RU2126393C1 - Substituted benzotriazoles and stabilized composition, and covering system comprising said benzotriazoles - Google Patents

Abstract

FIELD: chemical industry. SUBSTANCE: present invention describes substituted benzotriazoles of general formula (A)

wherein R is hydrogen, straight or branched alkyl containing 1-24 carbon atoms, or phenylalkyl containing 7-15 carbon atoms; R₂ is straight or branched alkyl containing 1-24 carbon atoms, and phenylalkyl containing 7-15 carbon atoms, said alkyl being substituted by one or more hydroxy groups, or radical of formula -CH₂CH₂COR₅ wherein R₅ is NH₂ or OR₆ wherein OR₆ is (OCH₂CH₂)_wOH wherein W is 1 to 12, or R₂ is (CH₂)_m-CO-X(Z)_p-Y-R₁₅ wherein X and Y are -O-; Z is alkylene containing 3-12 carbon atoms substituted by hydroxy group; R₁₅ is CO-C(R₁₈= CH₂ wherein R₁₈ is hydrogen or methyl, m is 0,1 or 2, and p is 1; R₃ is alkyl containing 8-20 carbon atoms, phenyl-alkyl containing 7-15 carbon atoms, aryl containing 6-10 carbon atoms, or R₃ is radical of formula

wherein E is C₂-C₁₂ alkylene, C₅-C₁₂ cycloalkylene or E is C₈-C₁₂ alkylene interrupted by cyclohexylene, r is 0 or 1. The present invention describes stabilized composition comprising polymer which becomes destructible when exposed to unfavorable effect of actinic radiation, and substituted benzotriazole of formula (A). The present invention also describes covering system comprising effective amount of substituted benzotriazole of formula (A) as stabilizer. The claimed compounds and compositions based on said compounds have higher UV spectral power at higher wave-length values than those of the well known analogs. EFFECT: improved properties of the covering system. 21 cl, 28 ex

Description

 The present invention relates to substituted benzotriazoles, in particular to 2- (2-hydroxyphenyl) -2H-benzotriazoles substituted at the 5-position with a thioether group, and to stabilized compositions and coating systems containing such compounds.

 2- (2-Hydroxyphenyl) -2H-benzotriazoles are a very important class of commercial UV absorbers, which are widely used as stabilizers to protect a wide range of organic substrates from the adverse effects of actinic radiation.

 The commercial and technical interest in this class of compounds is due to a number of publications and patents describing this general class of compounds. Several of these references relate to substituted 2H-benzotriazoles by any group containing sulfur, not to mention the thioether group.

 European Patent Application EP 0323853A (1989), relating to the stabilization of color photographic material, discloses in general terms 2H-benzotriazole derivatives which may be substituted on the benz ring, on the phenyl ring or on both rings by a number of possible substituents, including, inter alia, alkylthio - or arylthio groups. Only 5-methylthio-2- (2-hydroxy-3-sec-butyl-5-tert-butylphenyl) -2H-benzotriazole is specifically mentioned. This reference describes benzotriazoles very broadly without giving examples of compounds substituted with an alkylthio or arylthio group at position 5, and it does not disclose favorable stabilizing properties when the alkylthio or arylthio group is located at position 5 of the benz ring.

 US Pat. No. 3,766,205A describes 5-mercapto-2- (2-hydroxy-3,5-dimethylphenyl) -2H-benzotriazole and an ester obtained by Michael addition of the indicated mercaptan to ethyl acrylate. The present compounds are structurally different from the Michael addition products described in this link. Known Michael addition products are susceptible to thermal retroreflection by Michael with elimination of the acrylate group. Such compounds can be expected to have lower heat resistance compared to the proposed compounds.

 The proposed compounds and compositions differ from compounds known in this field. None of these references disclose that substitution of 2H-benzotriazole at position 5 of the benzene ring with an alkylthio, arylthio, or aralkylthio group leads to a significant increase in UV spectral absorption and also a shift of the maximum absorption value by about 20 nm in the direction of a longer wavelength relative to benzotriazole without 5 substitution. This increased spectral absorption, combined with a redshift of the maximum absorption towards higher wavelengths, increases the protection of substrates that are sensitive to UV light with a higher wavelength (almost visible), such as coating materials, plastics and fibers.

 An object of the present invention is to provide 5-thio-substituted 2H-benzotriazoles having increased UV spectral absorption at higher wavelengths compared to known benzotriazoles.

 Another objective of the present invention is to obtain stabilized compositions that contain an effective stabilizing amount of 5-thiosubstituted 2H-benzotriazole.

 Another objective of the present invention is to obtain 5-thio-substituted 2H-benzotriazoles, which contain reactive parts, ensuring their introduction through chemical bonds in a number of substrate materials, which gives a non-migratory character relative to these substrates.

 Another objective of the present invention is to develop a new method for producing such 5-thiosubstituted 2H-benzotriazoles.

где R₁ означает водород, прямоцепочечный или разветвленный алкил, содержащий от 1 до 24 атомов углерода или фенилалкил с 7-15 атомами углерода;
R₂ означает прямоцепочечный или разветвленный алкил, содержащий от 1 до 24 атомов углерода, фенилалкил, содержащий от 7 до 15 атомов углерода, причем указанный алкил может быть замещен одной или более гидроксигруппой, или радикал формулы -CH₂CH₂COR₅, где R₅ означает -NH₂ или -OR₆, где R₆ означает водород, алкил, содержащий от 1 до 24 атомов углерода, незамещенный или замещенный гидроксигруппой, или OR₆ означает -(OCH₂CH₂)_wОН, где w равно от 1 до 12, или
R₂ означает -(CH₂)_m-CO-X-(Z)-Y-R₁₅, где X и Y обозначают -O-, Z - алкилен с числом углеродных атомов от 3 до 12, замещенный гидроксильной группой, R₁₅ - группа -CO-C(R₁₈)=CH₂, где R₁₈ - водород или метил, m = 0, 1 или 2, а p = 1;
R₃ означает алкил с числом атомов углерода от 8 до 20, фенилалкил, содержащий от 7 до 15 атомов углерода, арил с числом атомов углерода от 6 до 10, или R₃ представляет собой радикал формулы В1

где E означает C₂-C₁₂алкилен, C₅-C₁₂циклоалкилен или C₈-C₁₂алкилен, прерванный циклогексиленом,
r = 0 или 1.The present invention relates to substituted benzotriazoles of the general formula A

where R ₁ means hydrogen, straight-chain or branched alkyl containing from 1 to 24 carbon atoms or phenylalkyl with 7-15 carbon atoms;
R ₂ is straight chain or branched alkyl containing from 1 to 24 carbon atoms, phenylalkyl containing from 7 to 15 carbon atoms, wherein said alkyl may be substituted with one or more hydroxy groups, or a radical of the formula —CH ₂ CH ₂ COR ₅ , where R ₅ means —NH ₂ or —OR ₆ , where R ₆ is hydrogen, alkyl containing from 1 to 24 carbon atoms, unsubstituted or substituted with hydroxy, or OR ₆ means - (OCH ₂ CH ₂ ) _w OH, where w is from 1 up to 12, or
R ₂ means - (CH ₂ ) _m —CO — X— (Z) —YR ₁₅ , where X and Y are —O—, Z is alkylene with the number of carbon atoms from 3 to 12, substituted with a hydroxyl group, R ₁₅ is a group -CO-C (R ₁₈ ) = CH ₂ , where R ₁₈ is hydrogen or methyl, m = 0, 1 or 2, and p = 1;
R ₃ means alkyl with the number of carbon atoms from 8 to 20, phenylalkyl containing from 7 to 15 carbon atoms, aryl with the number of carbon atoms from 6 to 10, or R ₃ represents a radical of the formula B1

where E is C ₂ -C ₁₂ alkylene, C ₅ -C ₁₂ cycloalkylene or C ₈ -C ₁₂ alkylene interrupted by cyclohexylene,
r = 0 or 1.

A preferred group of compounds includes substituted benzotriazoles of formula A, wherein
R ₁ means hydrogen, straight chain or branched alkyl with the number of carbon atoms from 1 to 24 or phenylalkyl with the number of carbon atoms from 7 to 15;
R ₂ means straight-chain or branched alkyl, with the number of carbon atoms from 1 to 24, or phenylalkyl containing from 7 to 15 carbon atoms, wherein said alkyl may be substituted with one or more hydroxy groups;
or R ₂ is a group of the formula —CH ₂ CH ₂ COR ₅ , where R ₅ is —NH ₅ or —OR ₆ , where R ₆ is hydrogen or alkyl with 1 to 24 carbon atoms, unsubstituted or substituted with one or more hydroxy groups, or OR ₆ means - (OCH ₂ CH ₂ ) _w OH, where w is from 1 to 12, or
R ₂ means - (CH ₂ ) _m —CO — X— (Z) _p —YR ₁₅ , where X and Y are —O—, Z is alkylene with 3 to 12 carbon atoms, substituted with a hydroxyl group, R ₁₅ means the group -CO-C (R ₁₈ ) = CH ₂ , where R ₁₈ is hydrogen or methyl, m = 0, 1 or 2, and p = 1;
R ₃ means alkyl with the number of carbon atoms from 8 to 20, phenylalkyl containing from 7 to 15 carbon atoms, aryl with the number of carbon atoms from 6 to 10.

Most preferred are substituted benzotriazoles of formula A, wherein
R ₁ means hydrogen, branched alkyl with the number of carbon atoms from 4 to 8, benzyl, α-methylbenzyl, α, α-dimethylbenzyl,
R ₂ means straight-chain or branched alkyl with the number of carbon atoms from 1 to 8, substituted by one or more hydroxyl groups; or R ₂ is benzyl, α-methylbenzyl or α, α-dimethylbenzyl; or R ₂ is a group of the formula —CH ₂ CG ₂ COR ₅ , where R ₅ is —NH ₂ or —OR ₆ , where R ₆ is hydrogen or alkyl with 1 to 24 carbon atoms, unsubstituted or substituted with one or more hydroxy groups, or OR ₆ means - (OCH ₂ CH ₂ ) _w OH, where w is from 1 to 12, or
R ₂ means - (CH ₂ ) _m —CO — X— (Z) _p —YR ₁₅ , where X and Y are —O—, Z is alkylene with 3 to 8 carbon atoms, substituted with a hydroxyl group, R ₁₅ means the group -CO-C (R ₁₈ ) = CH ₂ , where R ₁₈ is methyl, m = 2, and p = 1; and
R ₃ means phenyl or alkyl with the number of carbon atoms from 8 to 12.

