaction mixture was stirred at room temperature for 3 hours and filtered to remove m-chlorbenzoyl acid. Then the solvent is removed and the residue is dissolved in 200 ml of toluene. The solution is washed with 10% aqueous solution of sodium carbonate, then with water. After drying in the presence of anhydrous magnesium sulfate and filtration, the solution concentrated. At the first sign of crystallization of the concentrate is diluted with 150 ml of ethanol and crystallized. The crystals are filtered, washed with methanol and dried to obtain>/BR>5-n-Dodecylsulfate-2-(2-hydroxy-3,5-di-tert. -butylphenyl)-2H-benzotriazol

Following the General methodology described in example 15, compound tiefer of example 1 are oxidized with obtaining specified in the connection header with the release of 87% in the form of solid, which melts at a temperature of 93 - 95oC.

Example 17

5,5'-THIOBIS[2-(2-hydroxy-3,5-di-tert.-butylphenyl)-2H - benzotriazol]

6.4 g (0.06 mol) of 3-mercaptopropionic acid is dissolved in a solution containing 2.76 g of sodium in 80 ml of ethanol. The solvent is evaporated and replaced by 110 ml of N,N-dimethylacetamide with the addition of 17.9 g (0.05 mol) of 5-chloro-2-(2-hydroxy-3,5-di-tert.-butylphenyl)-2H - benzotriazole. The mixture is heated in nitrogen atmosphere at a temperature of 160 - 165oC for 48 hours. TCX shows the presence of some amount of unreacted source benzotriazole. The cooled mixture was poured into water containing 150 ml of toluene, and neutralize the hydrochloric acid. Toluene solution is separated and washed with water, dried in the presence of anhydrous magnesium sulfate and filtered. The solution is concentrated and diluted with ethanol. The obtained solid substance produce by filtration and washed with acetone to extract neproreagirovavshimi ablaut 35 ml of acetone, with the aim of precipitation of the product. The resulting crystals are filtered and washed with acetone to obtain 6.6 g specified in the title compound, melting point 245 - 246oC.

Example 18

5,5'-Sulfonyl-bis[2-(2-hydroxy-3,5-di-tert. -butylphenyl)-2H - benzotriazol

A solution of 6.9 g (0,022 mol) m-chlorbenzoyl acid 55% in 50 ml of methylene chloride added at a temperature of 25 - 27oC to a solution of 6.8 g (0.01 mol) of 5,5'-THIOBIS[2-(2-hydroxy-3,5-di-tert.-butylphenyl)-2H - benzotriazole], obtained in example 17, in 150 ml of methylene chloride for 15 minutes. Exothermic reaction regulate cooling on ice. Soon comes the precipitation of the product and m-chlorbenzoyl acid. After stirring the reaction mixture for 3 hours add 1.2 g (0.03 mol) of sodium hydroxide in the form of a 4% aqueous solution with the aim of dissolving m-chlorbenzoyl acid. The methylene chloride is removed from the reaction mixture under partial vacuum and diluted with 75 ml of methanol. The product is filtered and the filter cake washed thoroughly with water and methanol to obtain 6.5 g specified in the title compound, melting point above 300oC.

Example 19

5-Phenylthio-2-[2-hydroxy-3-tert. -butyl-5-(3-hydroxypropyl)- phenyl] -2H-benzotriazol

To a suspension of aluminum is Gnanou stirrer, added dropwise at room temperature a solution of 30.1 g (0,078 mol) 5-chloro-2-[2-hydroxy-3-tert.-butyl-5-(2-methoxycarbonylethyl)phenyl] -2H-benzotriazole in 500 ml of anhydrous diethyl ether. The mixture is stirred for 1.5 hours at room temperature, and the excess hydride is cooled by ethyl acetate. Add water until gel formation, the mixture is dried in the presence of anhydrous magnesium sulfate, filtered and the solvent is removed in vacuum with the receipt of 28.7 g (100% yield) of the intermediate as a yellow-orange solid, melting point 105 - 106oC.

