DD263068A5 - Use of substituted phenols as stabilizers - Google Patents

Abstract

The invention relates to the use of substituted phenols as stabilizers. According to the invention, in a composition comprising an elastomer or a tackifying resin, at least one compound of formula (I) wherein, for example: R1 is C1-C8 alkyl or C5-C12 cycloalkyl, R2 is C1-C16 alkyl groups, is unsubstituted or substituted by 1 or 2 hydroxyl groups or OCOR4 u. a., phenyl or benzyl, R3 is hydrogen or methyl, R4 is C1-C17-alkyl, C2-C8-alkenyl and the like. a. Formula (I)

Description

Λ. Ο O

Field of application of the invention

The invention relates to the use of substituted phenols as stabilizers for elastomers or tackifying resins

Characteristic of the known state of the art

Alkylthiomethyl-containing phenols are known as stabilizers. For example, US Pat. No. 3,660,352 describes the use of 2,4,6-tri-alkyl bis (3,5-alkylthiomethyl) phenols as antioxidants in polymers and elastomers. From US-PS 3,227,677 2,6-bis (alkoxycarbonylalkylenthiomethyl) -4-alkylphenols are also known as antioxidants for polyolefins.

According to British Pat. No. 1,184,533, 2,4-bis- (alkylthiomethyl) -3,6-dialkylphenols can be used as stabilizers for organic polymers as well as for synthetic oils.

Object of the invention

The object of the invention is to provide effective stabilizers for materials which are sensitive to thermal, oxidative or photoinduced degradation.

Explanation of the essence of the invention

It is an object of the present invention to provide compounds useful as stabilizers for materials which are sensitive to thermal, oxidative or photoinduced degradation, e.g. are suitable for elastomers or tacky resins.

According to the invention, in a composition comprising an elastomer or a tackifying resin, at least one compound of the formula I

263

CH ₂ -SR ₂

Il (D,

CH ₂ -SI

₂ -SR ₂

applied, in which

Ri Ci-Ce-alkyl or Cs-Cj ₂ -cycloalkyl, the radicals R ₂ independently of one another are Ci-Ci β- alkyl groups which are unsubstituted, or by 1 or 2 hydroxyl groups or by -OCO-Ri ,, -CO -OR5 or -CO-NR5R6 are substituted, or phenyl or benzyl,

R3 is hydrogen or methyl, with the proviso that when Ri is different from methyl, R3 is methyl, Ri, Ci-Ci7 alkyl, C ₂ -Cs-alkenyl or a residue of formula Ia

- (CH ₂ ) - ζ '; -0H (.Ia),

m is 0, 1 or 2, and the radicals

R 'independently of one another have the meaning mentioned for Ri, R5 is an optionally interrupted by -0-, -S- or -NR'- Ci alkyl, and

Re is hydrogen or has the meaning given for R5,

R ¹ and R ¹ as C 1 -C 6 -alkyl are, for example, methyl, ethyl, n-propyl, isopropyl, η-butyl, sec-butyl, t-butyl, n-pentyl, isopentyl, n-hexyl, 1,1-dimethylbutyl , n-heptyl, n-octyl or 2-ethylhexyl.

Preferably, Ri and R 'are Ci-Ci, alkyl, in particular methyl, ethyl, isopropyl or t-butyl, and especially methyl or t-butyl.

Ri and R 'are as C5-C1 ₂ -cycloalkyl, for example cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl or cyclododecyl. Preferably, R and R 'are C5-Ce-cycloalkyl, especially cyclohexyl.

η J ^ u

For example, in addition to the radicals mentioned for R 1, R 2 as C 1 -C 18 -alkyl also denotes n-nonyl, n-decyl, 1,1,3,3-tetramethylbutyl, 1,1,3,3-tetramethylhexyl, n-undecyl, n Dodecyl, 1,1,3,3,5,5-hexamethylhexyl, n-tetradecyl, n-hexadecyl or n-octadecyl. Preferably, R 2 is C 1 -C 6, especially C 1 -C 6, alkyl, e.g. n-octyl or n-dodecyl.

Ra as Ci-Cis-alkyl can be substituted by one or two hydroxyl groups. Examples of such radicals are 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl, 2-hydroxydodecyl, 2-hydroxyhexadecyl, 2-hydroxyoctadecyl or 2,3-dihydroxypropyl. Preference is given to 2-hydroxyethyl.

Ri, as Ci-Ci7-alkyl, for example, the radicals mentioned for R2 and methyl, preferably Ci-Ci2-alkyl, such as methyl, ethyl, n-propyl, isopropyl, η-butyl, t-butyl, n-hexyl, n-octyl, 2-ethylhexyl or n-dodecyl.

