The ethylene-unsaturated polymerizable monomers based on a derivative of piperidine

 

(57) Abstract:

Usage: as a Monomeric copolymerizate light stabilizers. The inventive product is ethanobotany polymerizable monomer based on a derivative of piperidine f-ly I, where R1-C1-C18-alkyl or cyclohexyl, E is the radical of f-crystals-X-CO-(CH=CH)2-COX-R3X-CO-CR2=CH2, -X-CH2-C6H4-CH= CH2, -X-CH2-CH=CH2or-O-CO-(C4H6)m-CO-O-R3where X denotes-O - or-NH-, R2is hydrogen or methyl, m is an integer from 1 to 30. Reagent 1: piperidinol f-ly II. Reagent 2: derived unsaturated carboxylic acid. Reaction conditions: inert organic solvent in the presence of amine.

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2 C.p. f-crystals, 8 PL.

The invention relates to ethyleneamines compositions containing 1-hydrocarbon-hydroxy-2,2,6,6-tetramethylpiperidine functional groups, and to polymers and copolymers produced from them.

Monomeric copolymerizate light stabilizers that contain spatial zatrudnieniu amine function, known from the prior art, as evidenced by the following list of typical patents and publications is ce, Poly. Chem. bd, 1974, v. 12, 1407.

None of the links above is not disclosed or offered to these compounds, the substituted atom 1-N hydrocarbonate group.

Not capable of polymerization employed amines, substituted atom 1-N hydrocarbonate-group described in European patent EP-A-309 402. However, it describes the connection cannot be homopolymerization or copolymerization; thus, lost key element of flexibility inherent here ethyleneamines materials.

According to the present invention using ethanobotany, polymerizable monomer containing the functional group of difficult amine, in which the 1-N atom is replaced by hydrocorax group.

According to the present invention also use the homopolymers of the specified monomer, which have increased resistance to migration and loss due to evaporation in the conditions of end use.

Another object of the present invention is the use of copolymers of these monomers with a wide variety of other ethanobotany monomers having no functional group difficult amine.

the e functional group difficult amine, in which the 1-N atom is replaced by hydrocarbonate group, and the specified functional group has the formula E

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where L1and L2are the stands and R1is alkyl with 1-18 carbon atoms or cyclohexyl, and this monomer selected from the group consisting of formulas I-VI

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When X is-O - or-NH-,

n is 1 or 2,

m is an integer in the range from 10 to 100,

R2is hydrogen or stands,

R3and R4are hydrogen.

Preferably m is an integer in the range from 10 to 30.

Preferably R2, R3and R4each is a hydrogen atoms, or R3and R4are hydrogen atoms and R2is methyl.

When R1alkyl is, for example, stands, ethyl, bootrom, AMISOM, actilon, nannilam, dodecyl, tetradecyl, octadecyl, akosile, triazolam or tricontrol.

Each of the monomers of formulas I-VI contains ethylenevinylalcohol group, which allows the polymerization of monomers using free radical initiation, photoinitiator, the polymerization migration groups, grafted polymerization or cationic or anionic poly is Omer formulas I-VI.

In addition, each of the monomers of formulas I-VI may copolymerisate with separate vinyl monomer not having a group of formula E, to obtain a copolymer having as an integrated part of the main polymer chain stabilizing units, which are attached side groups of the formula E.

The specified polymer or copolymer comprises the polymerization product of: a) from 1 to 100 wt. in calculating the amount of polymer or copolymer, at least one ethyleneamines, polymerizable monomer containing the functional group of difficult amine, in which the 1-N atom substituted hydrocarbon-oxy group, and this function has a formula that is

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where L1and L2are the stands and R1is alkyl with 1-18 carbon atoms or cyclohexyl, and this monomer selected from the group consisting of formulas I-VI

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When X is-0 - or-NH-,

n is 1 or 2,

m is an integer from 10 to 100,

R2is hydrogen or stands,

R3and R4are hydrogen.

Preferably m is an integer from 10 to 30.

b) from 99 to 0 wt. in calculating the amount of polymer or copolymer, at least one group, consisting of esters and amides of acrylic and methacrylic acids, itaconates, citraconate, styrene, vinylpyridine, divinylbenzene, Acrylonitrile, Methacrylonitrile, N-vinyl-2-pyrrolidone, N-vinylcarbazole, maleimido, vinylsulfonate, alpha-olefins, isoprene, butadiene, vinyl esters, vinyl ethers and halogenated olefins.

Such copolymers containing even a small amount of the component (a) may create links with a high degree of svetozarauladocy that cannot migrate, be lost through volatilisation or otherwise leave critical protection center copolymer from the damaging effects of chemically active rays.

Ethylenevinylacetate copolymers can also contain the function of absorbing UV rays, such as hydroxyphenylarsonic benzotriazol or sym-triazine, replacement benzophenone, oxanilide or alpha cyanocinnamate. Examples of such ethylene unsaturated UV absorbers are described in several U.S. patents, which are listed in this patent as prior art.

Acrylic benzotriazole described in U.S. patent N 4 413 095, 4 716 234, 4 785 063 and 4 803 254. Aryloxyalkyl-benzotriazole described in U.S. patent N 4 HN in U.S. patent N 3 493 539. Acrylic benzophenone described in U.S. patent No. 4 310 650.