In one litre round bottom flask, equipped with magnetic stirrer, condenser, nitrogen atmosphere loaded with 27.7 g (0,077 mol) of the intermediate obtained above, 10.6 g (0,077 mol) of potassium carbonate and 1.2 g of potassium iodide and 8,48 g (0,077 mol) of thiophenol in 240 ml of N,N-dimethylformamide. Use a preheated oil bath (165oC) and the mixture was stirred at this temperature for 4.5 hours. After cooling to room temperature, stirring is continued for 18 hours. Then the reaction mixture is poured into 500 ml of water. The aqueous layer was neutralized with concentrated hydrochloric acid and then extragere is the notes, 1 time a saline solution and then dried in the presence of magnesium sulfate. The solvent is removed under reduced pressure to obtain 30.1 g of a yellow-orange solid. The crude substance is recrystallized from heptane receipt of 26.3 g (79% yield) specified in the title compound as a yellow powder. Analysis: calculated for C25H27N3O2S: C AND 69.3; H, 6,3; N, 9,7. Found: C For 68.9; H, 6,0; N 9,7.

Example 20

5-Benzazolyl-2-[2-hydroxy-3-tert. -butyl-5-(3 - hydroxypropyl)phenyl]-2H-benzotriazol

In one litre round-bottom flask equipped with a magnetic stirrer, under nitrogen atmosphere download solution of 13.1 g (0,030 mol) 5-phenylthio-2-[2-hydroxy-3-tert. -butyl-5-(3-hydroxypropyl)phenyl] -2H-benzotriazol in 400 ml of methylene chloride. The solution is cooled in an ice bath and quickly add small portions of 20.7 g (to 0.060 mol) of m-chloroperbenzoic acid, MCPBA (50 - 60%). The reaction mixture is stirred at low temperature for 2 hours. The formed precipitate is filtered off and the solvent is removed under reduced pressure. The residue is dissolved in ethyl acetate and washed 1 time 10% sodium sulfite, 5 times with a saturated solution of sodium bicarbonate and 1 times with saline. After drying in the presence of beswt the product is recrystallized from a mixture of 1/1 ethyl acetate/heptane to obtain 10.1 g (72% yield) specified in the title compound as a yellow powder, melting point 159 - 161oC. Analysis: calculated for C25H27N3O4S: C, AND 64.5; H, 5,8, N, 9,0. Found: C, 63,5; H 5,2; N 8,8.

Example 21

3(5-Phenylthio-2H-benzotriazol-2-yl)-5-tert. -butyl-4 - hydroxyvitamin acid

In one litre chetyrehosnuju round-bottom flask equipped with a mechanical stirrer, under nitrogen atmosphere download 100.0 g (0,258 mol) of methyl-3-(5-chloro-2H-benzotriazol-2-yl)-5-tert. -butyl-4 - hydroxyhydrocinnamate, 350 ml of N, N-dimethylformamide and 61.9 g (0,773 mol) of 50% aqueous sodium hydroxide solution. The mixture is heated at a temperature of 75-80oC for 3 hours and is currently completing the hydrolysis of ester. Add a catalytic amount of potassium iodide (5.0 g). Then within 20 minutes add thiophenol (32,2 g, 0,258 mol), maintaining the temperature at 75-80oC. Add an additional amount of N,N-dimethylformamide (200 ml) while adding thiophenol for better mixing. Remove 25 ml fractions of water/methanol and the solution heated under reflux for 48 hours. Then the reaction mixture is cooled, partitioned between 1.0 liter of 1N hydrochloric acid and 1.0 l of ethyl acetate. The phases are separated and the organic phase is dried in the presence of bitweaver 500 ml. Add 200 ml of heptane and the solution advocated during the night. The resulting crystals are collected by filtration under vacuum, washed with 9:1 heptane: ethyl acetate and dried with getting to 83.5 g (72% yield) specified in the title compound, melting point 154-156oC.

Example 22

3-(5-Benzazolyl-2H-benzotriazol-2-yl)-5-tert-butyl-4 - hydroxyvitamin acid

According to the method of example 15 from the compound obtained in example 21 as an initial matter, get listed at the beginning of the connection.

