BE1009749A3 - PIPERIDINE COMPOUNDS AND CONTAINING TRIAZINE silicon groups, COMPOSITION CONTAINING SAME AND METHOD FOR USING THE STABILIZATION OF ORGANIC MATERIALS. - Google Patents

Abstract

The invention relates to compounds of formula (I) in which, among other values, m + n is a number from 1 to 60 and n varies between zero and 50% of the sum m + n; X is -0- or -NH-; R1 is a C1-C4 alkyl group or a 2,2,6,6-tetramethyl-4-piperidyl group; R2 is hydrogen or methyl; and A is a C8-C12 alkyl group.

Description

       

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  "Piperidine and triazine compounds containing silicon groups, composition containing them and method of using them to stabilize organic materials"
The present invention relates to novel piperidine and triazine compounds containing silicon groups, their use as stabilizers to protect organic materials, in particular synthetic polymers, against light, heat and oxidation, and organic materials thus stabilized.



   The use of 2,2,6,6-tetramethylpiperidine derivatives containing silicon groups, such as those mentioned in documents US Pat. No. 4,177,186, is already known.
US-A-4,859,759, US-A-4,895,885, US-A-4,946,880, US-A-
4,948,888, US-A-5,134,233, US-A-5,219,905, US-A-5,321,066, EP-A-162,524, EP-A-182,415, EP-A-244,026, EP -A-343 717,
EP-A-388 321, EP-A-480 466, DD-A-234 682 and DD-A-234 683 as stabilizers for synthetic polymers.



   The present invention relates to new compounds corresponding to formula (I)
 EMI1.1
 

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 in which m + n is a number from 1 to 100 and n varies between zero and 90% of the sum m + n;
X is -0- or -NH- i
R1 is hydrogen, a C1-C18 alkyl group, a C2-C4 alkyl group substituted at the 2,3 or 4 position
 EMI2.1
 by a Caca alkoxy group or by a di (C1-C4 alkyl) amino group, a C 1-6 cycloalkyl group unsubstituted or substituted by 1, 2 or 3 C 1-4 alkyl groups, a C7- phenylalkyl group C9 unsubstituted or substituted on phenylalkyl group in C e the phenyl nucleus by 1,2 or 3 alkyl groups in C1-C4, or a group of formula (II):

   
 EMI2.2
 
R2 is hydrogen, a C1-C8 alkyl group, O., OH, NO, CH2CN, a C1-C18 alkoxy group, a cyclo group
 EMI2.3
 C 1-6 alkoxy C 1-6 alkoxy, a Cy-Cn phenylalkyl group unsubstituted or substituted on the phenyl ring by 1,2 or 3 C1-C4 alkyl groups, or a C1-C8 acyl group; and
A is a Ce-C alkyl group. o.



   Examples of an alkyl group having up to 18 carbon atoms are methyl, ethyl, propyl, isopropyl, butyl, 2-butyl, isobutyl, t-butyl, pentyl, 2-pentyl, hexyl, heptyl, octyl, 2- ethylhexyl, t-octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl and octadecyl.



   Examples of a C2-C4 alkyl group substituted by a C1-C8 alkoxy group, preferably C1-C4 alkoxy, in particular methoxy and ethoxy, are the 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl groups, 3-ethoxypropyl, 3-butoxypropyl, 3-octoxypropyl and 4-methoxybutyl.



   Examples of a C 2 -C 4 alkyl group substituted by a di (C 1 -C 4) amino group, preferably

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 dimethylamino or diethylamino, are the 2-dimethylaminoethyl, 2-diethylaminoethyl, 3-dimethylaminopropyl, 3-diethylaminopropyl, 3-dibutylaminopropyl and 4-diethylaminobutyl groups.



   Examples of C1-C18 alkoxy groups are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy and octadecyloxy. Preferred examples are alkoxy groups
 EMI3.1
 in Cc-C. , especially heptoxy and octoxy.



  Examples of a Cc-C cycloalkyl group. unsubstituted or substituted by 1, 2 or 3 C1-C4 alkyl groups are cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethyl-cyclohexyl, trimethylcyclohexyl, b-butylcyclohexyl, cyclooctyl, cyclodecyl. A cyclohexyl group unsubstituted or substituted by a C1-C4 alkyl group is preferred.



   Examples of a C-Cn phenylalkyl group which is unsubstituted or substituted on the phenyl ring by 1,2 or 3 C1-C4 alkyl groups are the benzyl, methylbenzyl, dimethylbenzyl, trimethylbenzyl, t-butylbenzyl and 2-phenylethyl groups. The benzyl group is preferred.



   Examples of a Ce-C cycloalkoxy group. are the cyclopentoxy, cyclohexoxy, cycloheptoxy, cyclooctoxy, cyclodecyloxy and cyclododecyloxy groups. Cyclopentoxy and cyclohexoxy groups are preferred.



   Examples of a C1-C8 acyl group, which can be aliphatic or aromatic, are formyl, acetyl, propionyl, butyryl, isobutyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl and benzoyl. C 1-6 alkanoyl and benzoyl groups are preferred. The acetyl group is particularly preferred.



   The compounds of formula (I) which are of interest are those in which m + n is a number from 1 to 100; for example, n is zero or a number from 1 to 50 and can vary between zero and 50% of the sum m + n.

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   The sum m + n can also be, for example, a number from 2 to 100.4 to 100.8 to 100.2 to 70.4 to 70 or 8 to 70. The variable n preferably varies between 10 and 50% , for example between 20 and 50% or between 30 and 50%, of the sum m + n. In addition, the variable m can be, for example, a number from 10 to 50 and the variable n can be, for example, a number from 0 to 50.5 to 50 or 10 to 40.



   The radical A can be, for example, a group
 EMI4.1
 Cq-C alkyl. g, C-alkyl <o-C <g or C 1 -C 6 alkyl.



  Preferred species for R2 are hydrogen, a C1-C4 alkyl group, OH, a C1-C6 alkoxy group. , a Cc-C6 cycloalkoxy group, the benzyl group or the acetyl group, in particular hydrogen or the methyl group.



   Preferred compounds of formula (I) are those in which m + n is a number from 1 to 90 and n varies between zero and 90% of the sum m + n;
X is -O- or -NH-;
R 1 is hydrogen, a C1-C2 alkyl group, a C5-C7 cycloalkyl group, a C7-C9 phenylalkyl group or a group of formula (II); and
A is a C6-C12 alkyl group.