If R 1 denotes C 2 -C 3 -alkenyl, for example the radicals vinyl, allyl, methallyl, but-3-enyl, pent-4-enyl, hex-5-enyl, oct-7-enyl, dec-9- enyl or dodec-11-enyl in question. Preferred is Ri, vinyl or allyl.

R 1, as a radical of the formula Ia, may be, for example, 4-hydroxy-3,5-dimethylphenyl, 4-hydroxy-3,5-di-tert-butylphenyl, 4-hydroxy-3,5-dimethylbenzyl, 4-hydroxy-3, 5-di-t-butylbenzyl or 4-hydroxy-3,5-dimethylphenylethyl, preferably 4-hydroxy-3,5-di-t-butylbenzyl.

R 5 or R 6 as C 1 -C 20 -alkyl, for example, denotes the radicals mentioned for R 2 and also methyl, octadecyl or eicosyl, preferably methyl, ethyl, n-hexyl, n-octyl or n-dodecyl.

R 5 or R 6 as C ¹ -C 20 -alkyl interrupted by -O-, -S- or -NR ¹ - means, for example, 3-oxabutyl, 3-oxapentyl, 3,6-dioxaheptyl, 3,6,9-trioxadecyl, 3,6 , 9,12-tetraoxatridecyl, 3,6,9,12,15-pentaoxahexa

decyl, 3,6,9,12,15,18-hexaoxanonadecyl, 3-thiabutyl, 3-azabutyl, 3-methyl-3-azapentyl, 3-ethyl-3-a2-pentyl, 3-methyl-3-aza-6 oxahepty1, preferably 3-oxapentyl or 3-azabutyl.

Preference is given to compositions which comprise an elastomer and at least one compound of the formula I.

Particular preference is given to compositions comprising an elastomer and at least one compound of the formula I in which the radicals R a independently of one another represent C ₂ -C 18 -alkyl groups which are unsubstituted or denoted by 1 or 2 hydroxyl groups or by -OCO-R 1. OR5 or -CO-NR5R6 are substituted, wherein Ri ,, Rs and Re have the abovementioned meaning.

Very particular preference is given to compositions comprising an elastomer or a tackifying resin, in which R 1 in the formula I is C ₁ -C 12 -alkyl, in particular methyl or t-butyl.

Also preferred are compositions comprising an elastomer or a tackifying resin, wherein R ₂ in the formula I is C 1 -C 6 -alkyl, -CH ₂ CH ₂ -OH-CH ₂ CH ₂ -O-CO-R i, -CH ₂ -CO- R ₅ or -CH ₂ CH ₂ -CO-R ₅ , where Ri, and R _{5 have} the abovementioned meaning. R ₂ is particularly preferably C 1 -C 8 -alkyl or -CH ₂ -COO-Rs, where R 0 has the abovementioned meaning. Most preferably, R _{2 is} Ci, -Ci alkyl.

Examples of representatives of compounds of the formula I are the substances listed below:

2,4-bis (2'-hydroxyethylthiomethyl-6-methylphenol, 2,4-bis (2 ', 3'-dihydroxypropylthiomethyl) -3,6-dimethylphenol, 2,4-bis (2'-acetyloxyethylthiomethyl ) -3,6-dimethylphenol, 2,4-bis (2'-n-decanoyloxyethylthiomethyl) -6-methylphenol, 2,4-bis (n-octylthiomethyl) -6-methyl-phenol, 2,4-bis (t-octylthiomethyli-o-methyl-phenol,

t-Octyl is 1,1,3,3-tetramethylbutyl

oil / *: y

2 2,4-bis (t-dodecylthiomethyl-6-methylphenol, 2,4-bis (benzylthiomethyl) -6-methylphenol, 2,4-bis (phenylthiomethyl) -3-methyl-6-t-butyl -phenol, 2,4-bis (2 ^l -ethylhexyloxycarbonyl-ethyl-thiomethyl) -6-methyl-phenol, 2,4-bis (n-octadecyloxycarbonylmethyl-thiomethyl) -3,6-dimethyl-phenol, 2,4-bis [ 2 '- <2 "-äthylhexyloxycarbonyl) -äthylthiomethylJ-3-methyl-6-t-butyl-phenol.

As an elastomer, the compositions according to the invention may contain, for example, the following materials:

1. Polydienes such as polybutadiene, polyisoprene or polychloroprene; Block polymers such as styrene / butadiene / styrene, styrene / isoprene / styrene or acrylonitrile / butadiene copolymers.

2. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, e.g. Ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers and terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidenenorbornene.

3. Halogen-containing polymers, e.g. Polychloroprene, chlorinated rubber, chlorinated or chlorosulfonated polyethylene, epichlorohydrin homopolymers and copolymers, chlorotrifluoroethylene copolymers, polymers of halogen-containing vinyl compounds, e.g. Polyvinylidene chloride, polyvinylidene fluoride; and their copolymers, such as vinyl chloride-vinylidene chloride, vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate.