There are several methods of synthesis, which can be used for the preparation of these monomers. They include:

a) transesterification using 4-hydroxy-2,2,6,6-tetramethylpiperidine and complex ester of lower alkyl unsaturated acids such as acrylic, fumaric, Mukanova or etc.

b) esterfication using 4-hydroxy-2,2,6,6-tetramethylpiperidine and carboxylic acids, such as acryloyl or methacryloyl-chloride;

in) amidarone using 4-amino-2,2,6,6-tetramethylpiperidine and carboxylic acids, such as acryloyl or methacryloyl-chloride;

d) limitirovanie using 4-amino-2,2,6,6-tetramethylpiperidine and a cyclic anhydride such as maleic anhydride, followed by cyclization of the intermediate melaminovoi acid;

d) substitution of the halogen with the use of unsaturated benzyl or allyl-halide and metal alcoholate 4-hydroxy-2,2,6,6-tetramethylpiperidine, and

(e) catalytic oxidation prior 4-acelolocle-2,2,6,6-tetramethylpiperidine tert-butylhydroperoxide or hydrogen peroxide in the presence of a catalyst trioxide is the service of the compounds according to the invention, are mainly commercially available reagents or can be obtained is known from the prior art, the traditional ways.

In table. 1-4 shows a typical Monomeric compounds of the present invention:

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The polymers and copolymers of the present invention can be obtained from the above-mentioned monomers using conventional methods of polymerization, which are in General described in Houben-Weyl in the book. "Methods of organic chemistry, 1962, volume 14/1, S. 1010-73 and disclosed for unsaturated derivatives of piperidine in U.S. patent No. 4 210 612.

The substrates, in which the most effective substances according to the invention are the polyolefins, such as polyethylene and polypropylene; polystyrene, especially including high impact polystyrene; Acrylonitrile-butadiene-styrene (ABS) resin; elastomers such as butadiene rubber, a copolymer of ethylene with propylene, a copolymer of ethylene, propylene and diene, styrene-butadiene and nitrile rubbers.

In General, the compounds of the invention are used in quantities of from about 0.01 to 5 wt. the weight of the stabilized composition, although this number may vary for the particular substrate and application. Best interval evenecence polymers according to traditional methods, at any convenient stage prior to the production of these molded products. For example, the stabilizer may be mixed with the polymer in the form of a dry powder or in suspension, or emulsion of the polymer. The resulting stabilized polymer compositions can also optionally contain various conventional additives.

Of particular interest is the use of these derivatives in many coating systems, including systems that are cured in air and cured acid catalyst. In particular, the physical integrity is maintained at a high level, with significant loss of gloss and yellowing. Key improvements include a significant lack of inhibition of curing due to light-stabilizers-N-alkyl dull amines; substantial absence of flocculation and destabilization of the dispersion observed in the use of N-alkyl difficult amines in some pigmented covering systems, and no loss of adhesion between the coatings and polycarbonate substrate. Accordingly, the present invention also relates to the use of these compounds, optionally together with further stabilizers, for stabilizing peacelove alkyd or polyester resins, optionally modified with silicon, isocyanates, isocyanurates, kamiminami or oxazolidinone; and epoxy resins, crosslinked carboxylic acids, anhydrides, polyamines or mercaptans; and acrylic and polyester resin systems modified with reactive groups in the main chain and cross-linked epoxides; against present and degrades the action of light, moisture and oxygen.

Additionally, if the industrial application of enamel with a high content of solids on the basis capable of crosslinking acrylic, polyester, urethane or alkyd resins otverzhdajutsja adding an acid catalyst. Light stabilizers containing a group of basic nitrogen, usually unsatisfactory in this area. The salt formation between the acid catalyst and the light-stabilizer will result in incompatibility or insolubility and precipitation of salts and to decrease the degree of cure, and the lower light shielding effect, and poor moisture resistance.

These acid catalyzed, dried in an oven varnishes based on thermally changeable acrylic, polyester, polyurethane, polyamide or alkyd resins. Varnishes of acrylic resins, which can be stabilisation acrylic paints, drying in the oven, or thermosetting resins including acrylic-melamine system, which is described, for example, in the textbook by H. Kittel "paints and coatings", vol 1, h 2, on pages 735 and 742 (Berlin 1972), in the book by H. Wagner and H. F. Sarks "Synthetic resins for lacquers" (1977), pages 229-238, and in the book of S. Pauls "Surface coatings: science and technology", (1985).

Polyester lacquers which can be stabilized against the action of light and moisture, are traditional varnishes, drying in the oven, which is described, for example, on pages 86-99 cited in the book by H. Wagner and H. F. Sarks.

Varnishes alkyd resins which can be stabilized against the effects of light and moisture in accordance with the invention, are conventional, dried in an oven lacquers, which are used in particular for coating automobiles (automobile finishing lacquers), for example lacquers based on Alcide/melamine resins and Alcide/acrylic/melamine resins (see H. Wagner and H. F. Sarx, pages 99-123). Other crosslinking agents include glycoluril resins, blocked isocyanates or epoxy resins.

Acid catalyzed, dried in an oven lucky stabilized in accordance with the invention, suitable DL is observed as well as for use in the coating of various coins. Lucky stabilized in accordance with this invention is preferably applied in a traditional way, in two ways: either by a single coating, or by the method of double coverage. In the latter case, first apply a base coat containing a pigment, and then on top of it applied top coating of transparent varnish.

It should also be noted that these substituted spatial employed amines suitable for use in thermosetting resins with nicolato catalyzed curing, such as epoxy, epoxy-polyester, vinyl, alkyd, acrylic and polyester resins, optionally modified with silicon, isocyanates or isocyanurates. These epoxy and epoxy-polyester resin bound traditional staplers, such as acids, acid anhydrides, amines, etc.

Accordingly, the epoxide can be used as a crosslinking agent for a variety of acrylic or polyester resin systems modified due to the presence of reactive groups in the structure of the main chain.

In order to achieve maximum resistance to light in takigami are above the absorbers UV-irradiation benzophenones, benzotriazoles, the production of acrylic acid or oxanilide type, or aryl-s-triazine, or metal-containing light stabilizers, for example, michelangelesque connection. In double-covered systems these additional light stabilizers can be added to the transparent coating and/or pigmented main floor.

When using such combinations, the sum of all light stabilizers constitutes from 0.2 to 20 wt. preferably from 0.5 to 5 wt. in the calculation of the film-forming resin.