   Particularly preferred compounds of formula (I) are those in which m + n is a number from 1 to 80 and n varies between zero and 90% of the sum m + n;
X is -O- or -NH-;
R 1 is hydrogen, a C1-C8 alkyl group, a cyclohexyl group, a benzyl group or a group of formula (II); and
A is a Cg-C alkyl group.



   Compounds of formula (I) of particular interest are those in which m + n is a number from 1 to 70 and n varies between zero and 50% of the sum m + n;

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X is -O- or -NH-; R1 is hydrogen, a C1-C4 alkyl group or a group of formula (II); and
A is a C8-C12 alkyl group.



   Compounds of formula (I) which are particularly advantageous are those in which m + n is a number from 1 to 60 and n varies between zero and 50% of the sum m + n;
X is -O- or -NH-; R1 is a C1-C4 alkyl group or a group of formula (II); and
A is a C8-C12 alkyl group.



   Examples of compounds of formula (I) are
 EMI5.1
 

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 EMI6.1
 

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 EMI7.1
 

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 EMI8.1
 and

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 EMI9.1
 
The compounds of the present invention can be prepared, for example, by reacting a compound of formula (III)
 EMI9.2
 where m and n are as defined above, with the appropriate amounts of alkenes capable of forming a group
 EMI9.3
 

  <Desc / Clms Page number 10>

 and a group A-, where R <, R, X and A are as defined above, by carrying out the hydrosilylation reaction in the presence of catalytic amounts of Pt or Rh complex as described in documents EP-A-343,717 and EP-A-388 321 (Chemical Abstracts 115, 160 562f; Derwent 90-284499 / 38) and by Speier (JAC

   S. 79.974, 1957).



   The compounds of formula (III) are commercially available or can be prepared by known methods.



   Alkenes capable of forming a group
 EMI10.1
 are prepared, for example, as described in US-A-4,731,393 or according to known methods, while the alkenes capable of forming a group A are commercially available.



   The compounds of the present invention are very effective in improving the resistance to light, heat and oxidation of organic materials, in particular synthetic polymers and copolymers, and they are particularly suitable for stabilizing polypropylene fibers due to their greater high resistance to volatilization.



   Examples of organic materials that can be stabilized are:
1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, poly-but-l-ene, poly-4-methylpent-l-ene, polyisoprene or

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 polybutadiene, as well as polymers of cycloolefins such as cyclopentene or norbornene, polyethylene (which can optionally be crosslinked), for example high density polyethylene (HDPE), high molecular weight high density polyethylene (HDPE-PME) , ultra-high molecular weight high density polyethylene (HDPE-PMUE), medium density polyethylene (PEMD), low density polyethylene (LDPE),

   linear low density polyethylene (LDPE), branched low density polyethylene (LDPE).



   The polyolefins, that is to say the polymers of monoolefins illustrated by examples in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by various processes, and in particular those which follow: a) radical polymerization (normally under high pressure and at high temperature). b) Catalytic polymerization using a catalyst which normally contains one or more metals from Groups IVb, Vb, VIb or VIII of the Periodic Table. These metals usually have one or more ligands, typically oxides, halides, alcoholates, esters, ethers, amines, alkyl groups, alkenyl groups and / or aryl groups which may be coordinated by n or a bonds.

   These metal complexes can be in the free form or be fixed on substrates, typically on an activated form of magnesium chloride, titanium-III chloride, alumina or silicon oxide. These catalysts can be soluble or insoluble in the polymerization medium. The catalysts can be used alone in the polymerization or else other activators can be used, typically alkylmetals, metal hydrides, alkylmetal halides, alkylmetal oxides or

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 alkylmetalloxanes, said metals being elements of Groups la, IIa and / or IIIa of the Periodic Table. The activators can be conveniently modified with other ester, ether, amine or silyl ether groups.

   These catalytic systems are usually called
Phillips, Standard Oil Indiana, Ziegler (-Natta),
TNZ (Du Pont), metallocenes or monosite catalysts (SSC).



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



   3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example, ethylene / propylene copolymers, linear low density polyethylene (LDPE) and its mixtures with low density polyethylene (LDPE), copolymers propylene / but-1-ene, propylene / isobutylene copolymers, ethylene / but-1-ene copolymers, ethylene / hexene copolymers, ethylene / methylpentene copolymers, ethylene / heptene copolymers, ethylene / octene copolymers, copolymers propylene / butadiene, isobutylene / isoprene copolymers, ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers,

   ethylene / vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene / acrylic acid copolymers and their salts (ionomers) as well as ethylene terpolymers with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidenenorbornene; and mixtures of these copolymers with each other and with the polymers mentioned in 1) above, for example polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate (EVA) copolymers, LDPE / ethylene-acrylic acid copolymers (EAA) ), PEBDL / EVA and PEBDL / EAA and alternating or random polyalkylene / copolymers

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 carbon monoxide and mixtures thereof with other polymers, for example polyamides.



   4. Hydrocarbon resins (eg Ce-Cg), including their hydrogenated modification products (eg tackifiers), and mixtures of polyalkylenes and starch.



   5. Polystyrene, poly (p-methylstyrene), poly- (a-methylstyrene).



   6. Copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives, for example styrene / butadiene, styrene / acrylonitrile, styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate, styrene / butadiene / methacrylate alkyl, styrene / maleic anhydride, styrene / acrylonitrile / methyl acrylate; blends with high impact strength of styrenic copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene / propylene / diene terpolymer; and block copolymers of styrene, for example styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene.



   7. Grafted copolymers of styrene or α-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and alkyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene / propylene / diene terpolymers;

   styrene and acrylonitrile on alkyl polyacrylates or alkyl polymethacrylates, styrene and acrylonitrile on acrylate / butadiene copolymers, as well as their mixtures with the copolymers listed in 6), for example mixtures of copolymers known as ABS polymers, MBS, ASA or AES.

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   8. Halogenated polymers such as polychloroprene, chlorinated rubbers, a chlorinated and brominated isobutylene-isoprene copolymer (halogenated butyl rubber), chlorinated or chlorosulfonated polyethylene, copolymers of ethylene and chlorinated ethylene, homo- and epichlorohydrin copolymers, in particular polymers of halogenated vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as their copolymers such as vinyl chloride / chloride chloride vinylidene, vinyl chloride / vinyl acetate or vinylidene chloride / vinyl acetate.



   9. Polymers which are derived from unsaturated acids in a, ss and their derivatives, such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles modified with butyl acrylate to improve impact resistance.



