JPH057404B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel phenolic oligomers obtained by adding mercapto or vinylphenols to butadiene oligomers and which can be used as stabilizers to protect organic materials against oxidative degradation. It is already known to stabilize organic materials, in particular polymers, by means of mercaptophenol stabilizers which are mixed into the material whose stabilization is desired and exert their effect (see EP 17614). However, the extraction stability of these stabilizers is not always satisfactory. In order to overcome this drawback, it is effective to stabilize the polymer by grafting each stabilizer onto the polymer in the presence of a radical polymerization initiator. The grafting of stabilizers onto polymers is described in detail in DE 2509654 A1. However, the presence of the above-mentioned stabilizers
It has been found that problems can occur during the manufacture of polymers, such as undesired chain scission.
It is also suggested in the same publication that polymers modified with such antioxidants can themselves be used as polymer stabilizers. However, the addition of such polymer additives to polymer-based formulations can lead to significant challenges in the form of non-uniform dispersion of the additive and modification of the polymer to be protected. Polymeric antioxidants containing sterically hindered phenols are described, for example, in German Published Patent Application No. 2143362
However, their stabilizing effect does not always meet the practical requirements. Now, the present inventors have discovered that a new phenol oligomer can be obtained by adding mercapto or vinyl phenol in a specific ratio to a reactive diene oligomer, and that even when the phenol oligomer is mixed with a polymer, it has good interaction with the base material. It does not cause problems due to its compatibility and good dispersibility, and it guarantees a surprisingly good protective effect against thermo-oxidative decomposition, as well as excellent stability against color migration and extractability. I discovered that. Therefore, the present invention provides the formula: [In the formula, m represents an integer from 30 to 150, and t represents an integer from 3 to 50, provided that t: m
The ratio of is 10:100 to 35:100; A is a formula or: {In the formula, R ₂ represents a methyl group or tert-butyl group, R ₃ represents a hydrogen atom or a methyl group, and X represents -CH ₂ - or -CH ₂ CH ₂ -C(O)O-
represents one of the groups represented by } representing CH ₂ CH ₂ -, and the butadiene oligomer chain represented by [-C ₄ H ₆ ]- _n contains a double bond in the main chain and/or side chain. and [-A] and [-H] are bonded to the butadiene oligomer chain, where if A is a group of the formula, q is the same as t, and if A is a group of the formula q represents O]. Among the compounds represented by the formula, those in which A represents a group of the formula are preferred. m preferably represents an integer from 50 to 80, and t represents an integer from 7 to 28. The ratio of t:m is preferably 12:100 to 30:100. Of particular interest among the compounds represented by the formula are those in which m represents an integer from 50 to 80, t represents an integer from 7 to 28, and the ratio t:m is 12:
100 to 30:100, A is a formula, or: {In the formula, R ₂ represents a methyl group or a tert-butyl group, and X is -CH ₂ - or -CH ₂ CH ₂ -C(O)O-
This is a compound that represents one of the groups represented by } representing CH ₂ CH ₂ -. The phenol oligomer represented by the formula can be prepared by a method similar to a known method (see, for example, German Published Patent Application No. 2509654), that is, the formula: Mercaptophenol represented by or formula: {In the formula, R ₂ represents a methyl group or a tertiary butyl group, R ₃ represents a hydrogen atom or a methyl group, and X represents -CH ₂ - or -CH ₂ CH ₂ -C(O)O-CH ₂
A vinylphenol monomer represented by } representing CH ₂ − is represented by the following formula: HO−(C ₄ H ₆ ) _n −OH () (in the formula, m represents an integer from 30 to 150). Obtained by addition to reactive diene oligomers. However, () or () of (
) should be between 10:100 and 35:100. () or () of ()
The preferred molar ratio is 15:100 to 30:100