Examples of different classes of absorbers of UV radiation, which can be used in these combinations together with the above-mentioned piperidine compounds discussed in the article by H. J. Heller in European Polymer Journal Supplement, 1969, pp. 105-132. These classes include phenylsalicylate, ortho-hydroxybenzophenone, hydroxyketone, benzoxazole, benzimidazole, oxadiazoles, triazoles, pyrimidines, heatline, SIMM-triazine, hydroxyphenyl-benzotriazole, alpha cyanoacrylate and benzoate.

Typical absorbers of UV radiation of particular importance are:

a) 2-(2-Hydroxyphenyl)-benzotriazole, for example 5,'-methyl-3', 5'-di-tert-butyl-, 5'-tert-butyl, 5'-(1,1,3,3-tetramet the t-amyl derivatives.

b) 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.

in) Acrylates, for example, alpha-cyano-beta, beta-diphenylacetone acid ethyl or isooctyl ester, methyl ester of alpha-carbamato-cinnamic acid, methyl or butyl ether of alpha-cyano-beta-methyl-p-methoxycatechol acid, alpha-carbomethoxy-p-methoxycatechol acid methyl ester, N-(beta-carbomethoxy-beta-cyanovinyl)-2-methylindolin.

g) Compounds of Nickel, for example, Nickel complexes of 2,2-thio-bis-/4-(1,1,3,3-TETRAMETHYLBUTYL)-phenol/, such as complexes of 1:1 or 1:2, optionally with additional ligands such as n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine, dibutyldithiocarbamate Nickel, Nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphthalate acid, monoalkyl esters, such as methyl, ethyl, or butyl, Nickel complexes of ketoximes, such as 2-hydroxy-4-phenylenediacetic, Nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazol, optionally with additional ligands.

d) a Diamide of oxalic acid, for example 4,4'-di-octyloxycinnamic, 2,2'-di-the IP-(3-dimethylamino-propyl)oxalate, 2 ethoxy-5-tert-butyl-2'-ethyloxazole, and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxyaniline and mixture of ortho - and para-methoxy-as well as ortho - and para-ethoxymethylene oxanilide.

(e) Hydroxyphenyl-SIMM-triazine, such as 2,6-bis-(2,4-dimetilfenil)-4-(2-hydroxy-4-octyloxyphenyl)-s - triazine, or the corresponding 4-(2,4-dihydroxy-phenyl)-derivative.

Especially valuable as co-stabilizers in the compositions containing the present compounds are benzotriazole with high molecular weight and low volatility, such as 2-[2-hydroxy-3,5-di(alpha-dimethylbenzyl)phenyl] -2H-benzotriazole, 2-[2-hydroxy-3,5-di-tert-octylphenyl] -2H-benzotriazole, 2-[2-hydroxy-3-alpha, alpha-dimethylbenzyl-5-tertoctylphenol]-2H-benzotriazol, 2-[2-hydroxy-3-tert-octyl-5-alpha, alpha-dimethylbenzylidene]-2H-benzotriazole, 2-[2-hydroxy-3,5-di-tert-amylphenol]-2H-benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(2-omega-hydroxycut(ethyleneoxy)carbonyl)-ethylphenyl] -2H-benzotriazol, modelirovanie 2-[2-hydroxy-5-were]-2H-benzotriazol, 2-[2-hydroxy-3-tert-butyl-5-(2-octyloxyphenyl)-ethylphenyl] -2H-without-triazole, and 5-Chloroaniline corresponding to each of the above benzotriazole.

Most preferably ensil)phenyl] -2H-benzotriazol, modelirovanie 2-[2-hydroxy-5-were]-2H-benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(2-omega-hydroxycut(ethyleneoxy)carbonyl)-ethylphenyl] -2H-benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(2-octyloxyphenyl)-ethylphenyl] -2H-benzotriazole and 5-chloro-2-[2-hydroxy-3-tert-butyl-5-(2-octyloxybiphenyl)-ethylphenyl]-2H-benzotriazole.

In addition, it is assumed that these compounds may be particularly effective as stabilizers for polyolefin fibers, especially polypropylene fibers when used in combination with other stabilizers selected from the group consisting of phenolic antioxidants, spatial obstructed light stabilizers, organic phosphorus compounds, absorbers of UV radiation and mixtures thereof.

In addition, the preferred usage of these compounds is the use of stabilized compositions containing additional postit or phosphonic. The number of phosphite or phosphonite, which is used in the compositions ranges from 0.05 to 2 wt. preferably from 0.1 to 1.0 wt. in the calculation of the film-forming resin.

Typical postit and phosphonites include triphenylphosphite, diphenylacetate, feild is, the rice-(2,4-di-tert-butylphenyl)FOSFA, di-isodicentric - diphosphite, di(2,4-di-tert-butylphenyl)pentaerythrityl, christianislamic - triphosphate, tetrakis-(2,4-di-tert-butylphenyl)-4,4-differentdifferent.

Acid catalyzed thermosetting enamel should stabilize, in order to have the corresponding functions in the areas of end use. Used stabilizers are sterically difficult amines, preferably those substituted at the nitrogen atom of inert blocking group to prevent the precipitation of the primary amine stabilized acidic catalyst, with a concomitant inhibition of curing, optionally in combination with absorbers of UV radiation, such as benzotriazole, benzophenone, substituted SIMM-triazine, phenylbenzoate or oxanilide.

To give increased durability utverzhdennym enamels (measured gloss at 20oWith the discernment of the image, cracking or clouding) these stabilizers should not slow down the curing (normal warming automotive coatings at 82oC, measured hardness, adhesion, resistance to solvents and resistance to moisture), the enamel does not have the Torah must be soluble in organic solvents, which are normally used in coatings, such as methylmercaptan, xylene, n-exilerated, alcohol, etc.