Particularly preferred are substituted benzotriazoles, which are compounds selected from the group consisting of:
(a) 5-n-dodecylthio-2- (2-hydroxy-3,5-di-tert.-butylphenyl) -2H-benzotriazole;
(b) 5-phenylthio-2- (2-hydroxy-3,5-di-tert.-butylphenyl) -2H-benzotriazole;
(c) 5-phenylthio-2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole;
(g) 5-benzylthio-2- (2-hydroxy-3-tert. butyl-5-methylphenyl) -2H-benzotriazole;
(e) 5-phenylthio-2- (2-hydroxy-3-tert. butyl-5-methylphenyl) -2H-benzotriazole;
(e) 5-n-octylthio-2- (2-hydroxy-3,5-di-tert.-butylphenyl) -2H-benzotriazole;
(g) 5-tridecylthio-2- (2-hydroxy-3,5-di-tert.-butylphenyl) -2H-benzotriazole;
(h) 5.5 '- (1,8-dithiaoctane-1,8-diyl) bis [2- (2-hydroxy-3,5-di-tert-butylphenyl) -2H-benzotriazole];
(i) 5.5 '- (dithihydrolylo-mononediyl) bis [2- (2-hydroxy-3,5-di-tert-butyl-phenyl) -2H-benzotriazole];
(k) 5-phenylthio-2- (2-hydroxy-3,5-di-tert.-octylphenyl) -2H-benzotriazole;
(l) 5-phenylthio-2- (2-hydroxy-3,5-di-α-cumylphenyl) -2H-benzotriazole;
(m) 5.5'-thiobis- [2- (2-hydroxy-3,5-di-tert.-butylphenyl) -2H-benzotriazole];
(m) 5-phenylthio-2- [2-hydroxy-3-tert.-butyl-5- - (β-carboxyethyl) phenyl] -2H-benzotriazole;
(o) 5-phenylthio-2- [2-hydroxy-3-tert. -butyl-5 - (β-octyloxycarbonylethyl) phenyl] -2H-benzotriazole;
(p) 5-phenylthio-2- {2-hydroxy-3-tert. -butyl-5- [2- (ω-hydroxyocta (ethyleneoxy) carbonylethyl] phenyl} -2H-benzotriazole;
(p) 5-phenylthio-2- [2-hydroxy-3-tert. -butyl-5- (3-hydroxypropyl) phenyl] -2H-benzotriazole;
(c) 3- (5-phenylthio-2H-benzotriazol-2-yl) -5-tert.-butyl-4-hydroxyhydrocinnamic acid;
(t) 3- (5-phenylthio-2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyhydrocinnamic acid amide;
(y) an isomeric mixture of 3- [3- (5-phenylthio-2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyhydrocinnamoyloxy] -2-hydroxypropylmethacrylate and 2- [3- (5-phenylthio- 2H-benzotriazol-2-yl) -5-tert. -butyl-4-hydroxyhydrocinnamoyloxy] -3-hydroxypropylmethacrylate;
(f) ω-hydroxypoly (ethyleneoxy) -3- (5-phenylthio-2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyhydrocinnamate.

When any of R ₁ -R ₃ is 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 any of these radicals is phenylalkyl, such groups include, for example, benzyl, phenethyl, α-methylbenzyl and α, α-dimethylbenzyl. When any of these radicals is aryl, such groups include, for example, phenyl, naphthyl, which may be substituted by alkyl, for example, tolyl and xylyl.

When R ₆ is alkyl substituted with OH, such groups include, for example, 2-hydroxyethyl, 2-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyethyl. When R ₆ is alkyl substituted with one or more —O— groups and / or substituted with one or more —OH groups, part of OR ₆ may mean - (OCH ₂ —CH ₂ ) _w OH, where w is 1-12.

As a C ₃ -C ₁₂ alkylene substituted with a hydroxyl group, Z is 2-hydroxytetramethylene, 2-hydroxyhexamethylene and especially 2-hydroxytrimethylene.

 When E is, for example, alkylene, the values are, for example, ethylene, tetramethylene, hexamethylene, 2-methyl-1,4-tetramethylene, hexamethylene, octamethylene, decamethylene and dodecamethylene; when E is cycloalkylene, values are, for example, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene and cyclododecylene; and when E is alkylene interrupted or terminated by cyclohexylene, the meanings are, for example, a saturated diyl radical derived from limonene, referred to herein as dihydrolimonenediyl.

When the compounds of the invention contain a free carboxyl moiety, R ₂ is —CH ₂ CH ₂ COOR ₂ , where R ₆ is hydrogen, alkali metal or amine salts of these acids are also intended to be 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 stabilized compositions, which include (a) a polymer subjected to destruction caused by the adverse effects of actinic radiation, and (b) an effective stabilizing amount of the above substituted benzotriazole of formula A.

 Such polymers, in particular, include polymers that contain aromatic parts, for example polystyrene, grafted copolymers of styrene, for example, a copolymer of acrylonitrile, butadiene and styrene (ABS), polyphenylene oxides, polyphenylene sulfides, polyurethanes, polyisocyanates, aromatic polyesters, aromatic polyamides, polyureas, polyimides, polyamidimides, polysulfones, polyethersulfones, polyethersetons, alkyd resins, aminos and epoxies.

 The most preferred synthetic polymer is epoxy.

 Preferably, the stabilized composition as component (b) contains 5-n-dodecylthio-2- (2-hydroxy-3,5-di-tert.-butylphenyl) -2H-benzotriazole; 5-phenylthio-2- (2-hydroxy-3,5-di-tert-butylphenyl) -2H-benzotriazole; 5-phenylthio-2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole; 5-n-octylthio-2- (2-hydroxy-3,5-di-tert-butylphenyl) -2H-benzotriazole; 5-phenylthio-2- (2-hydroxy-3,5-di-α-cumylphenyl) -2H-benzotriazole ω-hydroxypoly (ethyleneoxy) -3- (5-phenylthiobenzotriazol-2-yl) -5-tert-butyl - 4-hydroxyhydrocinnamate.

 Compositions of particular interest include those that contain (a) a polymer that is degraded by the adverse effects of actinic radiation, and which are a coating system consisting of a lower polymer layer that contains inorganic and / or organic pigments and an upper coating a polymer layer, and (b) an effective stabilizing amount of a substituted benzotriazole of formula A, either in the upper polymer layer, or in the lower polymer layer, or in both polymer layers.

 As a substituted benzotriazole, the coating system preferably contains 5-phenylthio-2- (2-hydroxy-3,5-di-tert-butylphenyl) -2H-benzotriazole, 5-phenylthio-2- [2-hydroxy-3-tert. -butyl-5 - (β-octyloxycarbonylethyl) phenyl] -2H-benzotriazole, 5-phenylthio-2- {2-hydroxy-3-tert-butyl-5- [2 - (ω-hydroxyocta (ethyleneoxy) -carbonylethyl] phenyl} -2H-benzotriazole, ω-hydroxypoly (ethyleneoxy) -3- (5-phenylthiobenzotriazol-2-yl) -5-tert-butyl-4-hydroxyhydrocinnamate.

 Of particular interest are 5-phenylthio-2- {2-hydroxy-3-tert.-butyl-5- [2 - (ω-hydroxyocta (ethyleneoxy) -carbonylethyl] phenyl} -2H-benzotriazole and ω-hydroxypoly (ethyleneoxy) - 3- (5-phenylthiobenzotriazol-2-yl) -5-tert-butyl-4-hydroxyhydrocinnamate as a stabilizer in these coating systems.

 Other compositions of particular interest include those that further comprise a UV absorber selected from the group consisting of benzophenones, benzotriazoles, derivatives of cyanoacrylic acid, hydroxyaryl-s-triazines, organic compounds of nickel and oxanilides located either in the upper or in the lower polymer layer, or in both polymer layers.

 Preferred UV absorbers are selected from the group consisting of 2- [2-hydroxy-3,5-di - (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (2-hydroxy-3,5-di tert. -amylphenyl) -2H-benzotriazole, 2- [2-hydroxy-3-tert.-butyl-5 - (ω-hydroxyocta (ethyleneoxy) carbonyl) ethylphenyl] -2H-benzotriazole, 2- [2-hydroxy-3 third. -butyl-5- (2-octyloxycarbonylethyl) phenyl] -2H-benzotriazole, 4,4'-dioctyloxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide, 2,2'-didodecyloxy- 5.5'-di-tert. -butyloxanilide, 2-ethoxy-2'-ethyloxanilide, 2,6-bis (2,4-dimethylphenyl) -4- (2-hydroxy-4-octyloxyphenyl) -8-triazine, 2,6-bis (2,4 -dimethylphenyl) -4- (2,4-dihydroxyphenyl) -s-triazine, 2,4-bis (2,4-dihydroxyphenyl) -5- (4-chlorophenyl) -s-triazine, 2,6-bis (2 , 4-dimethylphenyl) -4- [2-hydroxy-4- (2-hydroxy-3-dodecyloxypropanoxy) phenyl] -s-triazine and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone.

 The coating system preferably further comprises an effective stabilizing amount of a phenolic antioxidant in either the upper or lower polymer layer, or in both polymer layers. It may also additionally contain a derivative of the hindered amine, or additionally contain a phosphite or phosphonite stabilizer, either in the upper or lower or in both layers in an effective amount.

 Of particular interest are coating systems, which are enamel with a high solids content, which is used for industrial coating, for example, coating coils, as a penetrating wood finish or as a film-forming wood finish.

 When the compounds of the invention also contain a reactive functional group, such compounds can be chemically bonded either by a condensation reaction or by a radical reaction of addition to a polymer substrate. This results in a non-migratory, non-sublimable UV absorber stabilizer. Such reactive functional groups include hydroxy, amino, amido, carboxyl and ethylene unsaturated moieties.

 Various organic substances useful in the present invention are described in more detail below together with various co-additives, the co-use of which with the present compounds is often extremely beneficial.

 Another object of the present invention is a method by which substituted benzotriazoles of formula A are prepared, which comprises reacting 5-halogen-substituted 2H-benzotriazoles with aliphatic and aromatic thiols.

The reaction is preferably carried out in an aprotic solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and the like, at a temperature between 30 and 200 ^° C in the presence of a suitable acceptor of a hydrogen halide such as oxide, carbonate, hydroxide and so on alkali or alkaline earth metal.

с алифатическим, фенилалкильным или ароматическим меркаптаном формулы
R₃SH
где R₁, R₂ и R₃ имеют вышеприведенные значения, в апротонном растворителе при температуре от 30 до 200^oC в присутствии оксида, карбоната или гидроксида щелочного или щелочноземельного металла.This process for the preparation of a compound of formula A involves the reaction of a 5-halogen substituted 2H-benzotriazole derivative of the formula

with an aliphatic, phenylalkyl or aromatic mercaptan of the formula
R ₃ SH
where R ₁ , R ₂ and R ₃ have the above meanings, in an aprotic solvent at a temperature of from 30 to 200 ^o C in the presence of an oxide, carbonate or hydroxide of an alkali or alkaline earth metal.

 The reaction can also be carried out in non-polar hydrocarbon solvents, such as xylene or mesitylene, or using the above polar solvents as co-solvents or only in hydrocarbon solvents under phase transfer conditions.