Example 23

3-(5-Phenylthio-2H-benzotriazol-2-yl)-5-tert. -butyl-4 - hydroxyhydrocinnamate

In a dry 500-ml round bottom flask, equipped with magnetic stirrer, condenser and intake of nitrogen load 3.0 g (0,0067 mol) of 3-(5-phenylthio-2H-benzotriazol-2-yl)-5-tert.-butyl-4-hydroxyvitamin acid, 6 ml of oxalicacid and sufficient chloroform to the formation of homogeneous solution (approximately 4 ml). The solution is heated under reflux for 1 hour and then stirred overnight at room temperature. Oxalicacid distilled off under reduced pressure to obtain about 3.5 g of yellow solid. The IR spectrum of the solid (thin film tropolone flask, equipped with a magnetic stirrer, load 250 ml of anhydrous ethanol. After cooling to a temperature of -5oC gaseous ammonia bubbled through the solvent to obtain about 1 g (0.06 mol). To the ammonia solution quickly in small portions add the acid chloride, getting red color solution. The mixture is heated to room temperature and stirred over night. The ethanol is removed under reduced pressure and the residue is dissolved in ethyl acetate. The solution was washed with water (1x), saturated sodium carbonate solution (1x) and brine (1 time). The combined aqueous layers are extracted twice with ethyl acetate and the combined organic layers are dried in the presence of anhydrous magnesium sulfate. After removal of the solvent to obtain 3.1 g of brown solid. The crude product is recrystallized from ethanol/water to obtain 1.85 g (62% yield) of the pure amide as a brown solid, melting point 128-130oC. Analysis: calculated for C25H26N4O2S; C, AND 67.2; H, 5,9; N, 12,5. Found: C, From 66.7; H, 5,7; N, 12,3.

Example 24

3-(5-Benzazolyl-2H-benzotriazol-2-yl)-5-tert. -butyl-4 - hydroxyhydrocinnamate

In a 100-ml round-bottom flask equipped with a magnetic stirrer, methylene chloride. With stirring, the solution is cooled in an ice bath, and then quickly in small portions add around 0.70 g 50-60% solution of m-chloroperbenzoic acid, MCPBA, (2 equivalent). The solution is heated to room temperature and stirred for additional 15 minutes. The solvent is removed under reduced pressure and the residue re-dissolved in ethyl acetate. The solution was washed 1 time with water, 5 times with saturated sodium bicarbonate and 1 times with saline. After drying in the presence of anhydrous magnesium sulfate the solvent is removed with the receipt of 0.53 g of yellow solid. The crude product is introduced into a column with medium-pressure silica gel with 80% ethyl acetate/heptane as eluent. Pure fractions combined with the receipt of 0.30 g (63% yield) specified in the title compound as yellow crystals, melting point 144-145oC. Analysis: calculated for C25H26N4O4S: C, 62,7; H, 5,5, N, 11,7. Found: C, 61, 8mm; H, 5,4, N, 11,1.

Example 25

Isomeric mixture of 3-[3-(5-phenylthio-2H-benzotriazol-2-yl)-5-tert.-butyl-4 - hydroxyhydrocinnamate] -2-hydroxypropylmethacrylate and 2-[3-(5-phenylthio-2H-benzotriazol-2-yl)-5-tert. -butyl-4-hydroxy - hydrocinnamate]-3-hydroxypropylmethacrylate

In a 250 ml CRU.-butyl-4-hydroxyvitamin acid, 0.20 g of 4-methoxyphenol, 1.50 g of tetrabutylammonium, 6.60 g (0,0460 mol) glycidylmethacrylate and 150 ml of toluene. With stirring, the mixture is heated under reflux for 6 hours. After cooling to room temperature the mixture was washed 1 time with water and the solvent is removed in vacuum to obtain 27,3 g (100% yield) specified in the title compounds as pale yellow viscous oil. Analysis by NMR shows that the product is an isomeric mixture of compounds A and B (A: B, 78:22). Analysis: calculated for C32H35N3O6S; C, TO 65.2; H, 6,0; N, 7,1. Found: C, Of 66.9; H, 6,6, N, 6,5.