These light stabilizers employed amines, substituted on the nitrogen atom colorazione function, satisfy each of these requirements and provide by themselves or in combination with absorber UV rays effective protection of light-stabilizing utverzhdennym, acid catalyzed thermoset enamels.

The preferred embodiment of this requirement relates to stable compositions comprising an acid catalyzed thermosetting coating or enamel-based

a) thermally changeable acrylic, polyester or alkyd resins containing

b) NO-R1-substituted 2,2,6,6-tetraammineplatinum connection and

C) a UV-absorber selected from the group consisting of benzophenone, benzotriazole, acrylic acid derivatives, michelangelesque compounds, aryl-s-triazines and oxanilide.

Additional ingredients that may be contained in enamels and coatings, are antioxidants, such as sterically difficult phenolic derivatives, phosphorus compounds, such as phosphites, phosphines Ziya or dispersers.

Another preferred combination of stabilizers is to combine them with hydroxylamine to protect polypropylene fibers from gas fading.

Example 1. Bis-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)TRANS, TRANS-muconate. A solution of 1.70 g of dimethyl ester of TRANS, TRANS-Mukanova acid, 5,62 g 1 cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-ol and 0.025 g of lithium amide in 100 ml of toluene is heated under reflux and a trap Dean and stark for 8 hours Then the reaction mixture was diluted with ethyl acetate and washed with water, brine and dried over anhydrous magnesium sulfate. Upon concentration under reduced pressure followed by chromatographic separation of the receive specified in the header of the substance in the form of a white solid, melting point 181-184oC.

Example 2. 1 Cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-silt ester of carboxy-terminated polybutadiene (HYCAR 2000162). Chloride, oxalyl (2.10 ml) are added to a solution of HYCAR 2000162 (25,0 g) in 75 ml of toluene. After stirring at room temperature overnight, the reaction mixture was concentrated under reduced pressure to remove excess chlorine oxalyl. The residue is dissolved in 50 ml dry that is wala. After stirring over night the reaction mixture was filtered and concentrated under reduced pressure to obtain specified in the title compound as a light oil n2D01,5138. Analyses of IR - and NMR-spectroscopy indicate the completion of the reaction and the introduction of the polymer functional groups difficult amine.

Example 3. 1 Cyclohexyloxy-2,2,6,6-tetramethyl-4-acryloyl-oxopiperidin. A solution of 1.6 ml of chloride acryloyl in 20 ml of methylene chloride is added to mixed solution of 5.11 g of 1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-ol and 3,10 ml of triethylamine in 20 ml of methylene chloride at 0oC. After stirring at room temperature for 2 h the solvent is removed under reduced pressure. Then the resulting residue is purified by liquid chromatography to obtain specified in the title compound as a white solid with a melting point 49-52oC.

Analysis. Calculated for C18H31NO3: C 69,9 H 10,1 N 4,5.

Found C 60,0 H 10,5 N 4,5.

Example 4. 1-Cyclohexyl-2,2,6,6-tetramethyl-4-methacryloyloxyethyl. The procedure of example 3 is repeated, using 5,11 g 1 cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-ol, 2.0 ml letnogo oil n2D01,4874.

Analysis. Calculated for C19H33NO3: C 70,6 H 10,3 4,3 N.

Found: C 70,0 H 10,6 4,3 N.

Example 5. 1-Methoxy-2,2,6,6-tetramethyl-4-acryloylmorpholine. The procedure of example 3 is repeated, using 3.51 g of 1-methoxy-2,2,6,6-tetramethylpiperidine-4-ol, 1,6 ml of chloride acryloyl and 3,10 ml of triethylamine in methylene chloride. The above product is isolated in the form of a colourless liquid n2D01,4680.

Analysis. Calculated for C13H23NO3: C 64,7 H 9,6 N 5,8.

Found: C 64,0 H 9,8 N 5,6.

1-Methoxy-4-methacryloyloxy-2,2,6,6-tetramethylpiperidine get by substituting an equivalent quantity of methacryloylamido instead of akriloilkhlorida.

Example 6. 1-Cyclohexyl-2,2,6,6-tetramethyl-4-acrylamidoethyl. The procedure of example 3 is repeated using 3.0 g of 4-amino-1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine, 0,92 ml akriloilkhlorida and 1.8 triethylamine in methylene chloride. Specified in the header of the substance isolated in the form of a white solid compound, melting point 154-161oC.

Analysis. Calculated for C18H32N2O2: C 70,1 H 10,5 N 9,1.

Found: C 70,5 H 10,8 9,0 N.

Example 7. N, N-Bis-(1-cyclog the e of example 6 equivalent amount of 4-amino-1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine replaced by N,N-bis-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)amine.

Example 8. 1-Octyloxy-2,2,6.6-tetramethyl-4-acryloylmorpholine. The procedure of example 3 is repeated using an equivalent amount of 1-octyloxy-2,2,6,6-tetramethylpiperidine-4-ol instead of 1-cyclohexyl-2,2,6,6-tetramethylpiperidine-4-ol to obtain specified in the title compound as a colourless liquid. n2D51,4673.

Analysis. Calculated for C20H37NO3: C 70,8 H 11,0 N 4,1.

Found: C 71,0 H 10,8 4,6 N.

Example 9. 4 Maleimido-1 cyclohexyloxy-2,2,6,6-tetramethylpiperidine. To a solution of 5.29 g of 4-amino-cyclohexyloxy-2,2,6,6-tetramethylpiperidine in 50 ml of acetone are added dropwise over 10 min a solution of maleic anhydride (1,96 g) in acetone. After heating under reflux for 30 min receive intermediate melaminovuyu acid. The solution melaminovoi acid, sodium acetate (0.3 g) and 6.4 ml of acetic anhydride is heated at 80oC for 2 h Then the solution is concentrated under reduced pressure and the residue purified by liquid chromatography to obtain specified in the title compound as a white solid with a melting point 135-139oC.