It is. The addition reaction is carried out in the presence of a free radical initiator selected from the group consisting of azo or peroxide compounds, such as azodiisobutyronitrile, cumyl hydroperoxide or dibenzoyl peroxide, if desired with the addition of a sensitizer or initiator. The process is carried out solvent-free or in an inert solvent such as benzene, toluene, xylene, tetrahydrofuran hexane or ligroin in the presence of UV irradiation. Suitable diene oligomers have non-terminal double bonds in the oligomer backbone or terminal double bonds in the side chains and preferably have between 1500 and 10000
It has an average molecular weight of 2,500 to 5,000. They are known and 1,3-
Conjugated diolefin monomers such as 1,3-butadiene, isoprene, chloroprene, 2-cyano-
1,3-butadiene, 2,3-dimethyl-1,3
- Obtained from butadiene. Preferred diene oligomers are those derived from 1,3-butadiene. Mercapto or vinylphenols suitable for obtaining the compounds according to the invention are known and the methods for their preparation are likewise known to the expert. Examples of such compounds: A further object of the invention is the use of the compounds of the formula as stabilizers for organic materials against destruction by oxygen, heat, light and ionizing radiation such as beta and alpha radiation. Examples of organic materials which can be advantageously stabilized by the compounds of the invention are: 1 Mono- or diolefin polymers, such as polyethylene (optionally cross-linked), polypropylene, polyisobutylene, polybutene-
1. Polymethylpentene-1, polyisoprene or polybutadiene and cycloolefins such as cyclopentene or norbornene polymers. 2 Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene and polyethylene or polyisobutylene. 3 Copolymers of mono- and diolefins with each other or with other vinyl monomers, such as ethylene/propylene copolymers, propylene/butene-1 copolymers, propylene/
Isobutylene copolymer, ethylene/butene
1 copolymer, propylene/butadiene copolymer, isobutylene/isoprene copolymer,
ethylene/alkyl acrylate copolymer,
Ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers or ethylene/acrylic acid copolymers and their salts (ionomers) and terpolymers of ethylene with propylene and dienes such as hexadiene, dicyclopentadiene or ethylidenenorbornene 4. Polystyrene. 5 Copolymers of styrene or α-methylstyrene with diene or acrylic derivatives, such as styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylates,
Styrene/acrylonitrile/methyl acrylate; high impact strength mixtures obtained from styrene copolymers and other polymers such as polyacrylates, diene polymers or ethylene/propylene/diene terpolymers; also block copolymers of styrene such as styrene/butadiene/styrene, Styrene/isoprene/styrene, styrene/ethylene-butylene/styrene or styrene-ethylene/propylene-styrene. 6 Graft copolymers of styrene, such as styrene and polybutadiene, styrene and acrylonitrile and polybutadiene, styrene and maleic anhydride and polybutadiene, styrene and alkyl acrylate or alkyl methacrylate and polybutadiene, styrene and acrylonitrile and ethylene-propylene-diene terpolymers, Styrene and acrylonitrile with polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile with acrylate-butadiene copolymers and the known copolymers mentioned under 5), e.g.
Mixtures with ABS, MBS, ASA or AES polymers. 7 Halogen-containing polymers, such as polychloroprene, chlorinated rubber, chlorinated or chlorosulfonated polyethylene, especially polymers of halogenated vinyl compounds, such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, and the like. Copolymers of vinyl chloride/vinylidene chloride, vinyl chloride/vinylidene acetate or vinylidene chloride/
Vinyl acetate copolymer. 8 Polymers derived from α,β-unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates, polyacrylamides and polyacrylonitrile. 9 Copolymers of the monomers mentioned under 8) with each other or with other unsaturated monomers, such as acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/vinyl chloride copolymers or acrylonitrile/alkyl methacrylate/
Butadiene terpolymer. 10 Polymers derived from unsaturated alcohols, amines or their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate,
Polyvinyl butyrate, polyallyl phthalate, polyallyl melamine. 11 Homopolymers and copolymers of cyclic ethers, such as polyethylene glycol, polyethylene oxide, polypropylene oxide or their copolymers with bis-glycidyl ethers. 12 Polyacetals such as polyoxymethylene and also polyacetals such as polyoxymethylene containing comonomers such as ethylene oxide. 13 Polyphenylene oxide and polyphenylene sulfide. 14 Polyurethanes derived from polyethers, polyesters and polybutadienes with terminal hydroxyl groups on the one hand and from aliphatic or aromatic polyisocyanates and their precursors (polyisocyanates, polyols, prepolymers) on the other hand. 15 Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or aminocarboxylic acids or the corresponding lactams, such as polyamide 4, polyamide 6, polyamide 66, polyamide 610, polyamide 11, polyamide 12, polyamide