Альтернативная методика получения предлагаемых соединений состоит в присоединении 5-меркаптозамещенного 2Н-бензотриазола посредством одной или более двойных связей ненасыщенной молекулы. При использовании диена или циклодиена получают бис-соединение, присоединенное частью -S-E-S-, где E обозначает алкилен или циклоалкилен.This reaction is schematically shown in the equation below:

An alternative method for preparing the compounds of the invention is the addition of a 5-mercapto-substituted 2H-benzotriazole via one or more double bonds of an unsaturated molecule. By using diene or cyclodiene, a bis compound is attached, attached by the —SES— part, where E is alkylene or cycloalkylene.

 As shown in Example 12 below, when using 5-halogen-substituted 2H-benzotriazole with an alkoxycarbonyl-substituted mercaptan, the expected thioether compound is not isolated. Instead, a Michael reverse reaction occurs, and the isolated product is a bis-sulfide molecule, where in formula B1 r = 0.

In general, polymers that can be stabilized include:
1. Polymers of monoolefins and diolefins, for example, polyethylene (which can optionally be structured), polypropylene, polyisobutylene, polybutene-1, polymethylpentene-1, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for example, 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 / isobutylene, ethylene / butene-1, propylene / butadiene, isobutylene / isoprene, ethylene / alkyl acrylates, ethylene / alkyl methacrylates, ethylene / vinyl acetate or ethylene / acrylic acid, as well as their salts (ionomers) and ternary copolymers of ethylene with propylene and diene, for example, hexadiene, dicyclopentadiene or ethylidene norbornene.

 4. Polystyrenes, poly - (α-methylstyrene).

 5. Copolymers of styrene or methyl styrene with dienes or acrylic derivatives, for example styrene / butadiene, styrene / acrylonitrile, styrene / ethyl methacrylate, styrene / butadiene / ethyl acrylate, styrene / acrylonitrile / methyl acrylate, mixtures of high strength upon impact with another styrene copolymer, for example, styrene copolymer from a polyacrylate, diene polymer or ethylene / propylene / diene ternary copolymer, as well as styrene block copolymers, for example styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene.

 6. Grafted styrene copolymers, for example styrene on polybutadiene, styrene and acrylonitrile on polybutadiene, styrene and alkyl acrylates or methacrylates on polybutadiene, styrene and acrylonitrile on triple copolymers of ethylene / propylene / diene, styrene and acrylonitrile polyacrylonitrile or polyacrylate acrylate / butadiene copolymers, as well as mixtures thereof with the copolymers described in Part 5, for example, copolymer mixtures known as acrylonitrile butadiene styrene (ABS) polymers, a methyl methacrylate butadiene terpolymer styrene (MBS), thermoplastic acrylonitrile-styrene-acrylic ester (ASA) or thermoplastic (quadruple) acrylonitrile, ethylene, propylene and styrene (AES).

 7. Halogen-containing polymers, such as polychloroprene, chlorinated rubbers, chlorinated or sulfochlorinated polyethylene, epichlorohydrin homo- and copolymers, polymers from halogen-containing vinyl compounds, for example, polyvinyl chloride, polyvinylidene chloride, polyvinylideneidene fluoride, vinylideneideneidene fluoride vinyl chloride / vinyl acetate, vinylidene chloride / vinyl acetate, or vinyl fluoride / vinyl ether copolymers.

 8. Polymers derived from α, β-unsaturated acids and their derivatives, for example, polyacrylates and polymethacrylates, polyacrylamide and polyacrylonitrile.

 9. Copolymers of the monomers mentioned in Part 8, with each other or with other unsaturated monomers, for example, copolymers of acrylonitrile / butadiene, acrylonitrile / alkoxyalkyl acrylate or acrylonitrile / vinyl halide / acrylonitrile / acrylonitrile copolymers.

 10. Polymers derived from unsaturated alcohols and amines, or their acyl derivatives or their acetals, for example, polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine.

 11. Homopolymers and copolymers of cyclic ethers, for example polyalkylene glycols, such as polyethylene oxide, polypropylene oxide or their copolymers with bis-glycidyl ethers.

 12. Polyacetals, such as polyoxymethylene, and those polyoxymethylenes that contain ethylene oxide as a comonomer.

 13. Polyphenylene oxides or polyphenylene sulfides, as well as mixtures of polyphenylene oxides with polystyrene.

 14. Polyurethanes, which are obtained 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 precursors (polyisocyanates, polyols or prepolymers).

 15. Polyamides and copolyamides which are obtained from diamines and dicarboxylic acids and / or from aminocarboxylic acids or corresponding lactams, for example, polyamide-4, polyamide-5, polyamide-6/6, polyamide-6/10, polyamide-11, polyamide -12, poly-2,4,4-trimethylhexamethylene terephthalamide, poly-p-phenylene terephthalamide or poly-m-phenylene isophthalamide, as well as their copolymers with polyesters, for example, polyethylene glycol, polypropylene glycol or polytetramethylene glycols.

 16. Polyureas, polyimides and polyamidimides.

 17. Polyesters derived from dicarboxylic acids and diols and / or from hydroxycarboxylic acids or corresponding lactones, for example, polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, poly- [2,2- (4-hydroxyphenyl) propane ] terephthalate and polyhydroxybenzoates, as well as block copolyesters-polyesters derived from polyesters having hydroxyl end groups.

 18. Polycarbonates.

 19. Polysulfones, polyethersulfones and polyethersetones.

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

 21. Drying and non-drying alkyd resins.

 22. Unsaturated polyesters, which are obtained from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, as well as their halogen-containing modifications with low flammability.

 23. Thermoset polyacrylates derived from substituted acrylic esters, for example, epoxy acrylates, urethane acrylates or polyesters.

 24. Alkyd resins, polyesters or polyacrylates mixed with melamine resins, urea resins, polyisocyanates or epoxies as crosslinking agents.

 25. Crosslinked epoxies that are derived from polyepoxides, for example, from bis-glycidyl ethers or from cycloaliphatic diepoxides.

 26. Natural polymers, such as cellulose, rubber, gelatin and their derivatives, which are chemically modified in a polymer-homologous manner, for example, cellulose acetates, cellulose propionates and cellulose butyrates, or cellulose ethers such as methyl cellulose.

 27. Mixtures of the polymers mentioned above, for example, polypropylene / triple copolymer of ethylene, propylene and diene (PP / EPDM), polyamide-6 / EPDM, or a copolymer of acrylonitrile, butadiene and styrene (ABS), polyvinyl chloride / copolymer of ethylene and vinyl acetate (PVC / EVA), PVC / ABS, PVC / copolymer of methyl methacrylate, butadiene and styrene (MBS), chlorinated polyvinyl chloride (PC) / ABS, polybutadiene terephthalate (PBTP) / ABS.

 28. Naturally occurring synthetic organic substances that are pure monomer 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 (eg phthalates, adipates phosphates or trimellitates), as well as mixtures of synthetic esters with mineral oils in any mass ratio, and these substances can be used as plasticizers for polymers or as a tech stylish lubricants, as well as aqueous emulsions of such substances.

 29. Aqueous emulsions of natural or synthetic rubber, for example, natural latex or latexes of carboxylated styrene / butadiene copolymers.

 30. Polysiloxanes, such as soft, hydrophilic polysiloxanes, described, for example, in US Pat. No. 4,294,467A, and solid polyorganosiloxanes, described, for example, in US Pat. No. 4,355,147A.

 31. Polyketimines in combination with unsaturated acrylic polyacetoacetate resins with unsaturated polyacrylates. Unsaturated polyacrylates include urethane acrylates, polyester acrylates, vinyl or acrylic copolymers of the unsaturated groups in question, and acrylate melamines. Polyketimines are prepared from polyamines and ketones in the presence of an acid catalyst.

 32. Radiation-curable compositions containing ethylene unsaturated monomers or oligomers and a polyunsaturated aliphatic oligomer.

 33. Epoxymelamine resins, such as light-resistant epoxy resins cross-linked by epoxy function with co-esterified high hardness melamine resins, for example, LSE-4103 (Monsanto).

 In general, the compounds of the present invention are used in an amount of from about 0.01 to 5% by weight of the stabilized composition, although it may vary depending on the particular substrate and purpose.

 A preferred range is from about 0.5 to 2%, and especially from 0.1 to 1% by weight.

 The stabilizers of the present invention can be easily incorporated into organic polymers by conventional methods at any convenient stage before 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 the suspension or emulsion of the stabilizer may be mixed with a solution, suspension or emulsion of the polymer. The obtained stabilized 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 the substances listed below, or mixtures thereof .

1. Antioxidants
1.1. Alkylated monophenols, e.g.
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-isobutylphenol,
2,6-dicyclopentyl-4-methylphenol,
2- α methylcyclohexyl) -4,6-dimethylphenol,
2,6-dioctadecyl-4-methylphenol,
2,4,6-tricyclohexylphenol,
2,6-di-tert.-butyl-4-methoxymethylphenol.

1.2. Alkylated hydroquinones, e.g.
2,6-di-tert.-butyl-4-methoxyphenol,
2,5-di-tert.-butylhydroquinone,
2,5-di-tert.-amylhydroquinone,
2,6-diphenyl-4-octadecyloxyphenol.

1.3. Hydroxylated thiodiphenyl ethers, e.g.
2,2'-thio-bis- (6-tert.-butyl-4-methylphenol),
2,2'-thio-bis- (4-octylphenol),
4,4'-thio-bis- (6-tert.-butyl-3-methylphenol),
4,4'-thio-bis- (6-tert.-butyl-2-methylphenol).

1.4. Alkylidenebisphenols, 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 '- (α-methylcyclohexyl) phenol],
2,2'-methylene-bis- (4-methyl-6-cyclohexylphenol),
2,2'-methylene-bis- (6-nonyl-4-methylphenol),
2,2'-methylene-bis- [6 - (α-methylbenzyl) -4-nonylphenol],
2,2'-methylene-bis- [6 - (α, α-dimethylbenzyl) -4-nonylphenol],
2,2'-methylene-bis- (4,6-di-tert.-butylphenol),
2,2'-ethylidene-bis- (4,6-di-tert.-butylphenol),
2,2'-ethylidene-bis- (6-tert.-butyl-4-isobutylphenol),
4,4'-methylene-bis- (2,6-di-tert.-butylphenol),
4,4'-methylene-bis- (6-tert.-butyl-2-methylphenol),
1,1-bis- (5-tert.-butyl-4-hydroxy-2-methylphenylbutane),
2,6-di- (3-tert.-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol,
1,1,3-tris- (5-tert.-butyl-4-hydroxy-2-methylphenyl) butane,
1,1-bis- (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecyl mercaptobutane,
ethylene glycol bis- [3,3-bis- (3'-tert.-butyl-4'-hydroxyphenyl) butyrate],
di- (3-tert.-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene,
di- [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate.

1.5. Benzyl compounds, e.g.
1,3,5-tri- (3,5-di-tert.-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzyl,
di- (3,5-di-tert.-butyl-4-hydroxybenzyl) sulfide,
3,5-di-tert.-butyl-4-hydroxybenzyl-mercaptoacetic acid isooctyl ester,
bis- (4-tert.-butyl-3-hydroxy-2,6-dimethylbenzyl) dithiol terephthalate,
1,3,5-tris- (3,5-di-tert.-butyl-4-hydroxybenzyl) isocyanurate,
3,5-di-tert. dioctadecyl ester -butyl-4-hydroxybenzylphosphoric acid, calcium salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphoric acid monoethyl ester.