Example 26

Isomeric mixture of 3-[3-(5-benzazolyl-2H-benzotriazol-2-yl)-5-tert.-butyl-4 - hydroxyhydrocinnamate] -2-hydroxypropylmethacrylate and 2-[3-(5-benzazolyl-2H-benzotriazol-2-yl)-5-tert. -butyl-4 - hydroxyhydrocinnamate]-3-hydroxypropylmethacrylate

Adding glycidylmethacrylate in accordance with the method of example 25 to substituted hydracarina acid obtained in example 22, receive specified in the header of the isomeric mixture.

Example 27

5-Benzazolyl-2-{ 2-hydroxy-3-tert. -butyl-5-[2-( -hydroxycut(ethylenoxy)carbonylethyl]phenyl}-2H-benzotriazole.

In a 250 ml KRU the-butyl-5-[2 -(- hydroxycut(ethylenoxy)carbonylethyl] phenyl} -2H-benzotriazole in 40 ml of methylene chloride. To a stirred solution quickly add small portions of 3.9 g (0.012 mol) of m-chloroperbenzoic acid (50-60%). The mixture is stirred for 30 minutes and then filtered, followed by removal of solvent. The residue is dissolved in ethyl acetate. The solution is washed twice with saturated aqueous sodium carbonate solution, three times with saturated aqueous sodium bicarbonate solution and once with brine. After drying in the presence of anhydrous magnesium sulfate the solvent is removed under reduced pressure to get 2,43 g (64% yield) specified in the title compound as a viscous yellow oil. Analysis by NMR (CDCl3) is consistent with the desired structure.

Example 28

5-Benzazolyl-2-[2-hydroxy-3-tert. -butyl-5 -(- octyloxy - carbonylethyl)phenyl]-2H-benzotriazol

In a 500-ml round-bottom flask equipped with a magnetic stirrer and a nitrogen atmosphere, load the solution of 14.3 g (0,026 mol) 5-thiophenyl-2-[2-hydroxy-3-tert. -butyl-5 -(- octyloxyphenyl)phenyl]-2H-benzotriazole in 250 ml of methylene chloride. The solution is cooled in an ice bath, and then quickly in small portions add to 14.7 g (0,052 mol) of m-chloroperbenzoic acid (50-60%). The reaction mixture is brought to room temperature and filtered. Resto sodium bicarbonate (5 times), 1 time brine and finally dried in the presence of anhydrous magnesium sulfate. Removal of solvent followed by purification by medium pressure chromatography (ethyl acetate/heptane) to receive 11,5 g (75% yield) of pure compound indicated in the title, in the form of a solid yellow color, melting point 62-63oC. Analysis: calculated for C33H41N3O5S; C, 67,0; H, 7,0; N, 7,1. Found: C, To 66.8; H, 6,9, N, 7,1.

Example 29

Spectral properties of UV absorbers on the basis of substituted 5-sulfonylmethane

The next table. 2 shows maximum absorbance, molar and specific extinction coefficients of a number of UV absorbers, based on 2H-benzotriazole. Examine the known commercial benzotriazole UV absorber: 2-[2-hydroxy-3,5-di - (- dimethylbenzyl)phenyl]-2H-benzotriazol, and some of the proposed 5-sulfoxide and 5-sulfonamide compounds. The concentration of each of the samples are identical, namely 20 mg/l Maximum absorbance values sulfoxide and sulfonic compounds at 356-365 nm are Krasnoznamennyj, i.e. shifted towards the visible for at least 12 nm relative to the commercial control sample, which has a m is to protect substrates, sensitive to UV light with relatively large wavelengths. They include many of the aromatic system. An important example is epoxy resin, which is the main primers in the automotive and other applications. Light can penetrate in the car the soil and destroy the primer at the interface of the primer/primer. This phenomenon is accompanied by loss of adhesion to the upper layer even if the upper layer can have a excellent condition. Exposure to high humidity contributes to this phenomenon of delamination.