2,4,4-trimethylhexamethylene terephthalamide, poly-m-phenylene-isophthalamide and their copolymers with polyethers such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol. 16 Polyurea, polyimide and polyamideimide. 17 Polyesters derived from dicarboxylic acids and dialcohols and/or hydroxycarboxylic acids or corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate and poly-1,4-dimethylolcyclohexane terephthalate, as well as polyethers with terminal hydroxyl groups and dicarboxylic acids. Block polyether ester derived from. 18 Polycarbonate. 19 Polysulfones and polyethersulfones. 20 From aldehydes on the one hand, phenols on the other hand,
Crosslinked polymers derived from urea and melamine, such as phenol/formaldehyde resins, urea/formaldehyde resins and melamine/formaldehyde resins. 21 Drying and non-drying alkyd resins. 22 Unsaturated polyester resins derived from saturated and unsaturated dicarboxylic acids, polyhydric alcohols, and vinyl compounds as crosslinking agents, as well as halogen-containing, low-flammability modified products thereof. 23 Crosslinkable acrylic resins derived from substituted acrylic esters such as epoxy acrylates, urethane acrylates or polyester acrylates. 24 Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, polyisocyanates or epoxy resins. 25 Crosslinked epoxy resins derived from polyepoxides such as bisglycidyl ethers or cycloaliphatic diepoxides. 26 Natural polymers such as cellulose, rubber and gelatin, as well as their chemically modified homologous derivatives such as cellulose ethers such as cellulose acetate, cellulose propionate, cellulose butyrate and methylcellulose. 27 Oils and waxes derived from natural and synthetic organic substances such as mineral oils, animal and vegetable oils, waxes or synthetic esters (e.g. phthalates, adipates, phosphates or trimellitates) to produce pure monomers or mixtures thereof, and the plasticization of e.g. plastics. Mixtures of synthetic esters and mineral oils in any weight ratio used as agents or spinning oils as well as their aqueous emulsions. 28 Aqueous emulsions of natural or synthetic rubbers, such as natural rubber latexes or latexes of carboxylated styrene/butadiene copolymers. Compounds of the formula are particularly effective in stabilizing polyolefins, styrenic polymers and polyurethanes. Examples of substances that can be stabilized by compounds of the formula are high-density and low-density polyethylene, polypropylene, ethylene/propylene copolymers,
Polyurethanes based on polystyrene, styrene/butadiene/acrylonitrile copolymers, polyolefins or mixtures of styrene polymers, polyethers or polyesters in the form of films, filaments, lacquers, elastomers or foams. The compounds of the formula are particularly suitable for stabilizing high impact polystyrene (IPS) and ABS. They are also particularly suitable for stabilizing lubricating oils. Stabilizers are added to the plastic at a concentration of 0.01 to 5% by weight relative to the weight of the substance to be stabilized. 0.01 per weight of the substance to be stabilized
Preferably, from 2.0% by weight of the compound is incorporated into the material, and from 0.2 to 0.6% by weight is most preferred. After polymerization, before or during shaping, for example, the compound and, if desired, further additives may be incorporated into the melt by methods commonly used in the art, or alternatively dissolved or dispersed compounds may be added to the polymer; If desired, the solvent can then be evaporated to effect incorporation. Therefore, the present invention is stabilized by adding 0.01 to 5% by weight of a compound of the formula,
The invention relates to plastics which, if desired, can contain other known and customary additives.
Stabilized plastics can be utilized in a very wide range of forms, for example as sheets, filaments, ribbons, profiles or also as adhesives, adhesives or cements. Examples of other additives that can be used in conjunction with the stabilizers of the invention are: 1 antioxidants 1,1, alkylated monophenols, 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 -i-
Butylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,
6-di-octadecyl-4-methylphenol,
2,4,6-tri-cyclohexylphenol,
2,6-di-tert-butyl-4-methoxymethylphenol. 1,2, Alkylated Hydroquinone 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-hydroquinone or 2,5-di-tert-amyl-hydroquinone. 1,3, Hydroxylated thiophenyl ether 2,2'-thio-bis-(6-tert-butyl-4-