1.6. Acylaminophenols, for example,
4-hydroxylauric acid anilide,
4-hydroxystearic acid anilide,
2,4-bis-octyl mercapto-6- (3,5-tert.-butyl-4-hydroxyanilino) -s-triazine,
octyl-N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate.

1.7. Esters of β- (3,5-di-tert.-butyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols, for example,
methanol - diethylene glycol
octadecanol - triethylene glycol
1,6-hexanediol - pentaerythritol
neopentyl glycol - tris-hydroxyethyl isocyanurate
thioethylene glycol - diamine dihydroxyethyl oxalic acid
1.8. Esters of β- (5-tert.-butyl-4-hydroxy-3-methylphenyl) propionic acid, with monohydric or polyhydric alcohols, for example
methanol - diethylene glycol
octadecanol - triethylene glycol
1,6-hexanediol - pentaerythritol
neopentyl glycol - tris-hydroxyethyl isocyanurate
thioethylene glycol - diamine dihydroxyethyl oxalic acid
1.9. Amides of β- (3,5-di-tert.-butyl-4-hydroxyphenyl) propionic acid, e.g.
N, N'-di- (3,5-di-tert.-Butyl-4-hydroxyphenylpropionyl) - hexamethylenediamine,
N, N'-di- (3,5-di-tert.-butyl-4-hydroxyphenylpropionyl) trimethylenediamine,
N, N'-di- (3,5-di-tert.-butyl-4-hydroxyphenylpropionyl) hydrazine.

1.10. Diarylamines, for example,
diphenylamine, N-phenyl-1-naphthylamine, N- (4-tert.-octylphenyl) -1-naphthylamine, 4,4'-di-tert. -octyldiphenylamine, the product of the interaction of N-phenylbenzylamine and 2,4,4-trimethylpentene, the product of the interaction
diphenylamine and 2,4,4-triphenylpentene, the product of the interaction of N-phenyl-1-naphthylamine and 2,4,4-triphenylpentene.

2. UV absorbers and light stabilizers
2.1. 2- (2'-Hydroxyphenyl) benzotriazoles, e.g.
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'-octoxy, 3 ', 5'-di-tert.-amyl-, 3', 5'-bis- (α, α-dimethylbenzyl) -, 3 ' tert.-butyl-5 '- (2-omega-hydroxy-octa- (ethyleneoxy) -carbonylethyl-, decyl-5'-methyl-, 3'-tert-butyl-5' - (2-octyloxycarbonyl) ethyl - and dodecylated 5'-methyl-corresponding derivatives.

2.2. 2-hydroxybenzophenones, e.g.
4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2'4'-trihydroxy- and 2'-hydroxy-4,4'- dimethoxy derivatives.

2.3. Esters optionally substituted benzoic acid, for example,
phenyl salicylate, 4-tert. -butylphenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis- (4-tert-butylbenzoyl) -resorcinol, benzoylresorcinol, a complex 2,4-di-tert. butylphenyl ether, 3,5-di-tert.-butyl-4-hydroxybenzoic acid; and hexadecyl ester of 3,5-di-tert-butyl-4-hydroxybenzoic acid.

2.4. Acrylates, for example,
ethyl ester or iso-octyl ester of α-cyano-β, β- / diphenylacrylic acid, methyl ester of α-carbomethoxy cinnamic acid, methyl ester or butyl ester of α-cyano-β-methyl-p-methoxy cinnamic acid, methyl ester α-carbomethoxy-p-methoxycinnamic acid, N- (β-carbomethoxy-β-cyano-vinyl) -2-methylindoline.

2.5. Nickel compounds, for example,
nickel complexes of 2,2'-thio-bis- [4- (1,1,3,3-tetramethylbutyl) phenol], such as a 1: 1 or 1: 2 complex, optionally with additional ligands, such as n- butylamine, triethanolamine or N-cyclohexyl diethanolamine, nickel dibutyl dithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, for example methyl, ethyl or butyl ester, nickel complexes, e.g. hydroxy-4-methylphenylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, optionally with spruce ligands.

2.6. Spatially hindered amines, e.g.
bis- (2,2,6,6-tetramethylpiperidine) sebacinate,
bis- (1,2,2,6,6-pentamethylpiperidyl) sebacinate,
n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonic acid bis- (1,2,2,6,6-pentamethylpiperidyl) ester,
condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid,
condensation product of N, N '- (2,2,6,6-tetramethylpiperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-s-triazine,
tris- (2,2,6,6-tetramethylpiperidyl) nitrilotriacetate,
tetrakis- (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate,
1,1 '(1,2-ethanediyl) -bis- (3,3,5,5-tetramethylpiperazinone),
di- (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacinate,
di- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate,
1-octyloxy-2,2,6,6-tetramethyl-4-hydroxypiperidine,
poly {[6-tert. -octylamino-s-triazine-2,4] [2- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) iminohexamethylene- [4- (1-cyclohexyloxy-2,2,6,6 - tetramethylpiperidin-4-yl) imino},
2,4,6-tris [N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) -n-butylamino] -s-triazine.

2.7. Oxalic acid diamides for example
4,4'-dioctyloxyoxanilide;2,2'-dioxythyloxy-5,5'-di-tert. -butyloxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert. -butyloxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis- (3-dimethylaminopropyl) -oxanilide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and mixtures thereof with 2'-ethoxy -5,4'-di-tert.-butyloxanilide and a mixture of ortho- and para-methoxy-, as well as o- and p-ethoxy-disubstituted oxanilides.

2.8. Hydroxyphenyl-s-triazines, e.g.
2,6-bis- (2,4-dimethylphenyl) -4- (2-hydroxy-4-octyloxyphenyl) -s-triazine;
2,6-bis- (2,4-dimethylphenyl) -4- (2,4-hydroxyphenyl) -s-triazine; 2,4-bis- (2,4-dihydroxyphenyl) -6- (4-chlorophenyl) -s-triazine; 2,4-bis- [2-hydroxy-4- (2-hydroxyethoxy) phenyl] -6- (4-chlorophenyl) -s-triazine; 2,4-bis- [2-hydroxy-4- (2-hydroxy-4- (2-hydroxyethoxy) phenyl] -6- (2,4-dimethylphenyl) -s-triazine; 2,4-bis- [2 -hydroxy-4- (2-hydroxyethoxy) phenyl] -6- (4-bromphenyl) -s-triazine; 2,4-bis- [2-hydroxy-4- (2-acetoxyethoxy) phenyl] -6- (4 - chlorophenyl) -s-triazine; 2,4-bis- (2,4-dihydroxyphenyl) -6- (2,4-dimethylphenyl) -s-triazine.

3. Metal deactivators, for example,
N, N'-diamine diphenyl oxalic acid, N-calicylal-N'-calicyloylhydrazine, N, N'-bis-salicyloylhydrazine, N, N'-bis- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) - hydrazine, 3-salicyloylamino-1,2,4-triazole, bis-benzylidene-oxalic acid dihydrazide.

4. Phosphites and phosphonites, for example,
triphenylphosphite, diphenylalkylphosphites, diphenyldialkylphosphites, tri (nonylphenyl) phosphite, trilaurylphosphite, trioctadecylphosphite, distearyl-pentaerythritol diphosphite, tris- (2,4-di-tert-butylphenyl) phosphite, di-di-di-di-dithritol .-butylphenyl) pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis- (2,4-di-tert.-butylphenyl) -4,4'-diphenylylene diphosphonite.

5. Compounds that break down peroxide, for example
β-thiodipropionic acid esters, for example, lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or zinc salt of 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate, dioctadecyl disulphide, penta-di-tetra-dimer-nitrite.

6. Hydroxylamines, for example,
N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-ditetradecylhydroxylamine, N-dihexadecidehydroxylamine-N-dihexadecylhydroxylamine, N N-heptadecyl-N-octadecylhydroxylamine; N, N-dialkylhydroxylamine obtained from hydrogenated tall amine.

 7. Nitrons, for example, N-benzyl-α-phenyl nitron, N-ethyl-α-methyl nitron, N-octyl-α-heptyl nitron, N-lauryl-α-undecyl nitron, N-tetradecyl-α-gredecyl nitron, N-hexadecyl - pentadecyl nitron N-dialkylhydroxylamine obtained from hydrogenated tall amine.

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

9. Basic joint stabilizers, for example,
melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example, Ca-stearate, Zn-stearate, Mg-stearate, and Na-ricin - palmitate, antimony pyrocatecholate or zinc pyrocatecholate.

10. Nucleating agents, for example,
4-tert. -butylbenzoic acid, adipic acid, diphenylacetic acid.

11. Fillers and reinforcing fillers, for example,
calcium carbonate, silicates, fiberglass, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.

12. Other additives, for example
plasticizers, lubricants, emulsifiers, pigments, optical brighteners, flame retardants, antistatic agents, blowing agents and thiosynergic substances such as dilauryl thiodipropionate or distearyl thiodipropionate.

 Of particular interest, the phenolic antioxidant is selected from the group consisting of n-octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentane tetrayltetrakis (3,5-di-tert.-butyl-4-hydroxyhydrocinnamate), di-n-4-tert. -butyl-4-hydroxybenzylphosphonate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, thiodiethylenebis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert.-butyl-4-hydroxybenzyl) benzene, 3,6-dioxa-octamethylenebis (3-methyl-5-tert.-butyl- 4-hydroxyhydrocinnamate), 2,6-di-tert.-butyl-p-cresol, 2,2'-ethylidenebis (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-hydroxyhydrocinnamoyloxy) ethyl] isocyanurate, 3,5-di- (3 , 5-di-tert.-Butyl-4-hydroxybenzyl) mesite, hexamethylene bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1- (3,5-di-tert-butyl-4- hydroxyanilino) -3,5-di- (octylthio) -s-triazine, N, N'-hexamethylenebis (3,5-di-tert.-butyl-4-hydroxyhydrocinnamide), calcium bis (ethyl-3,5-di tert.-butyl-4-hydroxybenzylphosphonate), ethylene bis [3,3-di- (3-tert.-butyl-4-hydroxyphenyl) butyrate], octyl-3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate bis (3,5-di-tert. - butyl-4-hydroxyhydrocinnamoyl) hydrazide and N, N'-bis [2- (3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy) ethyl] oxamide.

 The most preferred phenolic oxidizing agents are neopentanetetrayltetrakis (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'-ethylidenebis (4,6-di-tert-butylphenol).