Steel test panels containing a commercial epoxy primer applied cathodic electrodeposition, get spray film thickness of 1.8-2.0 mil (0,046-0,051 mm) commercially supplied the highly rigid thermoset acrylic melamine, which is used as a layer on the panel UNIPRIME size h inches (10.16 cm x 30.48 cm), obtained in Advance Coating Technology, Inc. Panels coated then calcined at a temperature of 250 F (121oC) for 30 minutes. After storage for 1 week in a room with air-conditioning-covered panel exhibit within 55 days in Florida in the "black box" (5oSouth) in accordance with SAEJ Wed during exposure in the open air and not subject to further testing. The panels are then placed in the chamber for humidifying QCT (Q-Panel Co.) at 100% relative humidity and a temperature of 100oC and checked daily for swelling and delamination. The results are shown below in table. 3.

After 4 days of exposure in the humidity panel, stable compound of example 15, is examined for adhesion in accordance with method D-3359 American society for testing and materials (ASTM) and evaluate on a scale of 3-4B, where 5B shows no loss of adhesion and 0B indicates the presence of more than 65% loss of adhesion.

These results show that the proposed benzotriazole with increased absorption in colovaginal region, are particularly effective in protecting automotive coatings from the delamination after prolonged exposure to sunlight and high humidity conditions.

Example 31

The resistance to delamination of the highly rigid thermoset coatings, including UV absorbers, which are applied directly to elecrodeposition primer

Steel test panels containing a commercial epoxy primer applied cathodic electrodeposition, get spray film thickness of 1.8-2.0 mil (being 0.036-0,051 mm) commercial the panel UNIPRIMEsize h inches (10.16 cm x 30.48 cm), obtained in Advance Coating Technology, Inc. Panels coated then calcined at a temperature of 250 F (121oC) for 30 minutes. After storage for 1 week in a room with air-conditioning-covered panel exhibit within a certain period of time in Florida in the "black box" (5oSouth) in accordance with SAE J-1976. The panel evaluated every 7 days for the delamination and believe that the panel was spoiled in that case, if the delamination is clearly at least 10% of the total number of panels. The results of this test are shown below in table. 4.

Example 32

The copolymer isomeric mixture of 3-[3-(5-benzazolyl-2H-benzotriazol-2-yl)-5-tert.-butyl-4 - hydroxyhydrocinnamate]-2-hydroxypropylmethacrylate and 2-[3-(5-benzazolyl-2H-benzotriazol-2-yl)-5-tert. -butyl-4 - hydroxyhydrocinnamate]-3-hydroxypropylmethacrylate

When dissolved isomeric mixture of monomers of methacrylate obtained in example 26, in toluene in the presence of 2,2'-azobis (isobutyronitrile) and heated to a temperature of 80oC get the corresponding methacrylate copolymer mentioned above.

A stable composition is obtained when the introduction f the ri effect of neblagopriyatnyh effects of actinic radiation.

Example 33

Monomeric composition comprising 23.5% of butyl acrylate, 27% of butyl methacrylate, 30% 2-hydroxyethylacrylate, 15% styrene, 3% acrylic acid and 1.5% isomeric mixture of methacrylate obtained in example 26 (all values are given by weight), and 0.4 per 100 parts of resin initiator based on tert.-AMYLPEROXY-O-(2-ethylhexyl)monoperoxyphthalate will polimerizuet in xylene at reflux distilled with the formation of stabilized acrylic polyol copolymer with a moderate molecular weight.

Example 34

When acrylic polyisoprene obtained in example 33, add in standard acrylic-melamine composition, get stabilized thermosetting acrylic enamel with excellent resistance to damage caused actinic radiation, and has excellent preservation values Shine with the reflection of light at an angle of 20o.

Example 35

When acrylic polyisoprene obtained in example 33, to add to the standard two-component acrylic-urethane coating compositions for re-finishing, get coverage, with excellent preservation of magnitude Shine with the reflection of light at an angle of 20o.

Example 36

When acrylic poly is less enamel, having excellent preservation values Shine with the reflection of light at an angle of 60o.