Analysis. Calculated for C19H30N2O6C 68,2 H 9,0 N 8,4.

oC for 30 min add a solution of chloride vinylbenzyl (3,05 g) in 5 ml of N,N-dimethylformamide. The reaction mixture is heated at 75oC for 7 h and Then the reaction mixture was concentrated under reduced pressure and the residue distributed between ethyl acetate and water. The organic layer is washed with water, dried over anhydrous magnesium sulfate and then evaporated to obtain a yellow oil. By the method of preparative liquid chromatography receive specified in the title compound as light yellow oil. n2D01,5317.

Analysis. Calculated for C24H37NO2: C 77,6 H 10,0 3,8 N.

Found: C 77,4 H 10,2 3,7 N.

Example 11. 1-Octyloxy-2,2,6,6-tetramethyl-4-acryloylmorpholine. To a solution of 4-acryloyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl (10.0 g) in 150 ml of n-octane added 0.6 g of molybdenum trioxide. The resulting suspension is heated under reflux and inserted trap Dean and stark. Dropwise dobay for 8 h colorless reaction mixture is cooled to room temperature and the suspended catalyst is removed by filtration. The filtrate is stirred with an aqueous solution of sodium bisulfite for 1 hour the Organic layer was washed with brine, dried over anhydrous magnesium sulfate and then evaporated. By liquid chromatography of the residue receive specified in the title compound as a colourless liquid.

Analysis. Calculated for C20H37NO3: C 70,8 H 11,0 N 4,1.

Found: C 70,6 H 11,1 N 4,1.

Example 12. 4 Allyloxy-1-octyloxy-2,2,6,6 tetramethylpiperidine. To a solution of 4-hydroxy-1-octyloxy-2,2,6,6-tetramethylpiperidine (30.0 g, 105 mmol) in 150 ml of tetrahydrofuran, add sodium hydride (2.65 g, 110 mmol) under nitrogen atmosphere. The reaction mixture is heated under reflux for 3 h, cooled to 35oC and treated with 12.7 g (110 mmol) of allyl bromide. The reaction mixture is heated under reflux for 1 h, and then distributed between ethyl acetate (150 ml) and water (50 ml). The organic layer was washed with a saturated solution of sodium chloride (100 ml), dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue is dissolved in 50 ml of heptane and passed through a gasket with silica gel (eluent mixture 5:1 heptane + ethyl acetate). The crude product is purified by the method of flash chromatography (silage oil.

Analysis. Calculated for C20H39NO2: C 73,8 H 12,1 4,3 N.

Found: C 74,0 H 12,7 N 4,7.

Example 13. 1-Octyloxy-4-methacryloyloxy-2,2,6,6-tetramethylpiperidine. Repeat the procedure of example 3, using 1-octyloxy-4-hydroxy-2,2,6,6-tetramethylpiperidine, chloride methacryloyl and triethylamine in methylene chloride to obtain specified in the title compound as a colourless oil n2D51,4683. Data analysis of NMR and IR spectroscopy were consistent with the assigned structure.

Analysis. Calculated for C21H39NO3: C 71,3 H 11,1 4,0 N.

Found: C 71,3 H 11,2 4,2 N.

Example 14. Svetozarauladocy polypropylene. This example illustrates the effectiveness of the stabilizers of the invention as light stabilizers. The polypropylene powder (Himont Protect 6501), stabilized with 0.2 wt. n-octadecylamide ester 3,5-di-tert-butyl-4-hydroxyanisol acid is thoroughly mixed with the specified amount of additive. Then, the mixed materials are grounded on dvukhshagovoi mill at 182oC for 5 min, and then stabilized polypropylene rolls from the mill in sheet and cooled. The milled polypropylene is then cut into pieces and is formed of p is from the sample is exposed to fluorescent sunlight/black light (FS/4) in the chamber to destruction. Destruction is measured in hours, required to achieve 50 carbonyl absorption in the infrared spectrum exhibited films (see tab. 5).

Example 15. Monomeric composition comprising 23.5 butyl acrylate, 27 of butyl methacrylate, 30 2-hydroxyethylacrylate, 15 styrene, 3 acrylic acid and 1.5 acrylate monomer prepared in example 11 (all percentages are weight) and 0.4 tert-AMYLPEROXY-0-(20 ethylhexyl) monoisocyanates initiator, polimerizuet in boiling xylene to form a stabilized acrylic paleology polymer having a molecular weight of 1300 (srednetsenovoj) and 6000 (srednevekovoi).

Example 16. Stabilized acrylic polyol prepared in example 15, is mixed with a sufficient quantity of unstabilized acrylic polyol obtained by the same method of example 15, but with 1.5 wt. acrylate monomer of example 11 is replaced by butyl acrylate, so that in the following end-acrylic-melamine recipe is 1 spatial difficult amine acrylate based on the total solid resin. Acrylic-melamina recipe includes (all quantities are given in parts by weight): 70 parts of the above acrylic paleologou mixture, 18 frequent, the Irma American Cyanamide), 0.6 parts of promoter strength (FC 431, 30 solid ftoruglevodorodnye, ZM) and 8.8 parts of methylmercaptane. Thermosetting acrylic enamel is prepared using the above-quoted formulation. Pieces of steel sheet material 9,1630,48 cm, covered with polyester /epoxy primer, then coated with silver metal main floor and finally finishing enamel. The main floor is sprayed onto the coated sheet to a thickness of approximately 0,023 mm and dried in air for 3 minutes and Then the sheet is sprayed clear finishing enamel to a thickness of approximately 0.05 mm After drying in air for 10 minutes covered the sheets are heated for 30 min at 121oC. Then determined values Knapowski hardness heated surfaces.