   10. Copolymers of the monomers mentioned in 9) with one another or with other unsaturated monomers, for example acrylonitrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, acrylonitrile / alkoxyalkyl acrylate or acrylonitrile / vinyl halide copolymers or the acrylonitrile / alkyl methacrylate / butadiene terpolymers.



   11. Polymers which are derived from unsaturated alcohols and amines, or from their acylated derivatives or their acetals, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers formed with the olefins mentioned in 1) above.



   12. Homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, poly (ethylene oxide), poly (propylene oxide) or their copolymers formed with bisglycidyl ethers.



   13. Polyacetals such as polyoxymethylene and polyoxymethylenes which contain ethylene oxide

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 as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.



   14. Phenylene polyoxides and polysulphides and mixtures of phenylene polyoxides with styrenic polymers or polyamides.



   15. Polyurethanes which are derived, on the one hand, from polyethers, polyesters or polybutadienes having terminal hydroxyl groups, and, on the other hand, from aliphatic or aromatic polyisocyanates, as well as their precursors.



   16. Polyamides and copolyamides which are derived from diamines and dicarboxylic acids and / or amino carboxylic acids or corresponding lactams, such as polyamide 4, polyamide 6, polyamide 6-6, polyamides 6-10 , 6-9, 6-12,4-6, 12-12, polyamide 11, polyamide 12, aromatic polyamides obtained from m-xylenediamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic and / or terephthalic acid and optionally an elastomer as a modifier, for example poly-2,4, 4-trimethylhexamethylene-terephthalamide or poly-m-phenylene-isophthalamide; and also the block copolymers of the aforementioned polyamides with polyolefins, olefinic copolymers, ionomers or elastomers chemically linked or grafted;

   or with polyethers, for example polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified by EPDM or ABS; and polyamides condensed during processing (R.I.M systems for polyamides).



     17. Polyureas, polyimides, polyamide-imides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles.



   18. Polyesters which are derived from dicarboxylic acids and diols and / or hydroxy carboxylic acids or corresponding lactones, for example polyethylene terephthalate, polybutylene terephthalate, 1,4- polyterephthalate dimethylolcyclohexane and

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 polyhydroxybenzoates, as well as block copolyetheresters derived from polyethers having terminal hydroxyl groups; and also polyesters modified with polycarbonates or MBS.



   19. Polycarbonates and polyestercarbonates.



   20. Polysulfones, polyethersulfones and polyetherketones.



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



   22. Drying and non-drying alkyd resins.



   23. Unsaturated polyester resins which are derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyalcohols and vinyl compounds as crosslinking agents, and also their halogenated modification products with low flammability.



   24. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy-acrylates, urethane-acrylates or polyester-acrylates.



   25. Alkyd resins, polyester resins or acrylic resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.



   26. Crosslinked epoxy resins which are derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, for example the products of diglycidyl ethers of bisphenol A and bisphenol F, which are crosslinked with usual hardeners such as anhydrides or amines, with or without accelerators.



   27. Natural polymers such as cellulose, rubber, gelatin and their chemically modified homologous derivatives, for example cellulose acetates, cellulose propionates and cellulose butyrates, or cellulose ethers such as methylcellulose; as well as rosins and their derivatives.

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   28. Blends of the above polymers, for example PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE , PVC / acrylates, POM / PUR thermoplastic, PC / PUR thermoplastic, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA 6-6 and copolymers, PA / PEHD, PA / PP, PA / PPO, PBT / PC / ABS or PBT / PET / PC.



   29. Natural and synthetic organic materials which are pure monomeric compounds or mixtures of such compounds, for example mineral oils, animal and vegetable fats, oils and waxes, or oils, fats and waxes based on synthetic esters ( for example phthalates, adipates, phosphates or trimellates) and also mixtures of synthetic esters with mineral oils in all weight proportions, typically those used as spinning compositions, as well as the aqueous emulsions of these materials.



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



   The compounds of formula (I) are particularly suitable for improving the light stability, the heat stability and the stability against oxidation of polyolefins, in particular polyethylene and polypropylene.



   The compounds of formula (I) can be used in the form of mixtures with organic materials in various proportions, depending on the nature of the material to be stabilized, the end use and the presence of other additives.



   In general, it is suitable to use, for example, 0.01 to 5% by weight of the compounds of formula (I) relative to the weight of the material to be stabilized, preferably 0.05 to 1%.



   In general, the compounds of formula (I) can be added to the polymeric materials before, during or after the polymerization or crosslinking of said materials.



   The compounds of formula (I) can be incorporated into the polymeric materials in pure form or in form encapsulated in waxes, oils or polymers.

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   The compounds of formula (I) can be incorporated into the polymeric materials by various methods such as dry mixing in the form of powder, or wet mixing in the form of solutions or suspensions or also in the form of a mixture -master ; in these operations, the polymer can be used in the form of powder, granules, solution, suspension or in the form of latex.



   The materials stabilized with the compounds of formula (I) can be used for the production of molded articles, films, ribbons, monofilaments, fibers, surface coatings, etc.



   Optionally, other conventional additives for synthetic polymers, for example antioxidants, UV light absorbents, nickel stabilizers, pigments, fillers, plasticizers, corrosion inhibitors and metal deactivators, can be added to the mixtures of the compounds of formula (I ) with organic matter.



   Particular examples of additives which can be used in admixture with the compounds of formula (I) are as follows: 1. Antioxidants
 EMI18.1
 1. 1. Alkylated monophenols, for example: 2, 6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4, 6-dimethylphenol, 2, 6-ditert-butyl-4-ethylphenol, 2, 6-di-tert-butyl-4-n-butylphenol, 2, 6-di-tert-butyl-4-isobutylphenol, 2, 6-dicyclopentyl- 4-methylphenol, 2- (a-methylcyclohexyl) -4, 6- dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4, 6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linear or branched in side chains, for example 2.6 -dinonyl-4-methylphenol, 2,4-dimethyl- 6- (1'-methylundéc-1'-yl) phenol, 2,4-dimethyl-6- (1'-methyl-heptadéc-1'-yl) phenol , 2,

     4-dimethyl-6- (1'-methyltridec- 1'-yl) phenol and mixtures thereof.



  1.2. Alkylthiomethylphenols, for example: 2,4-dioctylthio-methyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol.

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 EMI19.1
 



  1. 3. Hydroquinones and alkylated hydroquinones, for example: 2, 6-di-tert-butyl-4-methoxyphenol, 2, 5-di-tert-butylhydroquinone, 2, 5-di-tert-amylhydroquinone, 2, 6- diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-ditert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di- stearate tert-butyl-4-hydroxyphenyl, bis adipate (3,5-dí-tert-butyl-4-hydroxyphenyl). 1.4. Tocopherols, for example: a-tocopherol, 0-tocopherol, y-tocopherol, 6-tocopherol and their mixtures (Vitamin E).