4. Polyurethanes derived from polyethers, polyesters and polybutadiene with terminal hydroxyl groups on the one hand and aliphatic or aromatic polyisocyanates on the other hand and their precursors.

t-Dodecyl is a mixture of 1,1,3,3,5,5-hexamethylhexyl and 1,1,4,6,6-pentamethylhept- (4) -yl

'1 1 i ί ο' ν

2 62

5. Natural rubber.

6. mixtures (polyblends) of the aforementioned polymers.

7. Aqueous emulsions of natural or synthetic rubbers, e.g. Natural rubber latex or latices of carboxylated styrene-butadiene copolymers.

Optionally, these elastomers are present as latices and can be stabilized as such.

Preference is given to compositions which contain as elastomer a polydiene, such as polybutadiene rubber, a halogen-containing polymer, such as polyvinylidene fluoride, or a polyurethane.

The compositions according to the invention conveniently contain 0.01-10% by weight of the stabilizer of the formula I, based on the elastomer, in particular 0.05-5.0% by weight. Mixtures of stabilizers of formula I can also be used.

The incorporation into the elastomers, for example, by mixing the compounds of formula I and optionally other additives according to the methods customary in the art, before or during molding, or by applying the dissolved or dispersed compounds to the polymer, optionally with subsequent evaporation of the Solvent done. The compounds of the formula I can also be added to the plastics to be stabilized in the form of a masterbatch which contains these compounds, for example in a concentration of from 2.5 to 25% by weight.

263 0

As tackifying resins, the compositions according to the invention may contain, for example, the following materials:

- Natural rosins such as gum rosin, wood rosin, tall oil rosin.

- Derivatives of rosin resins, such as glycerol ester, pentaerythritol, in each case hydrogenated or non-hydrogenated, disproportionated or not disproportionated

Synthetic C5 or Cg hydrocarbon resins

- indene resins, methyl indene resins, coumarone indene resins

- terpene resins

- Methylstyrene resins

- phenolic resins

- other tackifiers such as asphalt or bitumen

- Mixtures of the aforementioned resins

- Aqueous emulsions of the aforementioned resins.

Preferred are compositions containing a synthetic C5 or Cg hydrocarbon resin, a rosin resin or a derivative of rosin resins.

The tackifying resin compositions suitably contain 0.01-10% by weight of the stabilizer of the formula I, based on the tackifying resin, in particular 0.03-3.0% by weight. Mixtures of stabilizers of formula I can also be used.

The incorporation of the compounds of the formula I into the tackifying resins can be carried out by the methods customary in the art, before, during or after the preparation or modification.

The compositions according to the invention can be used in a wide variety of forms, e.g. as films, fibers, tapes, molding compounds, profiles or as a binder for paints, adhesives or putties.

The compounds of formula I are known in part.

<£ OJ .υ Q

The compounds of the formulas I and II are prepared by methods known per se, as described, for example, in GB-A-1 184 533 and in US Pat. No. 3,227,677. All starting materials are known compounds and can be prepared by known methods. Some of them are also available in stores.

The novel compositions comprising an elastomer or a tackifying resin and phenols of the formula I may also contain further additives. Examples of such additives are:

1. Antioxidants

1.1. Alkylated monophenols , for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di- tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-i-butylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2- (ot-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 hydroquinones , eg 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone, 2,6-diphenyl-4- octadecyloxyphenol.

1.3. Hydroxylated thiodiphenyl ethers , for example 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 ^I-thiobis (6-tert-butyl-2-methylphenol).

1.4. Alkylidene bisphenols , eg 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis-co-tert-butyl-4-ethylphenol), 2,2 ' -Methylenebis-l4-methyl-6- (o-methylcyclohexyl) phenol, 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (6-nonyl) 4-methylphenol), 2,2'-methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidene-bis (4,6-di-tert-butylphenol), 2,2 'Ethylidene bis (6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis [6- (ot-methylbenzyl) -4-nonylphenol], 2,2'-methylenebis [6 - (α, α-dimethylbenzyl) -4-nonylphenol], 4,4'-methylene-bis- (2,6-di-)

2 63

tert-butylphenol), 4,4'-methylenebis (6-tert-butyl-2-methylphenol), 1, 1-bis (S-tert-butyl-hydroxy-methyl-phenyl) -butane, 2, 6-di (3-tert-butyl-5-ethyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris- (5-tert-butyl-4-hydroxy-2-methylphenyl) - butane, 1, l-bis-iS-tert-butyl ^ - hydroxy ^ -methylphenyli-Sn dodecylinercaptobutan, 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'-methyl-benzyl) -6- tert-butyl-4-methyl-phenyl] terephthalate.