1. Substituted benzotriazole General formula

< / BR>
where R1means remotemachine or branched alkyl containing from 1 to 24 carbon atoms;

R2means remotemachine or branched alkyl containing from 1 to 24 carbon atoms, with the specified alkyl may be substituted by one or more hydroxy-group, or R2means-CH2CH2COR5where R5equal-NH2or6where R6means hydrogen, alkyl containing from 1 to 24 carbon atoms, unsubstituted or substituted by one or more hydroxy-group or OR6means - (OCH2CH2)wOH, where W is 1 to 12, or R2means -(CH2)m-CO-X-(Z)p-Y-R15where X and Y denotes-O-, Z - alkylen with the number of carbon atoms from 3 to 12, a substituted hydroxyl group, R15- group-CO-C(R18) = CH2where R18is hydrogen or methyl, m = 0, 1, or 2, and p = 1;

R3means alkyl with the number of carbon atoms from 8 to 20, aryl with the number of carbon atoms from 6 to 10, or R3represents a radical of the formula B2< / BR>
< / BR>
where E means C2- C12-a = 0 or 1, and L = -SO - or-SO2-.

2. Substituted benzotriazole formulas And p. 1, where R1remotemachine or branched alkyl with a number of carbon atoms from 1 to 24; R2means remotemachine or branched alkyl with a number of carbon atoms from 1 to 24; or R2means a group of formula-CH2CH2COR5where R5means-NH2or6where R6means hydrogen or alkyl with the number of carbon atoms from 1 to 24, or or6means - (OCH2CH2)wOH, where w is 1 to 12, or R2means -(CH2)m-CO-X-(Z)P-Y-R15where X and Y denote-O-, Z - alkylen with the number of carbon atoms from 3 to 12, a substituted hydroxyl group, R15means a group-CO-C(R18)=CH2where R18is hydrogen or methyl, m = 0, 1, or 2, and p = 1; R3means alkyl with the number of carbon atoms from 8 to 20, aryl with the number of carbon atoms from 6 to 10; L is-SO - or-SO2-.

3. Substituted benzotriazole formulas And p. 1, in which R1means branched alkyl with a number of carbon atoms from 4 to 8; R2means remotemachine or branched alkyl with a number of carbon atoms from 1 to 8, substituted by one or more hydroxyl group; or R2UB> means hydrogen or alkyl with the number of carbon atoms from 1 to 24, not substituted or substituted by one or more hydroxy-group or OR6means -(OCH2-CH2)wOH, where w is 1 to 12, or R2means -(CH2)m-CO-X-(Z)P-Y-R15where X and Y denote-O-, Z - alkylen with the number of carbon atoms from 3 to 8, a substituted hydroxyl group, R15means a group-CO-C(R18)=CH2where R18is methyl, m = 2 and p = 1, and R3means phenyl or alkyl with the number of carbon atoms from 8 to 12 and L represents-SO - or-SO2-.

4. Substituted benzotriazole formulas And p. 1, representing a compound selected from the group including:

(a) 5-n-dodecylsulfonate-2-(2-hydroxy-3,5-di-tert. -butylphenyl)-2H-benzotriazole;

(b) 5-benzosulfimide-2-(2-hydroxy-3,5-di-tert. -butylphenyl)-2H-benzotriazole;

(C) 5-benzazolyl-2-(2-hydroxy-5-were)-2H-benzotriazole;

(g) 5,5'-sulfonyl-bis[2-(2-hydroxy-3,5-di-tert. -butylphenyl)-2H-benzotriazol];

(d) 5-benzazolyl-2-[2-hydroxy-3-tert. -butyl-5-(- octyloxyphenyl)phenyl]-2H-benzotriazole;

(e) 5-benzazolyl-2-[2-hydroxy-3-tert. -butyl-5-(3-hydroxypropyl)phenyl]-2H-benzotriazole;

(W) 3-(5-benzazolyl-2H-what evils-2-yl)-5-tert.-butyl-4-hydroxyvitamin acid);

(I) an isomeric mixture of 3-[3-(5-benzazolyl-2H-benzotriazol-2-yl)-5-tert. -butyl-4-hydroxyhydrocinnamate]-2-hydroxypropylmethacrylate and 2-[3-(5-benzazolyl-2H-benzotriazol-2-yl)-5-tert. -butyl-4-hydroxyhydrocinnamate]-3-hydroxypropylmethacrylate;

(K) 5-benzazolyl-2-{2-hydroxy-3-tert.-butyl-5-[2-(- hydroxycut (ethylenoxy)carbonylethyl]phenyl}-2H-benzotriazole.