The hardness Knoop acid hardened coatings with high solids content (present light, dry wt.):

Control 9,3

1 copolymer of example 15 9,4

+ 3 copolymer of example 15 + 3 absorber of UV radiation*9,1

1 copolymer of difficult Amin, no group H-OR1**1,0

*2-(2-hydroxy-3,5-di-tert-amylphenol)-2H-benzotriazol

**acrylic polyol, PR is the hardness values for the Coop. Higher values correspond to increased hardness and improved curing. Compounds of the invention having N-hydrocarbonate group, do not cause inhibition of curing, which is typical of such compounds are N-alkylamine.

After storage for 1 week in a room with air-conditioned, these coated panels were vysetrovani in the QUV exposure in accordance with ASTM G-53/77 using bubbles FS-40 (see table. 6).

Example 17. Prepared two-component acrylic-urethane finish coat based polyol consisting of monomers, such as 2-hydroxyethylacrylate, butyl acrylate, butylmethacrylate, styrene and Aralova acid, and aliphatic isocyanate crosslinking resin (brand Desmodur N-3390 from company Moba Bldg. ) in a ratio of 1.05/1,00, so that it included 1 wt. sitosterolemia spatial difficult Amin. Industrial available steel panels 10,1630,48 cm (company Advanced Coatings technology) first ground commercially available epoxy primer and then coated by spraying thermoplastic silver metallic primary coating to a thickness of about 0,023 mm and air-dried in accordance with the thickness of about 0,049 mm. After storage for 1 month at room air-conditioned floor panel airs in Weatherometer with xenon light. Gloss and distinction of image (RO) was measured with an interval of 300 h (see tab. 7).

Example 18. Silver metallic acrylic-alkyd enamel stabilize the specified number of absorber UV-radiation and derived spatial difficult amine (by weight of the amount of solid resin) and then sprayed to a thickness of 0.07 mm for panels, primed with epoxy-amine primer. After aging the coated panels at room temperature for 1 month they were exhibited in Weatherometer with xenon radiation, and the gloss at 60omeasured with an interval of 100 h (see tab. 8).

1. The ethylene-unsaturated polymerizable monomers on the basis of the piperidine derivative of General formula

< / BR>
where R1WITH1WITH18-alkyl or cyclohexyl;

E is a radical of the formula

< / BR>
X-FROM-CR2=CH2,

< / BR>
< / BR>
-X-CH2-CHCH2< / BR>
or

< / BR>
where X is-Oh or-NH-;

R2hydrogen or methyl;

m 10 30 integer.

2. The monomers under item 1, where R2the hydrogen.

3. The monomers under item 1, where R2

 

Same patents:

w-geksamolibdenoalyuminat as material for articles of correction" target="_blank">

The invention relates to the field of synthesis of polymeric materials used to produce products vision correction contact lenses and artificial lenses

The invention relates to the production of copolymers of N-vinyl-3(5)-methylpyrazole (VMP), which can be used in the chemical industry for the manufacture of materials with improved thermal and chemical resistance

The invention relates to the field of polymer chemistry, namely to a new biologically active chemical compound to the copolymer of 2-methyl-5-vinylpyridine) - derivatives and N-vinylpyrrolidone formula

where the average number of links 2-methyl-5 - vinylpyridine) - derivatives n = 35 and srednevozrastnoe molecular mass M= 40000 daltons with antitumor activity

FIELD: organic chemistry, polymers, chemical technology.

SUBSTANCE: invention relates to a method for preparing oligomer based on epoxy resin E-40. Method involves carrying out the condensation reaction of epoxy resin E-40 and 4-hydroxy-2,2,6,6-tetramethylpiperidine in melt at temperature 130-200°C for 2-14 h. Prepared oligomer can be used as a highly effective non-staining photostabilizing agent of polymer materials (polyolefins, polyurethanes and others). Invention provides reducing the process time and energy consumptions and to carry out the process in the absence of solvent.

EFFECT: improved preparing method.

4 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing aminoxyl ethers, for example, N-hydrocarbyloxy-derivatives of steric hindranced amines that can be used as light- and/or thermostabilizing organic materials and/or a regulator in the polymerization reaction. Invention describes a method for preparing aminoxyl ethers by interaction of the corresponding N-oxyl derivative with hydrocarbon organic solvent in the presence of organic peroxide and a catalyst representing copper or copper compound, preferably, inorganic compound Cu (I) or Cu (II) as a solution in suitable solvent chosen in the catalytically effective amount. Method provides preparing the end product with the high yield by simplified technological schedule and without using high temperatures.

EFFECT: improved method of synthesis.

15 cl, 2 tbl, 27 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the chosen N-alkoxy-4,4-dioxypolyalkylpiperidine compounds comprising glycidyl or carbonyl functional groups and possessing acyclic or cyclic ketal structure. Invention describes compounds of formulae (Ia) , (IIa) or (IIIa) wherein D means group of the formula ; m means 1; n means 1; each among Y and Y' means independently (C1-C12)-alkyl, (C3-C12)-alkenyl, phenyl or benzyl, or Y and Y' form in common one of the following bivalent groups: -C(R1)(R2)-CH(R3)-, -CH(R1)CH2-C(R2)(R3)-, -CH(R2)-CH2-C(R1)(R3)-, -CH2-C(R1)(R2)-CH(R3)-, -CH2-CH=CH-CH2- wherein R1 means hydrogen atom, (C1-C12)-alkyl, -COO-(C1-C12)-alkyl or -CH2OR4; each among R2 and R3 means hydrogen atom, methyl, ethyl or -COO-(C1-C12)-alkyl; R4 means hydrogen atom, (C1-C12)-alkyl, benzyl or monovalent acyl residue of aliphatic, cycloaliphatic or aromatic monocarboxylic acid comprising up to 12 carbon atoms; one R12 means hydrogen atom (H) and another radical means -CH3 group. Also, invention describes a composition able for polymerization, a method for preparing oligomer, co-oligomer, polymer or co-polymer, using compounds of the formulae (Ia), (IIa) or (IIIa) for polymerization of ethylene-unsaturated monomers, using compounds of the formulae (Ia), (IIa) or (IIIa) for breaking chain in anionic polymerization of diene or vinyl monomer, compounds of the formulae (Xd), (XId) and (XIId) given in the invention description. Proposed compounds provide preparing polymeric resinous substances showing low polydispersity and carrying out the polymerization process with good effectiveness in conversion of monomer to polymer.