  1.5. Hydroxylated diphenyl thioethers, for example: 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis-
 EMI19.2
 (4-octylphenol), 4, 4'-thiobis (6-tert-butyl-3-methylphen01), 4, 4'-thiobis (6-tert-butyl-2-methylphenol), 4, 4'-thiobis- ( 3,6-di-sec-amylphenol), 4,4'-bis (2,6-dimethyl-4-hydroxyphenyl) disulfide.



  1.6. Alkylidene-bisphenols, for example: 2, 2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylene-bis (6-tertbutyl-4-ethylphenol), 2, 2'-methylene- bis [4-methyl- 6 - (&alpha; -methylcyclohexyl) phenol], 2,2'-methylene-bis (4-methyl- 6-cyclohexylphenol), 2,2'-methylene-bis (6-nonyl-4- methylphenol), 2,2'-methylene-bis (4,6-di-tert-butylphenol), 2,2'- ethylidene-bis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis ( 6-tert-butyl-4-isobutylphenol), 2,2'-methylene-bis-
 EMI19.3
 [6- (a-methylbenzyl) -4-nonylphenol], 2, 2'-methylene-bis- [6- (a, <x-dimethylbenzyl) -4-nonylphenol], 4,4'-methylenebis (2, 6-di-ert-butylphenol), 4,4'-methylene-bis (6-tertbutyl-2-methylphenol), 1, 1 -bis (S-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,

   6-bis (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-dodecylmercaptobutane,
 EMI19.4
 ethylene glycol bis [3, 3-bis (3'-tert-butyl-41-hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-S-methylphenyl) dicyclopentadiene, bis [2 terephthalate] - (31 - tert-butyl-21-hydroxy-S'-methylbenzyl) -6-tert-butyl-4-methyl-phenyl], 1, 1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2.2 -bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane,

  <Desc / Clms Page number 20>

 2, 2-bis- (S-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecyl- mercaptobutane, 1, 1, 5, 5-tetra (5-tert-butyl-4-hydroxy- 2-methylphenyl) pentane.



  1.7. 0-, N- and S-benzylated compounds, for example: 3.5, 3 ', 5'-
 EMI20.1
 tetra-tert-butyl-4, 4'-dihydroxy (dibenzyl oxide), 4-hydroxy-3, 5-dimethylbenzylmercaptoacetate octadecyl, 4-hydroxy-3, 5-di-tert-butylbenzylmercaptoacetate tridecyl, tris (3 , S-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-tert-butyl-) sulfide 4-hydroxybenzyl), 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate isooctyl.



  1.8. Hydroxybenzylated malonates, for example: 2,2-bis (3, 5-
 EMI20.2
 dioctadecyl di-tert-butyl-2-hydroxybenzyl), 2- (3-tert-butyl-4-hydroxy-S-methylbenzyl) dioctadecyl malonate, 2, 2-bis (3, S-di-tert-butyl -4-hydroxybenzyl) didodecylmercaptoethyl malonate, 2,2-bis (3,5-di-tert-butyl- 4-hydroxybenzyl) bis [4- (1, 1,3, 3-tetramethylbutyl) phenyl] malonate .
 EMI20.3
 



  1. 9. Aromatic hydroxybenzyl compounds, for example 1, 3, 5-tris (3, S-di-tert-butyl-4-hydroxybenzyl) -2, 4, 6-trimethylbenzene, 1, 4-bis (3, S -di-tert-butyl-4-hydroxybenzyl) - 2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol.



  1.10. Triazine compounds, for example: 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1, 3, 5triazine, 2-octylmercapto-4,6-bis (3 , 5-di-tert-butyl-
 EMI20.4
 4-hydroxyanilino) -1, 3, 5-triazine, 2-octylmercapto-4, 6-bis- (3, S-di-tert-butyl-4-hydroxyphenoxy) -1, 3, 5-triazine, 2, 4 , 6tris (3, S-di-tert-butyl-4-hydroxyphenoxy) -1, 2, 3-triazine, isocyanurate of 1, 3, 5-tris (3, S-di-tert-butyl-4-hydroxybenzyle) , 1,3,5-tris (4-tert-butyl-3-hydroxy- 2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3, S-di-tert-butyl-4-hydroxy- phenylethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hexahydro-1,3,5-triazine, isocyanurate of 1,3, 5-tris (3,5-dicyclohexyl-4-hydroxybenzyl).

  <Desc / Clms Page number 21>

 1.11.

   Benzylphosphonates, for example: dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-
 EMI21.1
 Diethyl 4-hydroxybenzylphosphonate, 3,5-di-tert-butyl- 4-hydroxybenzylphosphonate dioctadecyl, 5-tert-butyl- 4-hydroxy-3-methylbenzylphosphonate dioctadecyl, the calcium salt of the monoethyl ester of 3,5-di-tertbutyl-4-hydroxybenzylphosphonic acid.



  1.12. Octylaminophenols, for example: 4-hydroxylauranilide, 4-hydroxystearanilide, N- (3,5-di-tert-butyl-4-hydroxyphenyl) octyl carbamate.



  1.13. P- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid esters with mono or polyalcohols, for example with methanol, ethanol, n-octanol, isooctanol , octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentylglycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thia-undecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-
 EMI21.2
 1-phospha-2, 6, 7-trioxabicyclo [2. 2.2] octane.



  1. 14. Esters of P- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono or polyalcohols, for example with methanol, ethanol, n-octanol , isooctanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentylglycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide,
 EMI21.3
 3- thia-undecanol, 3-thiapentadecanol, trimethyhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha- 2, 6, 7-trioxabicyclo [2. 2.2] octane.



  1.15. P- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid esters with mono or polyalcohols, for example with methanol, ethanol, octanol, octadecanol, 1,6hexanediol, 1,9-nonanediol, ethylene glycol, 1,2propanediol, neopentyl-glycol, thiodiethylene-glycol,

  <Desc / Clms Page number 22>

 diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'bis (hydroxyethyl) oxamide, 3-thia-undecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane , 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2. 2.2] octane.