5. Stabilized composition containing the polymer is subjected to erosion due to adverse effects of actinic radiation, and substituted benzotriazole as a UV absorber, characterized in that the UV absorber it contains an effective stabilizing amount of substituted benzotriazole General formula As under item 1.

6. Stabilized composition on p. 5, characterized in that the polymer is chosen from the group consisting of polystyrene, graft copolymers of styrene, polyphenyleneoxides, polyphenylensulfide, polyurethanes, polyisocyanates, aromatic polyesters, aromatic polyamides, politician, polyimides, polyamideimides, polysulfones, polyethersulfones, polyetherketones, alkyd resins, aminos and epoxy resins.

7. Stable compo is the first song on p. 5, characterized in that substituted benzotriazole it contains 5-benzazolyl-2-(2-hydroxy-3,5-di-tert.-butylphenyl) - 2H-benzotriazole.

9. Stabilized composition on p. 5, characterized in that as substituted benzotriazole it contains 5-benzazolyl-2-(2-hydroxy-3,5-di-tert. -butylphenyl)-2H-benzotriazole, 5-benzazolyl-2-[2-hydroxy-3-tert. -butyl-5-(-octyloxyphenyl)phenyl] -2H-benzotriazole, 5-benzazolyl-2-{ 2-hydroxy-3-tert. -butyl-5-[2-(-hydroxycut(ethylenoxy)-carbonylethyl] phenyl}-2H-benzotriazole, -hydroxypoly(ethylenoxy)-3-(5-benzosulfonazole-2-yl)-5-tert. -butyl-4-hydroxyhydrocinnamate or poly(ethyleneoxy) bis[3-(5-benzosulfonazole-2-yl)-5-tert.-butyl-4-hydroxyhydrocinnamate).

10. Coating system made of upper and lower layers of polymer, characterized in that the bottom layer of polymer comprising an organic or inorganic pigment or a mixture thereof, and the upper light polymer layer or both layers together contain an effective amount of substituted benzotriazole General formula (A) under item 1 as a UV absorber.

11. Coating system on p. 10, characterized in that the polymer layers as substituted by benzotri the STI-3-tert. -butyl-5-(-octyloxyphenyl)phenyl] -2H-benzotriazole, 5-benzazolyl-2-{2-hydroxy-3-tert.-butyl-3-[2-(-hydroxycut(ethylenoxy)-carbonylethyl] phenyl}-2H-benzotriazole, - hydroxy-poly(ethylenoxy)-3-(5-benzosulfonazole-2-yl)-5-tert. -butyl-4-hydroxyhydrocinnamate or poly-(ethyleneoxy) bis[3-(5-benzosulfonazole-2-yl)-5-tert.-butyl-4-hydroxyhydrocinnamate].

12. Coating system on p. 11, characterized in that the polymer layers as substituted benzotriazole contain 5-benzazolyl-2-{2-hydroxy-3-tert. -butyl-5-[2-(-hydroxycut(ethylenoxy)-carbonylethyl] phenyl}-2H-benzotriazole.

13. Coating system on p. 10, characterized in that the polymer layers additionally contain a UV absorber selected from the group consisting of benzophenone, benzotriazole derived cyanoacrylate acid, hydroxyaryl-S-triazines, organic Nickel compounds and oxanilide present in either the upper or lower layer, or both layers.

14. Coating system on p. 10, characterized in that the polymer layers additionally contain an effective stabilizing amount of a phenolic antioxidant or at the top or bottom, or both layers.

15. Covering icesto difficult amine or at the top, either at the bottom or in both layers.

16. Coating system on p. 10, characterized in that the polymer layers additionally contain an effective stabilizing amount of phosphite or phosphonite either at the top or bottom, or both layers.

17. Coating system on p. 10, characterized in that it is applied for coating coils, penetrating or film-forming finishes under the tree.