EFFECT: valuable chemical properties of compounds.

15 cl, 7 tbl, 30 ex

FIELD: organic chemistry, chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to using hydroxylamine esters for decreasing molecular mass of polypropylene, propylene copolymers or polypropylene mixtures. Method involves addition to propylene polymers subjected for destruction at least one hydroxylamine ester chosen from group including compound of the formula (IA): wherein n means 1; Ra means aliphatic carboxylic acid acyl radical comprising from 2 to 18 carbon atoms; R'1, R'2 and R'3 mean independently of one another hydrogen atom or methyl group; G means aliphatic carboxylic acid acyl-acyl radical comprising from 1 to 18 carbon atoms or aromatic carboxylic acid acyl-acyl radical comprising from 7 to 18 carbon atoms of the formula (IB): wherein n means 1; Ra means aliphatic carboxylic acid acyl radical comprising from 2 to 18 carbon atoms; each R'1, R'2 and R'3 means independently of one another hydrogen atom or methyl group; G1 means hydrogen atom, (C2-C18)-alkanoyl; G2 means hydrogen atom, (C1-C8)-alkyl, aliphatic carboxylic acid acyl-acyl radical comprising from 1 to 18 carbon atoms of the formula (IC): wherein n means 1; Ra means aliphatic carboxylic acid acyl radical comprising from 2 to 18 carbon atoms; each R'1, R'2 and R'3 means independently of one another hydrogen atom or methyl group; G means (C2-C8)-alkylene, (C4-C22)-acyloxyalkylene or aliphatic carboxylic acid acyl radical comprising from 1 to 18 carbon atoms and this mixture is heated to temperature below 280°C. Addition of hydroxylamine esters results to increasing the destruction degree of used polypropylene polymer that is reflected by the melt efflux velocity value in comparison with this index of the parent polymer.

EFFECT: improved method for molecular mass decreasing.

3 cl, 15 tbl

FIELD: organic synthesis.

SUBSTANCE: preparation of 2,2,6,6-tetramethylpyperidine-1-oxyl depicted by general formula: comprises providing a stock solution at room temperature and is characterized by that through solution comprised of sodium sulfate, methylene dichloride, and 1-chloro-2,2,6,6-tetramethylpyperidine of general formula: in membrane-free electrolyzer with platinum electrodes, 1.5 A electric current is passed during 3 h.

EFFECT: expanded synthetic possibilities in nitroxyl compounds area and reduced process expenses.

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention relates to N-oxide and/or di-N-oxide derivatives of stabilisers/modulators of dopamine receptors, which have formula (2) (given in description) and to their pharmaceutical preparations, containing said compounds.

EFFECT: invention relates to application of said compounds for treating central nervous system disorders, in particular, for treatment of dopamine-mediated disorders, such as motor disorders, psychoses, anxiety disorders, impaired development of nerves, sleep disorders and disorders, associated with substances.

9 cl, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to compound of formula stabilised composition with thereof application, method for stabilisation of natural or synthetic organic polymer against destruction, caused by light, heating or oxidation, as well as to application of formula (A) compound for stabilisation of natural or synthetic organic polymer against thermal, oxidative or light destruction. In formula (A) R1 independently on each other represent methyl, ethyl or n-propyl, and X represents C2-C8alkylene or C2-C8alkylene, containing sulphur atom in chain.

EFFECT: elaboration of method for stabilisation of natural or synthetic organic polymer against destruction.

9 cl, 2 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: invention relates to compounds that are represented by the following structural formulas:

The intermediate compound of formula (I), wherein the radicals R1 independently represent methyl, ethyl or n-propyl, for preparing a compound of formula (A), wherein X represents a group of formula (A-I) or (A-II), Y represents C11-C17alkyl, and Z is a direct bond, - (CH2)8- or -CH2-S-CH2-.

EFFECT: compound of formula (A) may be used for stabilizing organic material against thermal, oxidative or light-decomposition.

13 cl, 2 tbl, 7 ex

FIELD: pharmaceutics.

SUBSTANCE: invention provides multifunctional nitric oxide derivatives of formula I: I, where Y is N, CH or N(→O), or its enantiomer, diastereomers, racemic mixture or its pharmaceutically acceptable salt or solvate, where A is a fragment of general formula II connected through its terminal -NH group with any atom of carbon of pyridine, phenyl or pyridine-oxide ring: II; X is absent or is -(CR2R2)n-; R1 is absent or is represented by from 1 to 5 substituents, each of which is independently selected from a halogen, -CN, -OH, -NO2, -N(R6)2, -OCF3, -CF3, -OR6, -COR6, -COOR6, -CON(R6)2, -OCOOR6, -OCON(R6)2, -(C1-C8)alkyl, -(C1-C8)alkylen-COOR6, -SR6, -SO2R6, -SO2N(R6)2 or -S(=O)R6; R2 is H; R3 each independently represents a (C1-C8)alkyl; R4 is selected from H or -(C1-C8)alkyl; R5 is selected from H or -CN; R6 each is independently selected from H or (C1-C8)alkyl and n is an integer equal to 1 or 2.

EFFECT: said compounds contain a potassium channels opener and a catalyst for degradation of reactive forms of oxygen (RFO), which can act as an antioxidant; also proposed are pharmaceutical compositions containing the said compounds, which can be used for treating diseases, disorders or conditions related to oxidative stress or endothelial dysfunction.