  1.16. Esters of 3, S-di-tert-butyl-4-hydroxyphenylacetic acid with mono or polyalcohols, for example with methanol, ethanol, octanol, octadecanol, 1,6hexanediol, 1,9-nonanediol, ethylene glycol, 1,2propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris isocyanurate (hydroxyethyl), N, N'-bis- (hydroxyethyl) oxamide, 3-thia-undecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,
 EMI22.1
 4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2. 2.2] octane. 1. 17.

   Amides of ss- (3, S-di-tert-butyl-4-hydroxyphenyl) propionic acid, for example: N, N'-bis (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine,
 EMI22.2
 N, N'-bis (3, S-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine, N, N'-bis (3, S-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine.



  1.18. Ascorbic acid (vitamin C) 1.19. Amino antioxidants, for example: N, N'-diisopropylp-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1, 4-dimethylpentyl) -p-phenylenediamine, N, N'-bis- (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis- (1-methylheptyl) -p-phenylenediamine, N, N'-dicyclohexylp-phenylenediamine, N, N'- diphenyl-p-phenylenediamine, N, N'-bis (2-naphthyl) -p-phenylenediamine, N-isopropyl-
 EMI22.3
 N'-phenyl-p-phenylenediamine, N- (1, 3-dimethylbutyl) -N'phenyl-p-phenylenediamine, N- (1-methylheptyl) -N'-phenyl- p-phenylenediamine, N-cyclohexyl-N ' -phenyl-p-phenylenediamine, 4- (p-toluene-sulfamoyl) diphenylamine, N, N'-dimethylN, N'-di-sec-butyl-p-phenylenediamine, diphenylamine,
 EMI22.4
 N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamin,

   N- (4-tert-octylphenyl) -1-naphthylamine,

  <Desc / Clms Page number 23>

 
 EMI23.1
 N-phenyl-2-naphthylamine, octylated diphenylamine such as p, p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, e 4-n-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoyinin (4-methoxyphenyl) amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N, N, N ', N'-tetramethyl-4,4 '-diaminodiphenylmethane, 1,2-bis- [(2-methylphenyl) amino] ethane, 1,2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1', 3'-dimethylbutyl) phenyl] amine, N-phenyl-1-naphthylamine tert-octylated, mixture of tert-butyl / tert-octyldiphenylamines mono- and dialkylated,

   mixture of mono-and dialkylated nonyldiphenylamines, mixture of mono-and dialkylated dodecyldiphenylamines, mixture of mono-and dialkylated isopropyl / isohexyldiphenylamines, mixture of mono-and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4 -1, 4-benzothiazine, phenothiazine, mixture of tert-butyl / tert-octylphenothiazines mono- and dialkylated, mixture of tert-octylphenothiazines mono- and dialkylated, N-allylphenothiazine, N, N, N ', N'-tetraphenyl-1 , 4-diaminobut-2-ene, N, N-bis (2,2,6,6-tetramethylpiperid-4-yl) hexamethylenediamine, bis (2,2,6,6-tetramethylpiperid-4-yl) sebacate, 2,2,6,6,6-tetramethylpiperidine-4-one, 2,2,6,6,6-tetramethylpiperidine-4-ol.



  2. UV light absorbents and light stabilizers
 EMI23.2
 2. 1. 2- (2'-hydroxypheny 1) benzotriazoles, for example 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'-ditert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (S'-tert-butyl- 2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-S'- (1, 1, 3, 3tetramethylbutyl) phenyl) benzotriazole, 2- (3 ', 5 '-di-tertbutyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'- <:

   ert: butyl-2'-hydroxy-5'-methylphenyl) -S-chlorobenzotriazole, 2- (3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy -4'-octyloxyphenyl) benzotriazole, 2- (3 ', 5'-di-tert-amyl-2'-hydroxyphenyl) benzotriazole, 2- (3', 5'-bis- (a, a-dimethylbenzyl) -2 '-hydroxyphenyl) benzotriazole, mixture of 2- (3'-tert-butyl-2'-hydroxy-5' - (2-octyloxycarbonylethyl) -

  <Desc / Clms Page number 24>

 
 EMI24.1
 phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-5 '- [2- (2- ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl -2'-hydroxy-5'- (2-methoxycarbonylethyl) phenyl) -S-chlorobenzotriazole, 2- (3'-tertbutyl-2'-hydroxy-5'- (2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3 '-tert-butyl-2'-hydroxy-5'- (2-octyloxycarbonyl-ethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5' - [2- (2-ethylhexyloxy)

   carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (3'-tert-butyl-2'-hydroxy-5'- (2 -isooctyloxycarbonylethyl) phenylbenzotriazole, 2, 2'-methylene-bis [4- (1, 1, 3, 3-tetramethylbutyl) -6-benzotriazole-2-ylphenol]; the transesterification product of 2- [3'-tert- butyl-5'- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300; [R-CHCH-COO (CH) g, where 2) 3421 0 'R = 3'- tert -butyl-4'-hydroxy-5'-2H-benzotriazole-2-ylphenyl.



  2. 2. 2-hydroxybenzophenones, for example derivatives carrying substituents 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4, 2 ', 4'-trihydroxy and 2 '-hydroxy-4,4'-dimethoxy.



  2. 3. Esters of substituted and unsubstituted benzoic acids, for example: 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylrésorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoylrésorcinol, 3, 5,4-di-tert-butyl-4-hydroxybenzoate of 3,5-di-tert-butylphenyl, 3,5-di-tert-butyl-4-hydroxybenzoate of hexadecyl, 3,5-ditert-butyl-4-hydroxybenzoate of octadecyl , 3, 5-di-tert-butyl-4-hydroxybenzoate of 2-methyl-4, 6-di-tert-butylphenyl.



  2. 4. Acrylates, for example: a-cyano-P, ss-ethyl diphenylacrylate, a-cyano-ss, isooctyl ss-diphenylacrylate, a-methyl carbomethoxycinnamate, a-cyano-P-methyl-p -methyl methoxycinnamate, butyl a-cyano-P-methyl-p-methoxycinnamate, methyl a-carbomethoxy-p-methoxycinnamate and N- (P-carbomethoxy-ss-cyanovinyl) -2-methylindoline.



  2. 5. Compounds of nickel, for example: complexes of nickel with 2, 2'-thio-bis [4- (1, 1, 3, 3-tetramethylbutyl) phenol] such as the 1: 1 or 1 complex : 2, with or without ligands

  <Desc / Clms Page number 25>

 additional such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters, for example methyl or ethyl ester, acid
 EMI25.1
 4-hydroxy-3, 5-di- <: er <: -butylbenzylphosphonique, nickel complexes with ketoximes, for example with 2-hydroxy-4-methylphenylundecyl ketoxime, nickel complexes with 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.