 The compound of hindered amine of particular interest is selected from the group consisting of bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacinate, bis (1,2,2,6,6-pentamethylpiperidin-4-yl) sebacinate, di- (1,2,2,6,6-pentamethylpiperidin-4-yl) (3,5-di-tert.-butyl-4-hydroxybenzyl) butyl malonate, 4-benzoyl-2,2,6,6 -tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8, -triaz-spiro [4.5] -decane-2 , 4-dione, tris (2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate, 1,2-bis (2,2,6,6-tetramethyl-3-oxopiperazin-4 yl) ethane, 2 2,4,4-tetramethyl-7-oxa-3,20-diaza-21- ksodispiro [5.1.11.2] geneykozana, polycondensation product of 2,4-dichloro-6-tert. -octylamino-s-triazine and 4,4'-hexamethylenebis (amino-2,2,6,6-tetramethylpiperidine), a polycondensation product of 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the polycondensation product of 4,4'-hexamethylene bis (amino-2,2,6,6-tetramethylpiperidine) and 1,2-dibromoethane, tetrakis (2,2,6,6-tetramethylpiperidin-4-yl)) - 1,2,3,4-butantetracarboxylate, tetrakis (1,2,2,6,6-pentamethylpiperidine) -1,2,3,4-butantetracarboxylate, a polycondensation product of 2,4-dichloro-6-morpholino-s-triazine and 4,4'-hexamethylene bis (amino-2,2,6,6-tetramethylpiperidine), N, N ', N' ', N' '' - tetrakis [(4,6-bi (butyl-2,2,6,6-tetramethylpiperidin-4-yl) amino-s-triazin-2-yl] -1,10-diamino-4,7-diazadecane mixed [2,2,6,6- tetramethylpiperidin-4-yl-β, β, β ′, β′-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5.5] undecane) diethyl] - 1,2,3,4- butanetetracarboxylate, mixed / 1,2,2,6,6-pentamethylpiperidin-4-yl-β, β, β ′, β′-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5.5] - undecane) diethyl] -1,2,3,4-butanetetracarboxylate, octamethylenebis (2,2,6,6-tetramethylpiperidin-4-carboxylate), 4,4'-ethylenebis (2,2,6,6-tetramethylpiperazine- 3-one), N-2,2,6,6-tetramethylpiperidin-4-yl-n-dodecyl succinimide, N-1,2,2,6,6-pentamethylpiperidin-4-yl dodecyl succinimide, N-1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl-n-dodecyl succinimide, 1-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8 triazaspiro [4.5] -decane-2,4-dione, di- (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacinate, di- (1-cyclohexyloxy-2,2,6, 6-tetramethylpiperidin-4-yl) succinate, 1-octyloxy-2,2,6,6-tetramethyl-4-hydroxypiperidine, poly - {[6-tert-octylamino-s-thiazin-2,4-diyl] [ 2- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) iminohexamethylene- [4- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) imino] and 2, 4,6-tris [N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) -n-but ilamino] -s-triazine.

 The most preferred hindered amine compounds are bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacinate, bis (1,2,2,6,6-pentamethylpiperidin-4-yl) sebacinate, di- (1,2 , 2,6,6-pentamethylpiperidin-4-yl) (3,5-di-tert.-Butyl-4-hydroxybenzyl) butyl malonate, polycondensation product 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl -4-hydroxypiperidine and succinic acid, the polycondensation product of 2,4-dichloro-6-tert. -octylamino-s-triazine and 4,4'-hexamethylene bis (amino-2,2,6,6-tetramethylpiperidine), N, N ', N' ', N' '' - tetrakis [(4,6-bis ( butyl-2,2,6,6-tetramethylpiperidin-4-yl) amino-s-triazin-2-yl] -1,10-diamino-4,7-diazadecane, di- (1-octyloxy-2,2, 6,6-tetramethylpiperidin-4-yl) sebacinate, di- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate, 1-octyloxy-2,2,6,6-tetramethyl-4 -hydroxypiperidine, poly - {[6-tert.-octylamino-s-triazine-2,4-diyl] [2- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) iminohexamethylene- [4 - (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) imino] or 2,4,6-tris [N- (1-cyclohexyloxy - 2,2,6,6-tetramethylpiperidin-4-yl) n-butylamino] -s-triazine.

 The invention is illustrated by the following examples.

Example 1
5-n-dodecylthio-2- (2-hydroxy-3,5-di-tert.-butylphenyl) -2H-benzotriazole
357.8 g (1 mol) of 5-chloro- (2-hydroxy-3,5-di-tert-butylphenyl) -2H- is charged into a three-liter, three-necked flask equipped with a stirrer, thermometer, nitrogen inlet and distillation device. benzotriazole supplied by CIBA-GEIGY Corp. both TINUVIN ^® 327, 216.8 g (1.05 mol) of n-dodecyl mercaptan 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 150 ^o C in nitrogen atmosphere. The water released as a result of the reaction is distilled off in the form of an azeotropic mixture until the temperature in the head reaches 132 ^o C. After 20 hours at a temperature of 150 ^o C, the starting 2H-benzotriazole is completely consumed. In a partial vacuum at a temperature of 80-100 ^o C most of the DMF is distilled off. To the resulting oil was added at a temperature of 80 ^o C 1 l of toluene and 500 ml of water. The aqueous phase is withdrawn. The toluene solution is washed twice with more than 500 ml of water containing 1 ml of acetic acid. The organic solution is freed from residual water by azeotropic distillation to obtain a clear solution. In a partial vacuum, all toluene, with the exception of about 100 ml, was distilled off at a temperature of 70 ^° C. The residue was diluted at 60 ^° C. with 2 L of isopropanol and seed crystals of the product were added. The product gradually crystallizes, after which the mixture is slowly cooled to a temperature of 10 ^o C. The product is filtered off and washed with 300 ml of isopropanol to obtain 490.4 g (93.6% of theory) of the title compound, melting point 62-64 ^o C.

Example 2
5-phenylthio-2- (2-hydroxy-3,5-di-tert.-butylphenyl) -2H-benzotriazole
In a two-liter three-necked flask equipped with a mixer, thermometer, distillation device and a nitrogen supply, 268.4 g (0.75 mol) of 5-chloro-2- (2-hydroxy-3,5-di-tert-butylphenyl) - are charged 2H-benzotriazole, 93.7 g (0.825 mol) of thiophenol and 400 ml of NN-dimethylformamide (DMF). The reactor is degassed and filled 3 times with nitrogen in order to establish an inert atmosphere. 66.0 g (0.825 mol) of a 50% aqueous sodium hydroxide solution are added to the suspension, and the mixture is heated to the distillation temperature. At this point, water is distilled off in the form of an azeotropic mixture until the temperature in the head reaches 132 ^° C. and the reaction temperature is 150 ^° C. After 18 hours, no residual starting benzotriazole compound (TLC) is detected. Under reduced pressure, most of the DMF is distilled off at a temperature of 80 ^° C. Then, 500 ml of toluene and 200 ml of water are added to the residue. After stirring slowly for several minutes at a temperature of 80 ^° C., the lower aqueous phase is withdrawn. The addition of 200 ml of water is repeated twice more, a second time using 1 ml of acetic acid. The residual water is azeotroped off until a clear solution is obtained. Approximately 300 ml of toluene is removed under partial vacuum at a temperature of 90 ^° C., and 800 ml of isopropanol is added to the concentrate, resulting in rapid crystallization. The reaction mixture is cooled to a temperature of 20 ^o C and filtered. The light yellow crystals are washed with 250 ml of isopropanol and dried to give 317.0 g (97.9% of theory) of the title compound, melting point 132-134 ^° C.

Alternatively, the title compound is synthesized as follows:
3.0 g (0.0084 mol) of 5-chloro-2- (2-hydroxy-3,5-di-tert-butylphenyl) are charged into a 250-ml round-bottom flask equipped with a magnetic stirrer, nitrogen inlet and condenser ) -2H-benzotriazole, 1.1 g (0.020 mol) of ground potassium hydroxide, 1.6 ml (0.016 mol) of thiophenol, 0.135 g (0.49 mol) of 18-crown-6 and 9 ml of mesitylene. The mixture was refluxed with stirring for 4 hours and then cooled to room temperature. Ethyl acetate and 2N were added. hydrochloric acid solution. The layers were separated and the organic layer was washed once with water and once with brine, and finally dried in the presence of anhydrous magnesium sulfate. Analysis of the crude mixture by NMR (CDCl ₃ ) shows that the conversion to the desired title compound is about 15%.

По методике примеров 1 и 2 получены следующие соединения, указанные в таблице 1, с выходом, превышающим 90%.Examples 3-13

By the method of examples 1 and 2, the following compounds are obtained, are shown in table 1, with a yield exceeding 90%.

Example 13
5-phenylthio-2- [2-hydroxy-3 tert.-butyl-5 - (β-octyloxycarbonyl-ethyl) -phenyl] -2H-benzotriazole
40.77 g (0.084 mol) of 5-chloro- [2-hydroxy-3-tert-butyl-5 - (β-octyloxycarbonyl) are charged into a liter three-necked round bottom flask equipped with a magnetic stirrer, nitrogen inlet and condenser ) phenyl] -2H-benzotriazole, available from CIBA-GEIGY Corp. as TINUVIN ^® 109, 5.8 g (0.042 mol) of potassium carbonate and 1 g of potassium iodide. The mixture was placed under nitrogen and 210 ml of N, N-dimethylformamide were quickly added. The solution is heated to a temperature of 130-140 ^o C and 10.1 g of 92 mol) of thiophenol is added immediately through a syringe. The reaction mixture was stirred at this temperature for 21 hours and then cooled to room temperature. The mixture was neutralized with a small portion of acetic acid, ethyl acetate and brine were added and the layers were separated. The aqueous layer was extracted twice with ethyl acetate, and the combined organic layers were washed twice with brine and twice with water, and finally dried in the presence of anhydrous magnesium sulfate. The mixture is filtered and passed through a plug of silica gel. The solvent was stripped to obtain 53.8 g of a yellow oil. The oil is purified by medium-pressure chromatography on a silica gel column to obtain 29.7 g (63%) of the title compound as a pale yellow oil.

Analysis:
Calculated for C ₃₃ H ₄₁ N ₃ O ₃ S: C, 70.8; H 7.4; N, 7.5.

 Found: C, 70.6; H 7.8; N, 7.9.

Similarly, 4.3 g (0.0096 mol) of 3- (5-phenylthio-2H-benzotriazole-2-yl) are charged into a 250 ml round bottom flask equipped with a magnetic stirrer, nitrogen inlet, condenser and Dean-Stark trap. ) -5-tert. -butyl-4-hydroxyhydrocinnamic acid, 3.4 g (0.026 mol) of Exxel 8, an isomeric mixture of octanols obtained from Exxon Chemicals, 70 mg of p-toluenesulfonic acid and 20 ml of xylene. The mixture was refluxed for 3.5 hours, cooled to room temperature and a portion of ethyl acetate was added. The solution is washed 1 time with water, 2 times with saturated sodium bicarbonate solution and 1 time with saline. After drying in the presence of anhydrous magnesium sulfate, the solvent was removed under reduced pressure to obtain 5.17 g (96% yield) of the title compound as a yellow viscous oil. NMR analysis (CDCl ₃ ) is consistent with the structure of the title compound.