methylphenol), 2,2'-thio-bis-(4-
octylphenol), 4,4'-bis-(6-tert-butyl-3-methylphenol) or 4,4'-
Thio-bis-(6-tert-butyl-3-methyl-phenol) or 4,4'-thio-bis-(6-tert-butyl-2-methyl-phenol). 1,4, alkylidene-bisphenol 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-(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-methylphenyl)-butane, 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-dodecylmercaptobutane, ethylene glycol bis-[3,3-bis-(3'-tert-butyl-4'-hydroxyphenyl)
-butyrate], di-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene or di-[2-(3'-tert-butyl-2'-hydroxy-5'-methyl-benzyl) )-6-tert-butyl-4-methyl-phenyl]terephthalate. 1,5, benzyl compound 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, di-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 3-butyl-4-hydroxy-benzyl) sulfide,
isooctyl 3,5-di-tert-butyl-4-hydroxy-benzyl-mercaptoacetate, bis-(4-tert-butyl-3-hydroxy-2,6-
dimethylbenzyl)-dithiol terephthalate,
1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,
1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, dioctadecyl 3,5-di-tert-butyl-4-hydroxy-phenyl-phosphonate or monoethyl Calcium salt of 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonoic acid. 1,6, acylaminophenol 4-hydroxy-laurylic acid anilide, 4-hydroxy-stearic acid anilide or 2,4-
Bis-octylmercapto-6-(3,5-di-
tert-butyl-4-hydroxyanilino)-S-triazine 1,7 β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid monohydric or polyhydric alcohols such as methanol, octa Esters with decanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris-hydroxyethyl isocyanurate or dihydroxyethyl oxalamide. 3-butyl-4-hydroxy-3-methylphenyl)-propionic acid and a monohydric or polyhydric alcohol, such as methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol,
Esters with diethylene glycol, triethylene glycol, pentaerythritol, tris-hydroxyethyl isocyanurate or dihydroxyethyl oxalamide 1,9, β-(3,5-di-tert-butyl-4-
hydroxyphenyl)-propionic acid amides, such as N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylene diamine, N,N'-di-(3,5 -G-
tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine or N,N'-di-
(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine. 2 UV absorbers and light stabilizers 2,1,2-(2'-hydroxyphenyl)-benztriazole, such as 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 Tributyl-5′-
Methyl, 3'-sec-butyl-5'-tert-butyl, 4'-
Octoxy, 3',5-di-tertiary amyl, 3',
5'-di-(1,1,3,3-tetramethylbutyl)
- and 3',5'-di-(α,α-dimethyl-benzyl)-2-(2'-hydroxyphenyl)-benztriazole. 2,2,2-hydroxybenzophenones such as 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, substituted and unsubstituted benzoic acid esters such as 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis-( 4-tert-butylbenzoyl)-resorcinol, benzoylresorcinol and 2,4-di-
tert-butyl-phenyl 3,5-di-tert-butyl-
4-Hydroxybenzoate. 2,4, Acrylates such as ethyl α-cyano-β,β-diphenyl-acrylate, isooctyl α-cyanoβ,β
-Diphenyl acrylate, methyl α-cyano-
β-Methyl-p-methoxy-cinnamate, butyl α-cyano-β-methyl-p-methoxy-cinnamate, methyl α-carbomethoxy-p-methoxy-cinnamate and N-(β-carbomethoxy-α-cyanovinyl)- 2-Methyl-indoline. 2,5, nickel compounds such as 2,2'-thio-bis-[4-(1,1,
3,3-tetramethylbutyl)phenol], e.g. 1:1 complexes or 1:2 complexes with or without ligands such as n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine. , nickel dibutyl dithiocarbamate, 4-hydroxy-3,5
- nickel salts of di-tert-butyl-benzyl-phosphonic acid monoalkyl esters, i.e. methyl or ethyl esters, nickel complexes of ketoximes,
For example, nickel complexes of 2-hydroxy-4-methyl-phenyl undecyl ketone oxime with or without appended ligands and nickel complexes of 1-phenyl-4-lauroyl-5-hydroxy-pyrazole. 2,6, sterically hindered amines such as bis-(2,2,6,6-tetramethylpiperidyl) sebacate, bis-(1,2,2,
6,6-pentamethylpiperidyl) sebacate,
Bis-(1,2,2,6,6-pentamethylpiperidyl)n-butyl-3,5-di-tert-butyl-
4-Hydroxybenzyl-malonate, condensate of 1-hydroxy-ethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, N,N'-(2,2,6,6- (tetramethylpiperidyl)-hexamethylene diamine and 4-tertiary octylamino-2,6-dichloro-1,3,5
-s-triazine condensate, and tris-(2,
2,6,6-tetramemelpiperidyl) nitrotriacetate. 2,7, oxalic acid diamide, e.g. 4,4'-dioctyloxyoxanilide, 2,2'-di-octyloxy-5,5'-di-
Tert-butyl-oxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert-butyl-oxanilide, 2-ethoxy-2'-ethyl-oxanilide,
N,N'-bis-(3-dimethylamino-propyl)-oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyl-oxanilide and its 2-