  2. 6. Sterically hindered amines, for example: bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2, 6,6-tetramethyl-4-piperidyl) succinate, bis- (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis- (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, n-butyl- 3, 5-di-tert-butyl-4-hydroxybenzylmalonate bis (1, 2,2, 6,6pentamethyl-4-piperidyl), condensation product of 1- (2-hydroxyethyl) -2, 2, 6, 6-tetramethyl-4-hydroxypiperidine and succinic acid, condensation product of N, N'-bis (2,2, 6, 6-tetramethyl-4-piperidyl) hexamethylene diamine and 4-tert- octylamino-2, 6-dichloro-1,3,5-triazine, nitrilotriacetate of tris (2,2, 6, 6-tetramethyl-4-piperidyl),

     butane-1,2,3,4-tetrakis- (2,2,6,6-tetramethyl-4-piperidyl) tetracarboxylate, 1, 1'- (1, 2-ethanediyl) - bis (3,3, 5 , 5-tetramethylpiperazinone), 4-benzoyl-2,2, 6,6tetramethylpiperidine, 4-stearyloxy-2,2, 6,6-tetramethylpiperidine, 2-n-butyl-2- (2-hydroxy-3, S-di -tert-butylbenzyl) - bis (1,2,2,6,6-pentamethylpiperidyl) malonate, 3-n-octyl- 7,7,9,9,9-tetramethyl-1, 3, 8-triazaspiro [4.

   5] decane-2, 4-dione, bis (1-octyloxy-2, 2, 6, 6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2, 2, 6, 6-tetramethylpiperidyl) succinate, condensation of N, N'-bis (2,2,6,6-tetramethyl-
 EMI25.2
 4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1, 3,5-triazine, condensation product of 2-chloro-4,6-bis (4-n-butylamino-2,2 , 6, 6-tetramethyl-piperidyl) -1, 3, 5-triazine and 1, 2-bis (3-aminopropylamino) - ethane, condensation product of 2-chloro-4, 6-di (4-nbutylamino -1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine

  <Desc / Clms Page number 26>

 and 1,2-bis (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl-7,7, 9,9-tetramethyl-1, 3, 8-triazaspiro [4.

   5] decane-2, 4-dione, 3-dodecyl-1- (2, 2,6, 6-tetramethyl-4-piperidyl) pyrrolidine- 2, 5-done, 3-dodecyl-1- (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) pyrrolidine-2, 5-dione, mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidines, condensation product of N, N ' -bis (2,2,6,6-tetramethyl-
 EMI26.1
 4-piperidyl) hexamethylenediamine and 4-cyclohexylamino-2, 6-dichloro-1, 3, 5-triazine, condensation product of 1, 2-bis (3-aminopropylamino) ethane and 2, 4, 6- trichloro- 1, 3, 5-triazine as well as 4-butylamino-2, 2, 6, 6-tetramethylpiperidine (CAS Reg.

   NO [136504-96-6], N- (2, 2, 6, 6tetramethyl-4-piperidyl) -n-dodecylsuccinimide, N- (1, 2, 2, 6, 6pentamethyl-4-piperidyl) -n-dodecylsuccinimide , 2-undecyl- 7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro [4. 5] decane, reaction product of 7.7, 9.9-tetramethyl-2-cycloundecyl-1oxa-3, 8-diaza-4-oxospiro [4. 5] decane and epichlorohydrin.



  2.7. Oxamides, for example: 4, 4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2, 2'-dioctyloxy-5, 5'-di-tertbutoxanilide, 2, 2'-didodecyloxy-5, 5'-di-tert -butoxanilide,
 EMI26.2
 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-S-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2'-ethyl- 5, 4'-di-tert-butoxanilide and mixtures of disubstituted ortho and para-methoxy-oxanilides and mixtures of disubstituted o- and p-ethoxy-oxanilides.



  2.8. 2- (2-hydroxyphenyl) -1, 3, 5-triazines, for example: 2,4, 6-tris (2-hydroxy-4-octyloxyphenyl) -1, 3, 5-triazine, 2- (2-hydroxy -4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) - 1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl ) -1, 3, 5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -
 EMI26.3
 6- (2, 4-dimethylphenyl) -1, 3, S-triazine, 2- (2-hydroxy- 4-octyloxyphenyl) -4, 6-bis (4-methylphenyl) -1, 3, 5-triazine, 2 - (2-hydroxy-4-dodecyloxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) - 1, 3, 5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4, 6-bis- (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-
 EMI26.4
 hydroxy-3-butyloxypropoxy) phenyl] -4,6-bis (2,

   4-dimethylphenyl) -1, 3, 5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl] -4, 6-bis (2, 4-dimethylphenyl) -1, 3 , 5-triazine,

  <Desc / Clms Page number 27>

   2- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine 2- [2-
 EMI27.1
 hydroxy-4- (2-hydroxy-3-dodecyloxypropoxy) phenyl] -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-hexyl-oxy ) phenyl-4, 6-diphenyl-1, 3, 5-triazine, 2- (2-hydroxy- 4-methoxyphenyl) -4, 6-diphenyl-1,3, 5-triazine, 2,4, 6-tris - [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl] -1, 3, 5triazine, 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl- 1,3, 5-triazine.



  3. Metal deactivators, for example: N, N'-diphenyloxamide, N-salicylal-N'-salicyloylhydrazine, N, N'-bis- (salicyloyl) hydrazine, N, N'-bis (3, 5-di- tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1, 2, 4-triazole, bis (benzylidene) oxalyldihydrazide, oxanilide, isophthaloyldihydrazide, sebacoylbisphenylhydrazide, N, N'-diacetyladipoyldihydrazide) oxalyldihydrazide, N, N'-bis (salicyloyl) thiopropionyldihydrazide.



  4. Phosphites and phosphonites, for example: triphenyl phosphite, diphenyl and alkyl phosphites, phenyl and dialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl and pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecyl and pentaerythritol diphosphite, bis (2,4-ditert-butylphenyl) and pentaerythritol diphosphite, bis (2,6-di-tert- diphosphite butyl-4-methylphenyl) and pentaerythritol, diisodecyl diphosphite and pentaerythritol, bis (2,4-di-tert-butyl-6-methylphenyl) and pentaerythritol diphosphite, bis (2,4,6-diphosphite) -tert-butylphenyl) and pentaerythritol, tristearyl and sorbitol triphosphite, 4,

  4'-biphenylene-diphosphonite of tetrakis- (2,4-di-tert-butylphenyl), 6-isooctyloxy-2,4, 8, 10-tetra-tert-butyl-12H-dibenz [d, g] -1, 3,2-dioxaphosphocine, 6-fluoro- 2,4, 8, 10-tetra-tert-butyl-12-methyl-dibenz [d, g] -1, 3,2-
 EMI27.2
 dioxaphosphocine, bis (2,4-di-tert-butyl-6-methylphenyl) and methyl phosphite, bis (2,4-di-tert-butyl-6-methylphenyl) and ethyl phosphite.