Example 14
5.5'-thiobis [2- (2-hydroxy-3,5-di-tert-butylphenyl) -2H-benzotriazole]
6.4 g (0.06 mol) of 3-mercaptopropionic acid are dissolved in a solution of 2.76 g of sodium and 80 ml of ethanol. The solvent was distilled off and replaced with 110 ml of N, N-dimethylformamide 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 under nitrogen at a temperature of 160-165 ^o C for 48 hours. TLC shows the presence of some unreacted starting benzotriazole. The cooled mixture was poured into water containing 150 ml of toluene and neutralized with hydrochloric acid. The toluene solution is separated and washed with water, dried in the presence of anhydrous magnesium sulfate and filtered. The solution was concentrated and diluted with ethanol. The resulting solid was isolated by filtration and washed with acetone in order to extract unreacted starting material. The filter cake was dissolved in 25 ml of toluene at a temperature of 70 ^o C and add 5 ml of acetone to precipitate the product. The resulting crystals were filtered and washed with acetone to give 6.6 g of the title compound, melting point 245-246 ^° C.

 The same product is obtained using mercaptoacetic acid instead of 3-mercaptopropionic acid.

Example 15
5-phenylthio-2- [2-hydroxy-3-tert. -butyl-5- (3-hydroxypropyl) - phenyl] -2H-benzotriazole
To a suspension of lithium aluminum hydride (6.0 g, 0.16 mol) in 500 ml of anhydrous diethyl ether in a 2 liter Erlenmeyer flask with a magnetic stirrer, a solution of 30.1 g (0.078 mol) of 5-chloro-2 is added dropwise at room temperature - [2-hydroxy-3-tert. -butyl-5- (2-methoxycarbonylethyl) phenyl] -2H-benzotriazole in 500 ml of anhydrous diethyl ether. The mixture was stirred for 1.5 hours at room temperature and the excess hydride was cooled with ethyl acetate. Water was added until a gel formed, the mixture was dried in the presence of anhydrous magnesium sulfate, filtered and the solvent was removed in vacuo to give 28.7 g (100% yield) of the intermediate as a yellow-orange solid, melting point 105-106 ^° C.

Into a liter round bottom flask equipped with a magnetic stirrer, condenser and nitrogen atmosphere, 27.7 g (0.077 mol) of the intermediate obtained above, 10.6 g (0.077 mol) of potassium carbonate, 1.2 g of potassium iodide and 8.48 are charged g (0.077 mol) of thiophenol in 240 ml of N, N-dimethylformamide. A preheated oil bath (165 ^° C.) was used and the mixture was stirred at this temperature for 4.5 hours. After cooling to room temperature, stirring was 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 extracted 3 times with ethyl acetate. The combined organic layers are washed 2 times with 1N. hydrochloric acid solution, 1 time with brine, and then dried in the presence of anhydrous magnesium sulfate. The solvent was removed under reduced pressure to obtain 30.1 g of a yellow-orange solid. The crude material was recrystallized from heptane to give 26.3 g (79% yield) of the title compound as a yellow powder.

Analysis:
Calculated for C ₂₅ H ₂₇ N ₃ O ₂ S: C 69.3; H 6.3; N, 9.7.

 Found: C, 68.9; H 6.0; N, 9.7.

Example 16
3- (5-phenylthio-2H-benzotriazol-2-yl) -5-tert. -butyl-4-hydroxyhydrocinnamic acid
100.0 g (0.258 mol) of methyl-3- (5-chloro-2H-benzotriazol-2-yl) -5-tert are charged into a 1-liter, 4-round round bottom flask equipped with a mechanical stirrer and a nitrogen atmosphere. -butyl-4-hydroxyhydrocinnamate, 350 ml of N, N-dimethylformamide and 61.9 g (0.773 mol) of a 50% aqueous solution of sodium hydroxide. The mixture is heated at a temperature of 75-80 ^o C for 3 hours, and at this time the hydrolysis of the ester is completed. A catalytic amount of potassium iodide (5.0 g) was added. Thiophenol (32.2 g, 0.258 mol) was then added over 20 minutes, keeping the temperature at 75-80 ^° C. An additional portion of N, N-dimethylformamide (200 ml) was added while thiophenol was added to facilitate mixing. 25 ml fractions of water / methanol are removed and the solution is heated under reflux for 48 hours. The reaction mixture was cooled, then partitioned between 1.0 L 1N. hydrochloric acid solution and 1.0 l of ethyl acetate. The phases are separated and the organic phase is dried in the presence of anhydrous magnesium sulfate, after which the solvent is removed under reduced pressure to a total volume of 500 ml. 200 ml of heptane is added and the solution is left to stand overnight. The resulting crystals were collected by suction filtration, washed with 9: 1 heptane: ethyl acetate and dried to obtain 83.5 g (72% yield) of the title compound, melting point 154-156 ^° C.

Example 17
3- (5-phenylthio-2H-benzotriazol-2-yl) -5-tert. -butyl-4-hydroxyhydrocinnamide
3.0 g (0.0067 mol) of 3- (5-phenylthio-2H-benzotriazol-2-yl) -5-tert are loaded into a dry, 500 ml round bottom flask equipped with a magnetic stirrer, condenser and nitrogen inlet . -butyl-4-hydroxyhydrocinnamic acid, 6 ml of oxalyl chloride and a sufficient amount of chloroform to form a homogeneous solution (approximately 4 ml). The solution was heated under reflux for 1 hour and then stirred overnight at room temperature. Oxalyl chloride is distilled off under reduced pressure to obtain about 3.5 g of a yellow solid. The IR spectrum of a solid (chloroform film) reveals the complete formation of an intermediate acid chloride (1795 cm ^-1 ).

A 500 ml round bottom flask equipped with a magnetic stirrer was charged with 250 ml of anhydrous ethanol. After cooling to a temperature of -5 ^° C., ammonia gas was bubbled through the solvent until approximately 1 g (0.06 mol) was obtained. The acid chloride is added to the ammonia solution quickly in small portions to give a red solution. The mixture was warmed to room temperature and stirred overnight. Ethanol was removed under reduced pressure and the residue was dissolved in ethyl acetate. The solution was washed with water (1 time), saturated sodium carbonate solution (1 time) and brine (1 time). The combined aqueous layers were extracted 2 times with ethyl acetate and the combined organic layers were dried in the presence of anhydrous magnesium sulfate. Removal of the solvent affords 3.1 g of a brown solid. The crude product is recrystallized from ethanol / water to obtain 1.85 g (62% yield) of pure amide as a brown solid, melting point 128-130 ^o C.

Analysis:
Calculated for C ₂₅ H ₂₆ N ₄ O ₂ S: C 67.2; H 5.9; N, 12.5.

 Found: C, 66.7; H 5.7; N, 12.3.

Example 18
Isomeric mixture of 3- [3- (5- (phenylthio-2H-benzotriazol-2-yl) -5-tert. Butyl-4-hydroxyhydrocinnamoyloxy] -2-hydroxypropylmethacrylate and
2- [3- (5-phenylthio-2H-benzotriazol-2-yl) -5-tert. -butyl- 4-hydroxyhydrocinnamoyloxy] -3-hydroxypropylmethacrylate
Into a 250 ml round bottom flask equipped with a magnetic stirrer, 20.0 g (0.0447 mol) of 3- (5-phenylthio-2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxycinnamic acid are charged, 0.20 g of 4-methoxyphenol, 1.50 g of tetrabutylammonium bromide, 6.60 g (0.0460 mol) of glycidyl methacrylate and 150 ml of toluene. The stirred mixture was heated under reflux for 6 hours. After cooling to room temperature, the mixture was washed 1 time with water and the solvent was removed in vacuo to give 27.3 g (100% yield) of the title compounds as a pale yellow viscous oil. NMR analysis reveals that the product is an isomeric mixture of A and B (A: B, 78:22).

Analysis:
Calculated for C ₃₂ H ₃₅ N ₃ O ₅ S: C 65.2; H 6.0; N, 7.1.

 Found: C, 66.9; H 6.6; N, 6.5.

 The isomeric mixture of this example is additively polymerized in the presence of an azo-free radical catalyst to give a methacrylate copolymer containing the considered substituted parts of 5-phenylthio-benzotriazol-2-yl.

 A stabilized composition is obtained when an effective stabilizing amount of this copolymer is introduced into an organic substance subject to degradation under the influence of adverse effects of actinic radiation.

Example 19
5-phenylthio-2- [2-hydroxy-3-tert.-butyl-5- [2 - (ω- hydroxyocta (ethyleneoxy) carbonylethyl) phenyl] -2H-benzotriazole and 3.6.9.12.15.18.21-heptaoxatricosylmethylenebis [3 - (5-phenylthio-2H-benzotriazol-2-yl) -5-tert.-butyl-4-hydroxyhydrocinnamate
4.43 g (0.01 mol) of 3- (5-phenylthio-2H-benzotriazol-2-yl) - are charged into a 250-ml round-bottom flask equipped with a magnetic stirrer, a nitrogen inlet, a condenser and a Dean-Stark trap. 5-tert-butyl-4-hydroxyhydrocinnamic acid, 8.0 g (0.027 mol) of a polyethylene glycol of the formula H (OCH ₂ CH ₂ ) _w OH (supplied by Shell Chemical Co. as PEG 300 with an average molecular weight of 300, where w equal to 4-11 and an average of about 7 or 8), 70 mg of p-toluenesulfonic acid and 20 ml of xylene. The mixture was refluxed for 23 hours and then cooled to room temperature. Ethyl acetate was added and the solution was washed three times with saturated sodium carbonate solution and 1 time with brine. The organic layer was separated and dried in the presence of anhydrous magnesium sulfate. The solvent was removed under reduced pressure to obtain a 50:50 mixture of the title compounds in 6.36 g (100%) yield as a viscous yellow oil. NMR analysis (CDCl ₃ ) is consistent with the desired compounds.

 Other products in which w is a mixture of integers from 4 to 11 are related to the title compounds and are prepared using the procedure of this example. These compounds are best designated as ω-hydroxy-poly (ethyleneoxy) - 3- (5-phenylthiobenzotriazol-2-yl) -5-tert-butyl-4-hydroxyhydrocinnamate and poly (ethyleneoxy) bis [3- (5- phenylthiobenzotriazol-2-yl) -5-tert.-butyl-4-hydroxyhydrocinnamate].

Example 20
Spectral properties of UV absorbers based on substituted 5-thiobenzotriazoles
The following table shows the maximum absorption values, molar and specific extinction coefficients of a number of UV absorbers based on 2H-benzotriazoles. A well-known commercial UV absorber based on benzotriazoles, 2- [2-hydroxy-3,5-di - (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, and a number of proposed 5-substituted compounds are studied. The concentrations of each sample are the same, namely 20 mg / L. The maximum absorption values of thio compounds at 363-369 nm are red-shifted, that is, shifted in the visible direction by at least 20 nm relative to the commercial control sample, which has a maximum absorption at 342 nm (ε 15500). The molar extinction coefficients of the thio-substituted compounds of the invention far exceed these control compound values at maximum absorption values. (Table 2).