19 cl, 9 dwg, 5 tbl, 14 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a composition of an amine-based additive for controlling and inhibiting polymerisation of vinyl aromatic monomers, including styrene containing (a) one or more of nitroxide (i.e. nitroxy) compounds and (b) one or more of aromatic nitro compounds; characterised by that said composition additionally contains one or more of (c) amines, characterised by that said amine contains hydroxyl alkyl tertiary amines, including tris(2-hydroxypropyl) amine (TIPA); Ν,Ν,Ν',Ν'-tetrakis(2-hydroxypropyl) ethylene-diamine (Quadrol); N,N,N',N'-tetrakis(2-hydroxyethyl) ethylene-diamine (THEED) or their mixture. Present invention also relates to a method of monitoring and inhibiting polymerisation of vinyl aromatic monomers, including styrene, by adding proposed composition, as well as methods of producing and using proposed composition for controlling and inhibiting said polymerisation.

EFFECT: control and inhibition of polymerisation of vinyl aromatic monomers.

16 cl, 6 tbl, 5 ex

FIELD: carbon materials.

SUBSTANCE: invention provides water-soluble C60-fullerene complexes with N-vinylcaprolactam homo- and copolymers described by general formula An or An-Bm, in which An represents N-vinylcaprolactam homopolymer and An-Bm copolymer wherein A are N-vinylcaprolactam units and B units selected from series including units of N-vinylpyrrolidone, N-methyl-N-vinylacetamide and N-isopropylacrylamide, n=10-90 mol % and m=10-90 mol %, provided that molecular mass of N-vinylcaprolactam homo- and copolymers ranges from 70000 to 170000 Da and content of C60-fullerene ranges from 0.75 to 3.3 wt %. The complexes are prepared via interaction of polymers with fullerene in organic solvents followed by removal of derivatives and dissolving dry residue in water. Starting polymer and fullerene are used in the form of their solution, the former in concentration 3.33-5.80% and the latter in concentration 0.09-0,32%, fullerene-to-polymer weight ratio ranging between 0.8:1 and 4.0:1.

EFFECT: expanded synthetic possibilities in the fullerene series.

2 cl, 1 tbl, 10 ex

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to a bicomponent polymerazible composition consisting of two components. The first component includes complex of organoborane and amine comprising trialkylborane and one or some compounds comprising at least one heterocyclic fragment with an opening cycle. The second component includes Lewis acid able to initiate polymerization of compounds comprising heterocyclic functionality with opening cycle. These compounds are able to take part in free-radical polymerization wherein heterocyclic fragment with opening ring represents a substituted three-membered ring with oxygen atom as a heteroatom. Also, invention relates to a method for polymerization of abovementioned composition, to method for gluing two or more substrates each with other, to method for modifying a polymer surface of low surface energy, to method for applying cover on substrate using the claimed composition, and to composition for applying a cover comprising abovementioned composition, and to laminate. Invention provides preparing adhesive compositions able providing adhesion to substrates of low surface energy and to glue their to other substrates without carrying out the vast preliminary treatment. The composition possesses improved stability, strength and adhesion at increased temperatures.

EFFECT: improved and valuable properties of compositions.

11 cl, 15 tbl, 81 ex

FIELD: chemistry of high-molecular compounds, chemical technology.

SUBSTANCE: invention relates to novel nitrogen- and sulfur-containing cross-linked copolymers of 1-vinyl-1,2,4-triazole with divinyl sulfide that can be used for extraction of gold, silver and platinum from acid solutions. Invention relates to a method for synthesis of cross-linked copolymer of 1-vinyl-1,2,4-triazole with divinyl sulfide for a single step and without using a solvent. Method involves the copolymerization reaction of divinyl sulfide being both as a second monomer and as a cross-linking agent. Synthesized copolymers show high chemical stability, multiple using in cycles sorption-desorption, effective chelating capacity and high values of sorption capacity with respect to ions of precious metals, possibility for extraction of precious metals from complex solution and high values of the partition coefficients that allows their using for extraction of low concentrations of precious metals. Above indicated copolymer comprising triazole cycles is synthesized by the copolymerization reaction of 1-vinyl-1,2,4-triazole and divinyl sulfide without solvent under condition of radical initiating with azobis-isobutyric acid dinitrile (2% of monomers mixture mass) at temperature 60°C for 0.25-2 h, in argon atmosphere followed by washing out copolymer with ethyl alcohol. Synthesized copolymer has the general formula given in the invention description wherein n = 35-81 mole%; m = k = 19-65 mole%.

EFFECT: improved method of synthesis.

3 cl, 5 tbl, 9 ex

FIELD: chemistry.

SUBSTANCE: invention pertains to the field of high molecular compounds, and specifically to new nitrogen and oxygen containing network copolymers of 1-vinyl-1,2,4-triazole with divinyl ester of diethylene glycol, which can be used for sorption of gold, silver, platinum, and palladium from acidic solutions. The given engineering problem can be solved by that, network copolymers of 1-vinyl-1,2,4-triazole with divinyl ester of diethylene glycol with general formula: , where n = 94-65 mol. %, m + k = 6-35 mol. %, used as an effective sorbent of gold, silver, platinum and palladium from acidic solutions are synthesised through copolymerisation of 1 -vinyl-1,2,4-triazole with divinyl ester of diethylene glycol in bulk, without a solvent under conditions of radical initiation through dinitrile oleic acid (2 % of the mass of the mixture of monomers), at 60 °C, for a period of 0.17-1.5 hours, in an argon atmosphere with subsequent washing of the network copolymer using ethanol in Soxhlet apparatus and drying in a vacuum until a constant mass is obtained. The ester of diethylene glycol is used as the second polymer and as a cross-linking agent at the same time.

EFFECT: invention can be used for sorbtion of gold, silver, platinum and palladium from acidic solutions.

3 cl, 5 tbl, 9 ex

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