  <Desc / Clms Page number 28>

 



  5. Hydroxylamines, for example: N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-ditetradecylhydroxylamine, N, N-dihexadecylhydroxylamine, N, N , N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N, N-dialkylhydroxylamine derived from hydrogenated tallow amine.



  6. Nitrones, for example: N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methylnitrone, N-octyl-alpha-heptylnitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnitrone, N-hexadecyl -alpha-pentadecylnitrone, N-octadecylalpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecylnitrone, N-octadecyl-alpha-pentadecylnitrone, N-heptadecylalpha-heptadecylnitrone, N-octadecyl-nitrone-hexadecone hydrogenated tallow amine.



  7. Sulfur synergists, for example: dilauryl thiodipropionate or distearyl thiodipropionate.



  8. Compounds eliminating peroxides, for example: esters of ss-thiodipropionic acid such as lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or zinc salt of 2-mercaptobenzimidazole, dibutyldithiocarbamate of zinc, dioctadecyl disulfide, (ss-dodecylmercapto) pentaerythritol propionate.



  9. Stabilizers for polyamides, for example: copper salts in combination with iodides and / or phosphorus compounds and divalent manganese salts.



  10. Basic co-stabilizers, for example: melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of acids higher fats such as calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or tin pyrocatecholate.

  <Desc / Clms Page number 29>

 



  11. Nucleating agents, for example: mineral substances such as talc, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates, preferably of alkaline earth metals; organic compounds such as mono or polycarboxylic acids and their salts, for example 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds such as ionic copolymers ("ionomers").



  12. Fillers and reinforcing agents, for example: calcium carbonate, silicates, glass fibers, hollow glass beads, asbestos, talc, kaolin, mica, barium sulphate, metal oxides and hydroxides, carbon black, graphite, sawdust wood and flours or fibers from other natural products, synthetic fibers.



  13. Other additives, for example: plasticizers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow control agents, optical brightening agents, flame retardants, antistatic agents and blowing agents.



  14. Benzofurannones and indolinones, for example: compounds proposed in documents US-A-4,325,863, US-A-4,338,244, US-A-5,175,312, US-A-5,216,052, US-A- 5 252 643, DE-A-4 316 611, DE-A-4 316 622, DE-A-4 316 876, EP-A-0 589 839 and EP-A-
 EMI29.1
 0 591 102, or 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-tertbutylbenzofuran-2-one, 5,7-di-erù-butyl-3- [4- (2-stearoyloxyethoxy) phenyl] benzofuran-2-one, 3, 3'-bis [5, 7-di-tertbutyl-3- (4- [2-hydroxyethoxy] phenyl) benzofuran-2-one], 5, 7-di-tert- butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3, 5-dimethylphenyl) -5, 7-di-tert-butylbenzofuran-2-one, 3- (3, 5- dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butylbenzofuran-2-one.



   The compounds of the invention can also be used as stabilizers, in particular as light stabilizers, for almost all materials known in photographic reproduction technology and other reproduction techniques, as described for example in Research Disclosure 1990, 31429 (pages 474 to 480).

  <Desc / Clms Page number 30>

 



   Some examples of the preparation and use of the compounds of formula (I) are given to illustrate the present invention in more detail. These examples are presented for illustrative purposes only and do not imply any restrictions.



  EXAMPLE 1 Preparation of a polysiloxane of formula
 EMI30.1
 
44.5 g (77.8 mmol) of 2-allyloxy-4,6-bis- [N- (1,2,2,6,6-pentamethyl-4-piperidyl) butylamino] -1.3 are dissolved. 5triazine in 50 ml of xylene and 2 mg of Pic12 (styrene) 2 are added.



   The solution is heated to 140 ° C. and, while being stirred, a solution of 10 g (3 mmol) of polymethylhydrosiloxane terminated with trimethylsilyl groups (having 53 Si-H units) in 150 ml of is slowly added thereto.
 EMI30.2
 xylene. The reaction mixture is kept at 140 ° C. for 3 hours. It is cooled to 700C and, while stirring continues, 15 g (133.9 mmol) of octene-1 are added, then another 2 mg of PtCl2 (styrene) 2.



  The mixture is heated to 100 ° C. with stirring for 6 hours and the solvent and the excess of octene-1 are removed by distillation under vacuum (140 ° C. / 10 Pa).



  A white solid is obtained having a P.F. of 75-79 C.



   NMR and IR analyzes confirm the planned structure.

  <Desc / Clms Page number 31>

 EXAMPLE 2 Preparation of a polymethylsiloxane of formula
 EMI31.1
 
Following a procedure analogous to that described in Example 1, 43.2 g (77.7 mmol) of 2-allylamino-4, 6-bis [N- (2, 2, 6, 6-) are reacted. tetramethyl-4-piperidyl) butylamino] -1, 3,5-triazine with 10 g of polymethylhydrosiloxane terminated by trimethylsilyl groups (having 53 Si-H units) and with 15 g (133.9 mmol) of octene-1 in presence of 4 mg of PtCl2 (styrene) 2 in xylene.



   After removing the solvent and excess octene-1 by vacuum distillation (150 C / 100 Pa), a solid is obtained having a P.F. of 110-115 C.



   NMR and IR analyzes confirm the planned structure.



  EXAMPLE 3 Preparation of a polymethylsiloxane of formula
 EMI31.2
 

  <Desc / Clms Page number 32>

 
Following a procedure analogous to that described in Example 1, 43.4 g (77.8 mmol) of 2-allyloxy-4,6-bis [N- (2, 2,6, 6 -) are reacted. tetramethyl-4-piperidyl) butylamino] -1, 3, 5-triazine with 10 g (3 mmol) depolymethyl-hydrosiloxane terminated by trimethylsilyl groups (having 53 Si-H units) and with 15 g (133.9 mmol) d octene-1 in the presence of 4 mg of PtCl2 (styrene) 2 in xylene.