Example 21
The novel UV absorbers of the present invention are particularly effective for protecting UV-sensitive substrates with a relatively long wavelength. They include many aromatic systems. An important example is epoxy resins, which are important primers in automotive and other industrial applications. Light can penetrate automobile soil and destroy the primer at the primer / soil interface. This phenomenon is accompanied by a loss of adhesion to the top layer, even though the top layer itself may be in excellent condition. Exposure to high humidity contributes to this delamination phenomenon.

Steel test panels containing a commercial epoxy primer deposited by cathodic electrodeposition produce a 1.8–2.0 mils (0.046–0.051 mm) thick film of commercially available thermosetting high-hardness acrylic melamine that is used as a layer on a 4 x 12-inch UNIPRIME panel ( 10.16 cm x 30.48 cm) obtained from Advance Coating Technology, Inc. The coated panels are then fired at a temperature of 250 ^o F (121 ^o C) for 30 minutes. After 1 week of storage in an air-conditioned room, the coated panels are exposed for 55 days in Florida in a black box (5 ^o south) in accordance with SAE J1976.

The panels are exposed to ultraviolet radiation at 56 MJ / m. The unstabilized control panel delaminates during exposure in the open air and is not subject to further testing. The remaining panels are then placed in a QCT humidification chamber (Q-Panel Co.) at 100% relative humidity and a temperature of 100 ^° C and checked daily for expansion and delamination.

 The moisture resistance of a thermosetting acrylic coating with a high solids content deposited on an electrodeposited primer after 55 days of exposure in Florida is shown in Table 3.

 After 4 days of exposure to moisture, panels containing coatings stabilized with 3% by weight of the present compound of Example 1, 2, 3, 6, or 11 were tested for adhesion in accordance with Method D-3359 of the American Society for Testing Materials. All panels are rated on a 3-4V scale, where 5V indicates a lack of adhesion and OB indicates a presence of over 65% loss of adhesion.

 These results show that the proposed 2H-benzotriazoles having increased absorption in the near-visible region are particularly effective in protecting automotive coatings from delamination after prolonged exposure to sunlight and high humidity conditions.

Example 22
Resistance to delamination of thermosetting coatings with a high solids content, including UV absorbers, which are deposited directly on the electrodeposited primer
Steel test panels containing a commercial epoxy primer deposited by cathodic electrodeposition produce a 1.8–2.0 mils (0.036–0.051 mm) thick film of commercially available thermosetting high hardness acrylic melamine that is used as a layer on 4 x 12-inch UNIPRIME ^® panels (10.16 cm x 30.48 cm) obtained from Advance Coatimg Technology, Inc. The coated panels are then fired at a temperature of 250 ^o F (121 ^o C) for 30 minutes. After 1 week of storage in an air-conditioned room, panels are exposed for a certain period of time in Florida in a black box (5 ^{o to the} south) in accordance with SAE J-1976. The panels are evaluated every 7 days for delamination and it is believed that the panels are damaged if delamination is evident by at least 10% of the total number of panels. The results of this test are shown below in table 4.

Example 23
Resistance to delamination of thermosetting highly hard coatings, including UV absorbers, which are applied directly to the electrodepositing primer
Steel test panels containing a commercial epoxy primer coated with cathodic electrodeposition produce a 1.8–2.0 mils (0.036–0.051 mm) thick film of commercially available thermosetting high-hardness acrylic melamine, which is used as the film layer on UNIPRIME ^® 4x12 panels inches (10.16 cm x 30.48 cm) obtained from Advance Coating Technology, Inc. The coated panels are then fired at a temperature of 250 ^o F (121 ^o C) for 30 minutes. After 1 week of storage in an air-conditioned room, panels are exposed for a certain period of time in Florida in a black box (5 ^{o to the} south) in accordance with SAE J-1976. The panels are evaluated every 7 days for delamination and it is believed that the panels are corrupted if delamination is evident by at least 10% of the total number of panels. The results of this test are shown in the following table 5.

Example 24
The copolymer of the isomeric mixture 3- [3- (5-phenylthio-2H-benzotriazol-2-yl) - 5-tert. -butyl-4-hydroxyhydrocinnamoyloxy] - 2-hydroxypropylmethacrylate and 2- [3- (5-phenylthio-2H-benzotriazol-2-yl) -5-tert. -butyl- 4-hydroxyhydrocinnamoyloxy] -3-hydroxypropylmethacrylate
By dissolving the isomeric mixture of methacrylate monomers obtained in Example 18 in toluene in the presence of 2,2'-azobis (isobutyronitrile) and heating to a temperature of 80 ^° C., the corresponding methacrylate copolymer mentioned above is obtained.

Example 25
A monomer composition containing 23.5% butyl acrylate, 27% butyl methacrylate, 30% 2-hydroxyethyl acrylate, 15% styrene, 3% acrylic acid and 1.5% isomeric methacrylate monomer obtained in example 18 (all values are given by weight), and 0.4 parts per 100 parts of tert-amylperoxy-O- (2-ethylhexyl) monoperoxycarbonate initiator is polymerized in reflux xylene to form a moderate molecular weight stabilized acrylic polyol copolymer.

Example 26
By adding the acrylic polyol copolymer obtained in Example 25 to a standard acrylic melamine composition, a stabilized thermoset acrylic enamel is obtained having excellent resistance to destruction by actinic radiation and having excellent gloss retention with light reflection at an angle of 20 ^° .

Example 27
By adding the acrylic polyol copolymer obtained in Example 25 to a standard two-component acrylic urethane coating composition for refinishing, a coating having excellent gloss retention with light reflection at an angle of 20 is obtained.

Example 28
By adding the acrylic polyol copolymer obtained in Example 25 to a silver metal polyacrylic alkyd enamel, an enamel having excellent gloss retention with light reflection at an angle of 60 ^{° is} obtained.

Comparative data obtained when testing new compounds B and C and known A
Compound A is 5-ethylthio-2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole corresponding to compound III-25 EP 0323853A.

Compound B is 5-octylthio-2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole obtained according to the method of Example 1, and
Compound C is 5-dodecylthio-2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole obtained according to the procedure for Example 1.

Test
Test I: Test panels were obtained by spray coating a 0.9-1.0 mil (0.023-0.0251 mm) thick film of a commercially available thermoset acrylic-melamine coating containing 2.0% by weight of the test compound; UNIPRIME ^® panels measuring 4 x 12 inches (10.16 x 30.48 cm) obtained from Advance Coatings Technology, Inc. The coated panels are then fired at 250 ^° F (121 ^° C) for 30 minutes. After storage for 1 week in a ventilated room, the panels are exposed in the QUV ^® Q-Panel Co.). The panels are evaluated daily to determine on which day the topcoat is peeling off the primer. The results of the observation indicating the number of hours before the onset of stratification are shown below in table 6.

From the above data it is seen that the known compound A in comparison with the unstabilized coating 2 times extends the shelf life of the non-stratified coating, and the claimed compounds B and C increase the stability compared to compound A by 1.5 times. Test II: The test panels were obtained by spray coating a film with a thickness of 0.8-2.0 mils (0.046-0.051 mm) used in industry thermosetting acrylic-polyamide coating containing 2.0% by weight. test compound; UNIPRIME ^® panels measuring 4 x 12 inches (10.16 x 30.48 cm) obtained from Advance Coatings Technology, Inc. The coated panels are then fired at 250 ^° F (121 ^° C) for 30 minutes, followed by further firing at 350 ^° F (177 ^° C) for 30 minutes. After storage for 1 week in a ventilated room, the panels were exposed in the QUV ^® device (Q-Panel Co.). The panels are evaluated daily to determine on which day the topcoat is peeling off the primer. The observation results indicating the number of hours before the onset of stratification are shown below in table 7.

 From the above data it is seen that the known compound A practically does not change the stability in comparison with the unstabilized coating, while compounds B and C 2.8 times improve the performance associated with stabilization compared with the known compound A, even in the case of when additional firing was applied1

Claims (20)

1. Substituted benzotriazoles of the general formula A

where R ₁ means hydrogen, straight-chain or branched alkyl containing from 1 to 24 carbon atoms, or phenylalkyl with 7-15 carbon atoms;
R ₂ means straight-chain or branched alkyl containing from 1 to 24 carbon atoms, phenylalkyl containing from 7 to 15 carbon atoms, wherein said alkyl may be substituted by one or more hydroxy groups, or a radical of the formula —CH ₂ CH ₂ COR ₅ where R ₅ means —NH ₂ or —OR ₆ , where R ₆ is hydrogen, alkyl containing from 1 to 24 carbon atoms, unsubstituted or substituted with hydroxy, or OR ₆ is - (OCH ₂ CH ₂ ) _w OH, where w is from 1 to 12, or R ₂ means - (CH ₂ ) _m —CO — X— (Z) _p —YR ₁₅ , where X and Y are —O—, Z-alkylene with carbon numbers from 3 to 12, substituted hydride a hydroxyl group, R _{15 is a} group-CO-C (R ₁₈ ) = CH ₂ , where R ₁₈ is hydrogen or methyl, m = 0, 1 or 2, and p = 1;
R ₃ means alkyl with the number of carbon atoms from 8 to 20, phenylalkyl containing from 7 to 15 carbon atoms, aryl with the number of carbon atoms from 6 to 10, or R ₃ represents a radical of the formula B ₁