Mixtures with ethoxy-2'-ethyl-5,4'-di-tert-butyl-oxanilide, ortho and para-
A mixture of methoxy-disubstituted oxanilides and o-
and a mixture of p-ethoxy-disubstituted oxanilides. 3 Metal deactivators, such as N,N'-diphenyl oxalic acid diamide, N
-Salicyral-N'-Salicyloylhydrazine,
N,N'-bis-salicyloylhydrazine, N,
N'-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine, 3
- Salicyloylamino-1,2,4-triazole and bis-benzylidene-oxalic acid dihydrazide. 4 Phosphites and phosphonites such as triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tri(nonylphenyl) phosphite, trilauryl phosphite, triotadecyl phosphite, distearyl-pentaerythritol diphosphite, tris-( 2,4-di-tert-butylphenyl) phosphite, diisodecyl-pentaerythritol diphosphite, di-
(2,4-di-tert-butylphenyl)-pentaerythritol diphosphite, tristearyl-sorbitol triphosphite and tetrakis-
(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite. 5 Compounds that decompose peroxides, such as esters of β-thio-dipropionic acid,
For example laurylstearyl, myristyl or tridecyl esters, mercaptobenzimidazole, zinc salts of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide and pentaerythritol tetrakis-(β-dodecylmercapto)propionate. 6 Polyamide stabilizers, such as copper salts and divalent manganese salts in combination with iodides and/or phosphorus compounds. 7 Basic costabilizers, such as melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, such as calcium stearate, Zinc stearate, magnesium stearate, sodium ricinoleate and potassium valmitate, antimony pyrocatechol or tin pyrocatechol. 8 Nucleating agents, such as 4-tert-butylbenzoic acid, adipic acid and diphenyl acetic acid. 9 Fillers and reinforcing agents, such as calcium carbonate, silicates, glass fibers,
Asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black and graphite. 10 Other additives, such as plasticizers, lubricants, emulsifiers, pigments, fluorescent whitening agents, flame retardants, antistatic agents and blowing agents. The following examples further illustrate the preparation and use of the compounds of the invention. Production Example A Adjunct of mercaptophenol and butadiene oligomer General procedure: “Polybutadiene resin R45-HT” {butadiene oligomer with terminal hydroxyl group and average molecular weight of 2800,
Manufactured by Atlantic Richfield Co.} 100g of benzene
Dissolve in 250 ml and heat to reflux in a nitrogen stream until boiling. The respective mercaptophenols, in the form of a 30% benzene solution also containing the catalyst (2 g of azodiisobutyronitrile), are added dropwise with stirring in the amounts indicated in the table over a period of 5 hours. The reaction mixture is then refluxed for a further 10 hours. The reaction mixture is then filtered and methanol is carefully added to precipitate the product. The stabilizer is obtained as a yellowish, highly viscous oil.

[Table] B Adduct example of vinyl phenol and butadiene oligomer 5: 100 g of “polybutadiene resin R45HT” and 2-tert-butyl-4,6-dimethyl-3-acroyloxymethylphenol (Note 1) (t: m ratio 16:
100) react as described in A). The adduct thus obtained is a highly viscous, almost colorless oil that can be used in the reaction without further purification.
The formation of copolymer bonds can be observed by NMR spectroscopy. Production of 2-tert-butyl-4,6-dimethyl-3-acroyloxy-methylphenol represented by 2-tert-butyl-4, while stirring and cooling under reflux.
6-dimethyl-3-chloromethylphenol
33.8 g and 14.1 g of dry powder of sodium acrylate are heated at 80 to 90° C. for 4 hours. The solvent is removed in vacuo and the residue is extracted with toluene and water. Separate the aqueous phase and remove the residue under high vacuum with a boiling point of 126 to 130
Distill at °C/0.005mmHg. Pure acrylic ester forms white crystals with a melting point of 60°C. Application example Example 6: Stabilization of high-impact polystyrene 8% by weight of high-cis polybutadiene and 0.035% by weight of 2,6-di-tert-butyl-p-cresol as basic stabilizer, 0.05% by weight as lubricant % zinc stearate and 0.1% by weight of one of the antioxidants of the invention (identified by the number of the corresponding preparation example in the table and inside) was extruded twice at 220°C. The obtained granules were pressed at 185° C. for 3 minutes to form a test piece with a thickness of 2 mm. These specimens were placed in an air circulation oven and the following physical properties were measured. a ASTM D1925 80℃ (0,250,500,
Measured after 750 and 1000 hours) and 160℃ (0,
Measure the yellowness index (YI) at 60, 90, 120 and 180 minutes later and report the results in the table.