18. Coating system on p. 13, characterized in that the polymer layers additionally contain a UV absorber selected from the group consisting of 2-[2-hydroxy-3,5-di-,-dimethylbenzyl)phenyl] -2H-benzotriazole, 2-(2-hydroxy-3,5-decret. -amylphenol)-2H-benzotriazole, 2-[2-hydroxy-3-tert.-butyl-5-(-hydroxycut(ethyleneoxy)carbonyl)ethylphenyl] -2H-benzotriazole, 2-[2-hydroxy-3-tert. -butyl-5-(2-octyloxyphenyl)phenyl] -2H-benzotriazole, 4,4'-distractionmanila, 2,2'-dioctyl-5,5' -di-tert. -butylacrylate, 2,2'-didodecyl-5,5'-di-tert. -butylacrylate, 2-ethoxy-2'-atrocinerea, 2,6-bis(2,4-dimetilfenil)-4-(2-hydroxy-4-octyloxyphenyl-S-triazine, 2,6-bis(2,4-dimetilfenil)-4-(2,4-dihydroxyphenyl)-S-triazine, 2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-S-triazine, 2,6-bis(2,4-dimetilfenil)-4-[2-hydroxy-4-(2-hydroxy-3-dodecyloxyethoxy)FA fact, that polymer layers additionally contain a hindered amine selected from the group comprising bis(2,2,6,6-tetramethylpiperidine-4-yl)sebacina, bis-(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacina, di(1,2,2,6,6-pentamethylpiperidin-4-yl) (3,5-di-tert. -butyl-4-hydroxybenzyl)butylmalonate, the polycondensation product of 1-(2-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, polycondensation product of 2,4-sodium dichloro-6-tert. -octylamine-S-triazine 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) -N,N',N",N"'-tetrakis [4,6-bis(butyl-2,2,6,6-tetramethylpiperidine-4-yl)amino-S-triazine-2-yl] -1,10-diamino-4,7-dosagecan, di-(1-octyloxy-2,2,6,6-tetramethylpiperidine-4-yl)sebacina, 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)imino-hexamethylene-[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)-H-butylamino]-S-triazine.

20. Methacrylic copolymer obtained additive polymerization isomeric mixture of 3-[3-(5-benzazolyl-2H-benzotriazol-2-yl)-5-tert.-butyl-4-hydroxyhydrocinnamate] -2-hydroxypropyl of prophylatically.

21. Stabilized composition containing the polymer is subjected to erosion due to adverse effects of actinic radiation, and an effective stabilizing amount of a copolymer on p. 20.

 

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< / BR>
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FIELD: chemistry.

SUBSTANCE: stabilising composition is described, containing (A) compound of 2,4-bis-(4-phenylphenyl)-6-(2-hydroxyphenyl)-1,3,5-triazine series by formula (I), and (B) one or more compounds chosen from group, which include benzotriazoles by formula (IIa), 2-hydroxybenzophenones by formula (IIb), oxanilides by formula (IIc), 2-hydroxyphenyltriazines by formula (IId), cinnamates by formula (IIe), and benzoates by formula (IIf). There are also described: composition, containing stabiliser composition and organic material; method for organic material stabilisation; and application of stabiliser composition to organic material stabilisation.

EFFECT: increase in efficiency of labile organic materials stabilisation.

17 cl, 19 tbl, 24 ex

FIELD: chemistry.

SUBSTANCE: described are novel derivatives of benzotriazole of general formula , where X is C3-C4 alkenylene, C3-C4 alkylene, CH2CH2CH2SCH2CH2 or CH2CH2CH2SCH2CH2CH2; Y is hydrogen, if X is C3-C4 alkenylene, or Y is -O-C(=O)-C(R1)=CH2, if X is C3-C4 alkylene, CH2CH2CH2SCH2CH2 or CH2CH2CH2SCH2CH2CH2; R1is CH3 or CH2CH3; R2 is C1-C4 alkyl, and R3is F, Cl, Br, I or CF3.

EFFECT: compounds are absorbers of UV/visible light and can be applied in production of materials for ophthalmological lenses.

5 cl, 3 dwg, 5 tbl, 6 ex

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