where E is C ₂ -C ₁₂ alkylene, C ₅ -C ₁₂ cycloalkylene or C ₈ -C ₁₂ alkylene interrupted by cyclohexylene;
r = 0 or 1. 2. Substituted benzotriazoles of the formula A according to claim 1, where R ₁ means hydrogen, straight-chain or branched alkyl with the number of carbon atoms from 1 to 24, or phenylalkyl with the number of carbon atoms from 7 to 15;
R ₂ is straight chain or branched alkyl with 1 to 24 carbon atoms or phenylalkyl containing 7 to 15 carbon atoms, said alkyl may be substituted with one or more hydroxy groups, or R ₂ is a group of the formula —CH ₂ CH ₂ COR ₅ where R ₅ means —NH ₂ or —OR ₆ , where R ₆ means hydrogen or alkyl with a carbon number of 1 to 24, unsubstituted or substituted with one or more hydroxy groups, or OR ₆ means - (OCH ₂ CH ₂ ) _w OH, where w is from 1 to 12, or R ₂ means - (CH ₂ ) _m —CO — X— (Z) _p —YR ₁₅ , where X and Y are —O—, Z-alkylene with the number of carbon at ohms from 3 to 12, substituted with a hydroxyl group, R ₁₅ means a group -CO-C (R ₁₈ ) = CH ₂ , where R ₁₈ is hydrogen or methyl, m = 0, 1 or 2, p = 1;
R ₃ means alkyl with the number of carbon atoms from 8 to 20, phenylalkyl containing from 7 to 15 carbon atoms, aryl with the number of carbon atoms from 6 to 10. 3. The substituted benzotriazoles of formula A according to claim 1, in which R ₁ means hydrogen, branched alkyl with carbon atoms from 4 to 8, benzyl, α-methylbenzyl, α, α-dimethylbenzyl, R ₂ means straight chain or branched alkyl with a number carbon atoms from 1 to 8, substituted by one or more hydroxyl groups; or R ₂ is benzyl, α-methylbenzyl or α, α-dimethylbenzyl; R ₂ is a group of the formula —CH ₂ CH ₂ COR ₅ where R ₅ is —NH ₂ or —OR ₆ , where R ₆ is hydrogen or alkyl with 1 to 24 carbon atoms, unsubstituted or substituted with one or more hydroxy groups, or OR ₆ means - (OCH ₂ CH ₂ ) _w OH, where w is from 1 to 12, or R ₂ means - (CH ₂ ) _m —CO — X— (Z) _p —YR ₁₅ , where X and Y are —O -, Z-alkylene with the number of carbon atoms from 3 to 8, substituted by a hydroxyl group, R ₁₅ means a group -CO-C (R ₁₈ ) = CH ₂ , where R ₁₈ is methyl, m = 2, p = 1; and R ₃ means phenyl or alkyl with carbon numbers from 8 to 12. 4. Substituted benzotriazoles of formula A according to claim 1, which are compounds selected from the group including:
(a) 5-n-dodecylthio-2- (2-hydroxy-3,5-di-tert.-butylphenyl) -2H-benzotriazole;
(b) 5-phenylthio-2- (2-hydroxy-3,5-di-tert.-butylphenyl) -2H-benzotriazole;
(c) 5-phenylthio-2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole;
(g) 5-benzylthio-2- (2-hydroxy-3-tert.-butyl-5-methylphenyl) -2H-benzotriazole;
(e) 5-phenylthio-2- (2-hydroxy-3-tert. butyl-5-methylphenyl) -2H-benzotriazole;
(e) 5-n-octylthio-2- (2-hydroxy-3,5-di-tert.-butylphenyl) -2H-benzotriazole;
(g) 5-tridecylthio-2- (2-hydroxy-3,5-di-tert.-butylphenyl) -2H-benzotriazole;
(h) 5.5 '- (1,8-dithiaoctane-1,8-diyl) bis [2- (2-hydroxy-3,5-di-tert-butylphenyl) -2H-benzotriazole];
(i) 5.5 '- (dithihydrolylo-mononediyl) bis [2- (2-hydroxy-3,5-di-tert-butylphenyl) -2H-benzotriazole];
(k) 5-phenylthio-2 - [(2-hydroxy-3,5-di-tert.-octylphenyl) -2H-benzotriazole];
(l) 5-phenylthio-2- (2-hydroxy-3,5-di-α-cumylphenyl) -2H-benzotriazole;
(m) 5.5'-thiobis [2- (2-hydroxy-3,5-di-tert-butylphenyl) -2H-benzotriazole];
(m) 5-phenylthio-2- [2-hydroxy-3-tert.butyl-5- (β-carboxyethyl) phenyl] -2H-benzotriazole;
(o) 5-phenylthio-2- [2-hydroxy-3-tert.butyl-5- (β-octyloxycarbonylethyl) phenyl] -2H-benzotriazole;
(p) 5-phenylthio-2- {2-hydroxy-3-tert.butyl-5- [2- (ω-hydroxyocta (ethyleneoxy) carbonylethyl] phenyl} -2H-benzotriazole;
(p) 5-phenylthio-2 - [(2-hydroxy-3-tert.butyl-5- (3-hydroxypropyl) phenyl] -2H-benzotriazole;
(c) 3- (5-phenylthio-2H-benzotriazol-2-yl) -5-tert. butyl 4-hydroxyhydrocinnamic acid;
(t) 3- (5-phenylthio-2H-benzotriazol-2-yl) -5-tert amide. butyl 4-hydroxyhydrocinnamic acid;
(y) an isomeric mixture of 3- [3- (5-phenylthio-2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyhydrocinnamoyloxy] -2-hydroxypropylmethacrylate and 2- [3- (5-phenylthio-2H -benzotriazol-2-yl) -5-tert. butyl-4-hydroxyhydrocinnamoyloxy] -3-hydroxypropylmethacrylate;
(f) β-hydroxypoly (ethyleneoxy) -3- (5-phenylthio-2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyhydrocinnamate.  5. A stabilized composition comprising a polymer subjected to destruction due to the adverse effects of actinic radiation and substituted benzotriazole as a stabilizer, characterized in that it contains an effective stabilizing amount of substituted benzotriazole as substituted benzotriazole according to claim 1.  6. The stabilized composition according to claim 5, characterized in that the polymer is selected from the group consisting of polystyrenes, grafted copolymers of styrene, polyphenylene oxides, polyphenylene sulfides, polyurethanes, polyisocyanates, aromatic polyesters, aromatic polyamides, polyureas, polyimides, polyamides, polysulfones , polyetherketones, alkyd resins, aminos and epoxies.  7. The stabilized composition according to claim 6, characterized in that the polymer is an epoxy resin.  8. The stabilized composition according to claim 5, characterized in that it contains 5-n-dodecylthio-2- (2-hydroxy-3,5-di-tert-butylphenyl) -2H-benzotriazole, 5-phenylthio as a stabilizer -2- (2-hydroxy-3,5-di-tert. Butylphenyl) -2H-benzotriazole, 5-phenylthio-2- (2-hydroxy-3-methylphenyl) -2H-benzotriazole, 5-n-octylthio-2 - (2-hydroxy-3,5-di-tert.-butylphenyl) -2H-benzotriazole, 5-phenylthio-2- (2-hydroxy-3,5-di-α-cumylphenyl) -2H-benzotriazole, ω-hydroxypoly (ethyleneoxy) -3- (5-phenylthiobenzotriazol-2-yl) -5-tert. butyl 4-hydroxyhydrocinnamate.  9. A coating system made of lower and upper polymer layers, characterized in that the lower polymer layer comprising an organic or inorganic pigment, or the upper polymer layer, or both layers contain an effective amount of the substituted benzotriazole according to claim 1 as a stabilizer.  10. The coating system according to claim 9, characterized in that the polymer layers as substituted benzotriazole contain 5-phenylthio-2- (2-hydroxy-3,5-di-tert-butylphenyl) -2H-benzotriazole, 5-phenylthio -2- [2-hydroxy-3-tert. -butyl-5- (β-octyloxycarbonylethyl) phenyl] -2H-benzotriazole, 5-phenylthio-2- {2-hydroxy-3-tert. -butyl-5- [2- (ω-hydroxyocta (ethyleneoxy) -carbonylethyl] phenyl} -2H-benzotriazole, ω-hydroxypoly (ethyleneoxy) -3- (5-phenylthiobenzotriazol-2-yl) -5-tert-butyl -4-hydroxyhydrocinnamate.  11. The coating system according to claim 9, characterized in that the polymer layers as substituted benzotriazole contain 5-phenylthio-2- {2-hydroxy-3-tert. -butyl-5- [2-ω-hydroxyocta (ethyleneoxy) -carbonylethyl] phenyl} -2H-benzotriazole, ω-hydroxypoly (ethyleneoxy) -3- (5-phenylthiobenzotriazol-2-yl) -5-tert. -butyl-4-hydroxyhydrocinnamate.  12. The coating system according to claim 9, characterized in that the polymer layers further comprise a UV absorber selected from the group consisting of benzophenones, benzotriazoles, derivatives of cyanoacrylic acid, hydroxyaryl-S-triazines, organic compounds of nickel and oxanilides located either in top, or bottom, or in both layers.  13. The coating system of claim 12, wherein the polymer layers further comprise a UV absorber selected from the group consisting of 2- [2-hydroxy-3,5-di- (α, α-dimethylbenzyl) phenyl] - 2H-benzotriazole, 2- [2-hydroxy-3,5-di-tertamylphenyl) -2H-benzotriazole, 2- [2-hydroxy-3-tert-butyl-5- (ω-hydroxyocta (ethyleneoxy) carbonyl) ethylphenyl] -2H-benzotriazole, 2- [2-hydroxy-3-tert-butyl-5- (2-octyloxycarbonyl-ethyl) phenyl] -2H-benzotriazole, 4,4'-dioxythyloxyoxanilide, 2,2'-dioctyloxy-5, 5'-di-tert-butyl-oxanilide, 2,5'-didodecyloxy-5,5'-di-tert-butyloxanilide, 2-ethoxy-2'-ethylox nilide, 2,6-bis (2,4-dimethylphenyl) -4- (2-hydroxy-4-octyloxyphenyl-s-triazine, 2,6-bis (2,4-dimethylphenyl) -4- (2,4- dihydroxyphenyl) -s-triazine, 2,4-bis (2,4-dihydroxyphenyl) -6- (4-chlorophenyl) -s-triazine, 2,6-bis (2,4-dimethylphenyl) -4- [2- hydroxy-4- (2-hydroxy-3-dodecyloxypropanoxy) phenyl] -s-triazine and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone.  14. The coating system according to claim 9, characterized in that the polymer layers additionally contain an effective stabilizing amount of a phenolic antioxidant in either the upper or lower or both layers.  15. The coating system according to claim 9, characterized in that the polymer layers additionally contain an effective stabilizing amount of the hindered amine in either the upper or lower or both layers.  16. The coating system according to clause 15, wherein the hindered amine is selected from the group consisting of bis) 2,2,6,6-tetramethylpiperidin-4-yl) sebacinate, bis- (1,2,2,6,6 pentamethylpiperidin-4-yl) sebacinate, di (1,2,2,6,6-pentamethylpiperidin-4-yl) (3,5-di-tert.-butyl-4-hydroxybenzyl) butyl malonate, polycondensation product 1- (2 -hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4'-hexamethylene bis (amino-2, 2,6,6-tetramethylpiperidine), N, N ', N' ', -N' '' - Tatrakis [(4,6-bis (butyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -S-triazin-2-yl-1,10-diamino-4,7-diazadecane, di- (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacinate, di- (1 -cyclohenyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate, 1-octyloxy-2,2,6,6-tetramethyl-4-hydroxypiperidine, poly [6-tert-octylamino-s-triazin-2 , 4-diyl] [2- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) iminohexamethylene- [4- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl ) imino] or 2,4,6-tris [N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) -H.-butylamino] -s-triazine.  17. The coating system according to claim 9, characterized in that the polymer layers additionally contain an effective stabilizing amount of phosphite or phosphonite in either the upper or lower or both layers.  18. The coating system according to claim 9, characterized in that it is used for coating coils, penetrating or film-forming wood finishes.  19. Methacrylic copolymer obtained by additive polymerization of an isomeric mixture of 3- [3- (5-phenylthio-2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyhydrocinnamoyloxy] -2-hydroxypropylmethacrylate and 2- [3- ( 5-phenylthio-2H-benzotriazol-2-yl) -5-tert. -butyl-4-hydroxyhydrocinnamoyl] -3-hydroxypropylmethacrylate.  20. A stabilized composition containing a polymer that is subject to destruction due to the adverse effects of actinic radiation, and an effective stabilizing amount of the copolymer according to claim 19.

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