[Table] b Impact strength after being left at 160℃ (IS, kp・
cm/cm ² ) (measured after 15, 30, 60, 120 and 150 minutes):

[Table] Example 7: Stabilization of Polybutadiene Approximately 5% of unstabilized polybutadiene was dissolved in toluene and then the antioxidant of the present invention (identified in the table by the number of the corresponding Preparation Example) was added. )
Add 0.5% by weight of one of the above. Next, the rubber is coagulated with boiling water at 90°C and vacuum dried at 40°C. Next, add 80 rubber
Press at ℃ for 20 minutes or more to obtain a 2 mm thick test piece. Perform the following test on these test pieces: a. Leave to age in silicone oil for 20 minutes or more at 160°C and measure gel content using the following formula: Gel content = WS/W・100 (%) Formula Medium, WS = Weighed test piece (1 g of rubber in 100 ml of toluene) W = Weight b of the residue after distilling off the solvent from the toluene solution After extraction with ethanol for 24 hours at room temperature, 40 ° C.
After vacuum drying for 24 hours, aging and gel content were measured as in a). Report the test results in a table.

【table】

Claims (1)

[Claims] 1 Formula: [In the formula, m represents an integer from 30 to 150, and t represents an integer from 3 to 50, provided that t: m
The ratio of is 10:100 to 35:100; A is a formula or: {In the formula, R ₂ represents a methyl group or tert-butyl group, R ₃ represents a hydrogen atom or a methyl group, and X represents -CH ₂ - or -CH ₂ CH ₂ -C(O)O-
represents one of the groups represented by } representing CH ₂ CH ₂ -, and the butadiene oligomer chain represented by [-C ₄ H ₆ ]- _n contains a double bond in the main chain and/or side chain. and [-A] and [-H] are bonded to the butadiene oligomer chain, where if A is a group of the formula, q is the same as t, and if A is a group of the formula q represents O]. 2. The compound according to claim 1, wherein A is a group represented by the formula. 3 In the formula, m represents an integer from 50 to 80, t represents an integer from 7 to 28, and t:
The ratio of m is 12:100 to 30:100, and A is a formula, or: {In the formula, R ₂ represents a methyl group or a tert-butyl group, and X is -CH ₂ - or -CH ₂ CH ₂ -C(O)O-
The compound according to claim 1, which represents one of the groups represented by } representing CH ₂ CH ₂ -. 4. The compound according to claim 3, wherein A represents one of the groups represented by the formula or. 5 Formula: [In the formula, m represents an integer from 30 to 150, and t represents an integer from 3 to 50, provided that t: m
The ratio of is 10:100 to 35:100; A is a formula or: {In the formula, R ₂ represents a methyl group or tert-butyl group, R ₃ represents a hydrogen atom or a methyl group, and X represents -CH ₂ - or -CH ₂ CH ₂ -C(O)O-
represents one of the groups represented by } representing CH ₂ CH ₂ -, and the butadiene oligomer chain represented by [-C ₄ H ₆ ]- _n contains a double bond in the main chain and/or side chain. and [-A] and [-H] are bonded to the butadiene oligomer chain, where if A is a group of the formula, q is the same as t, and if A is a group of the formula A stabilizer for protecting organic materials against oxidative decomposition, comprising a compound represented by: 6 Formula: Mercaptophenol represented by or formula: {In the formula, R ₂ represents a methyl group or a tertiary butyl group, R ₃ represents a hydrogen atom or a methyl group, and X represents -CH ₂ - or -CH ₂ CH ₂ -C(O)O-CH ₂
A vinylphenol monomer represented by } representing CH ₂ − is represented by the following formula: HO−(C ₄ H ₆ ) _n −OH () (in the formula, m represents an integer from 30 to 150). Added to a reactive diene oligomer, provided that
The molar ratio of the compound represented by the formula or to the compound represented by the formula is 10:100 to 35:100
provided that it must be within the range of
A formula characterized in that the reaction is carried out in the presence of a free radical initiator [In the formula, m represents an integer from 30 to 150, and t represents an integer from 3 to 50, provided that t: m
The ratio of is 10:100 to 35:100; A is a formula or: {In the formula, R ₂ represents a methyl group or tert-butyl group, R ₃ represents a hydrogen atom or a methyl group, and X represents -CH ₂ - or -CH ₂ CH ₂ -C(O)O-
represents one of the groups represented by } representing CH ₂ CH ₂ -, and the butadiene oligomer chain represented by [-C ₄ H ₆ ]- _n contains a double bond in the main chain and/or side chain. and [-A] and [-H] are bonded to the butadiene oligomer chain, where if A is a group of the formula, q is the same as t, and if A is a group of the formula q represents O].