   After removing the solvent and excess octene-1 by vacuum distillation (140 C / 100 Pa), a solid is obtained having a P.F. of 90-95 C.



   NMR and IR analyzes confirm the planned structure.



  EXAMPLE 4 Preparation of a polymethylsiloxane of formula
 EMI32.1
 
By following a procedure analogous to that described in Example 1, 45.5 g (77.8 mmol) of 2-allylamino-4,6-bis [N- (1,2,2,6,) are reacted. 6-pentamethyl-4-piperidyl) butylamino] -1, 3,5-triazine with 10 g (3 mmol) of polymethylhydrosiloxane terminated by trimethylsilyl groups (having 53 Si-H units) and with 15 g (133.9 mmol) octene-1 in the presence of 4 mg of PtCl2 (styrene) 2 in xylene.



   After removing the solvent and excess octene-1 by vacuum distillation (140oC / 100 Pa), a solid is obtained having a P.F. of 94-98 C.



   NMR and IR analyzes confirm the planned structure.

  <Desc / Clms Page number 33>

 



  EXAMPLE 5: Light stabilization action on polypropylene fibers
In a slow mixer, 2.5 g of each of the compounds indicated in Table 1.1 g of tris (2,4-di-t-butylphenyl) phosphite, 0.5 g of the calcium salt of monoethyl ester of 1 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid, 1 g of calcium stearate and 2.5 g of titanium dioxide are mixed with 1000 g of polypropylene powder having a melt index of 12 g / 10 min (measured at 230 C and 2.16 kg).



   The mixtures are extruded at 200-230 ° C. to form polymer granules which are then transformed into fibers using a pilot-type apparatus [Leonard-Sumirago (VA) Italy] and operating under the following conditions:
Extruder temperature: 200-230 C
Head temperature: 255-260 C
Draw ratio: 1: 3.5
Linear mass: 11 dtex per filament.



   After being mounted on white cardboard, the fibers thus produced are exposed in a Weather-O-Meter accelerated aging apparatus, model 65WR (ASTM D2565-85) with a black panel temperature of 63 C.



   The residual toughness is measured on samples taken after various times of exposure to light using a constant speed tensiometer and the exposure time, in hours, necessary to halve the initial toughness is then calculated (Te0 ).



   For comparison, fibers produced under the same conditions as above, but without addition of the stabilizers of the present invention, are also exposed.



   Table 1 presents the results obtained. Table 1
 EMI33.1
 
 <tb>
 <tb> Stabilizer <SEP> T ,, <SEP> (hours)
 <tb> Without <SEP> stabilizer <SEP> 150
 <tb> Compound <SEP> from <SEP> Example <SEP> 1 <SEP> 2540
 <tb> Compound <SEP> from <SEP> Example <SEP> 2 <SEP> 2680
 <tb>



    

Claims (1)

 CLAIMS 1. Compound characterized in that it corresponds to formula (I)  EMI34.1  in which m + n is a number from 1 to 100 and n varies between zero and 90% of the sum m + n; X is -O- or -NH-;  EMI34.2  R. is hydrogen, a C <-C alkyl group. g, a C 1 -C alkyl group. substituted in position 2, 3 or 4 a C a alkyl group by a C1-C8 alkoxy group or by a di (C1-C4 alkyl) amino group, a C5-C12 cycloalkyl group unsubstituted or substituted by 1 , 2 or 3 C1-C4 alkyl groups, one  EMI34.3  C7-C9 phenylalkyl group unsubstituted or substituted on the phenyl ring by 1, 2 or 3 C1-C4 alkyl groups, or a group of formula (II):    EMI34.4   R2 is hydrogen, a C1-C8 alkyl group, O., OH, NO, CH2CN, a C1-C18 alkoxy group, a C5-C12 cycloalkoxy group, an unsubstituted or substituted phenylalkyl C7-C9 group on the phenyl ring with 1,2 or 3 C1-C4 alkyl groups, or a C1-C8 acyl group; and A is a Ce-C alkyl group. not.  <Desc / Clms Page number 35>    2. Compound of formula (I) according to claim 1, characterized in that R2 is hydrogen, an alkyl group  EMI35.1  C1-C4, OH, alkoxy C1-C1, cycloalkoxy C1-C6, benzyl group or acetyl group.  3. Compound of formula (I) according to claim 1, characterized in that R2 is hydrogen or methyl group.  4. Compound of formula (I) according to claim 1, characterized in that m + n is a number from 1 to 90 and n varies between zero and 90% of the sum m + n; X is -O- or -NH-;  EMI35.2  R. is hydrogen, a C1-C2 alkyl group, a C1-C7 cycloalkyl group, a C1-C9 phenylalkyl group or a group of formula (II); and A is a C6-C12 alkyl group.  5. Compound of formula (I) according to claim 1, characterized in that m + n is a number from 1 to 80 and n varies between zero and 90% of the sum m + n; X is -O- or -NH-; R. is hydrogen, a C1-C8 alkyl group, a cyclohexyl group, a benzyl group or a group of formula (II); and A is a C8-C12 alkyl group.  6. Compound of formula (I) according to claim 1, characterized in that m + n is a number from 1 to 70 and n varies between zero and 50% of the sum m + n; X is -O- or -NH-; R. is hydrogen, a C1-C4 alkyl group or a group of formula (II); and A is a Cg-C alkyl group.  7. Compound of formula (I) according to claim 1, characterized in that it corresponds to the formula  <Desc / Clms Page number 36>    EMI36.1    <Desc / Clms Page number 37>    EMI37.1    <Desc / Clms Page number 38>    EMI38.1    <Desc / Clms Page number 39>    EMI39.1    <Desc / Clms Page number 40>   8. Compound of formula (I) according to claim 1, characterized in that m + n is a number from 1 to 60 and n varies between zero and 50% of the sum m + n; X is -0- or -NH-; R1 is a C1-C4 alkyl group or a group of formula (II); and A is a C 1 -C 12 alkyl group 9.  Composition containing an organic material subject to degradation caused by light, heat or oxidation, characterized in that it comprises at least one compound of formula (I) according to claim 1.  10. Composition according to claim 9, characterized in that the organic material is a synthetic polymer.    11. Composition according to claim 10, characterized in that it contains other conventional additives for synthetic polymers, in addition to the compound or compounds of formula (I).  12. Composition according to claim 9, characterized in that the organic material is polyethylene or polypropylene.  13. Method for stabilizing an organic material against degradation caused by light, heat or oxidation, characterized in that it consists in incorporating into said organic material at least one compound of formula (I) according to claim 1.