1.5 benzyl compounds , for example 1,3,5-tri (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, di- (3,5-di-tert-butyl-4 -hydroxybenzyl) sulfide, SS-di-tert-butyl-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, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 3,5- Di-tert-butyl-4-hydroxybenzyl-phosphonic acid dioctadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonic acid monoethyl ester, calcium salt.

1.6. Acylaminophenols , eg 4-hydroxy-lauric acid anilide, 4-hydroxystearic acid anilide, 2,4-bis-octylmercapto-6- (3,5-di-tert-butyl-4-hydroxyanilino) -s-triazine, N- (3,5- di-tert-butyl-4-hydroxyphenyl) -carbaminsäureoctylester.

1.7. Esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid

with monohydric or polyhydric alcohols, e.g. with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris-hydroxyethyl isocyanurate, dihydroxyethyl-oxalic acid diamide.

1.8. Esters of 6- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with monohydric or polyhydric alcohols, such as methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol , Tris-hydroxyethyl-isocyanurate, di-hydroxyethyl-oxy-diamide.

1.9. Amides of 8- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid _> such as N, N'-di-CS.S-di-tert-butyl-A-hydroxyphenyl-propionyl-hexamethylenediamine, N, N'- Di- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -triethylenediamine, N, N'-di- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hydrazine.

2. UV absorber and sunscreen

2.1. 2- (2'-hydroxyphenyl) -benzotriazoles , such as the 5'-methyl, 3 ', 5'-di-t-butyl, 5'-t-butyl, 5' - (I, 1,3 , 3-tetramethylbutyl) -, 5-chloro-3 ', 5'-di-t-butyl, 5-chloro-3'-t-butyl-5'-methyl, 3'-sec-butyl-5' -t-butyl, 4'-0ctoxy, 3 ', 5'-di-t-amyl, 3', 5'-bis (et, ct -dimethylbenzyl) derivative.

2.2. 2-hydroxybenzophenones , such as 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy, 2'hydroxy-4,4'-dimethoxy derivative.

2.3. Esters of optionally substituted benzoic acids, such as 4-t-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-t-butylbenzoyl) -resorcinol, benzoylresorcinol, 3,5-di-t-butyl-4-hydroxybenzoic acid 2,4-di-t-butylphenyl ester, 3,5-di-t-butyl-4-hydroxybenzoic acid hexadecyl ester.

2.4. Acrylates , such as, for example, α-cyano-β-diphenylacrylic acid ethyl ester or isooctyl ester, methyl ct-carbomethoxycinnamate, methyl ct-cyano-β-methylp-methoxycinnamate or butyl ester, methyl α-carbomethoxy-p-methoxycinnamate , N- (β-carbomethoxy-β-cyanovinyl) -2-methyl-indoline,

2.5. Nickel compounds , such as nickel complexes of 2,2'-thio-bis [4- (l, 1,3,3-tetramethylbutyl) phenol], such as the 1: 1 or the 1: 2 complex, optionally with additional Ligands such as n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-t-butylbenzylphosphonsäuremonoalkylestern such as methyl or ethyl ester, nickel complexes of

2 63 06 ι

Ketoximes, such as 2-hydroxy-4-methylphenyl undecyl ketone oxime, nickel complexes of 1-phenyl-1-lauroyl-S-hydroxy-pyrazole, optionally with additional ligands.

2.6. Sterically hindered amines such as bis (2,2,6,6-tetramethylpiperidyl) sebacate

Bis (1,2,2,6,6-pentamethylpiperidyl) sebacate n-butyl-3,5-di-t-butyl-4-hydroxybenzyl malonic 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-tetramethyl-4-piperidyl) hexamethylenediamine and 4-t-octylamino-2,6-dichloro-l, 3,5-s-triazine, tris (2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis (2,2, 6,6-tetramethyl-4-piperidyl) -1,3,3,4-butanetetracarboxylic acid, 1,1 '- (1,2-ethanediyl) bis- (3,3,5,5-tetramethylpiperazinone).

2.7. Oxalic acid diamides such as 4,4'-dioctyloxy-oxanilide, 2,2'-dioctyloxy-5,5'-di-t-butyl-oxanilide, 2,2'-di-dodecyloxy-5,5'di t-butyloxanilide, 2-ethoxy-2'-ethyl-oxanilide, N, N'-bis- (3-dimethylaminopropyl) -oxalamide, 2-ethoxy-5-t-butyl-2'-ethyloxanilide and its mixture with 2- Aethoxy-2'-ethyl-5,4'-di-t-butyl-oxanilide, mixtures of o- and p-methoxy as well as of o- and p-ethoxy-di-substituted oxanilides.

3. phosphites and phosphonites such as triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites , tri (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-t-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, Di- (2,4-di-t-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene diphosphonite, 3,9-bis - (2,4-di-tert-butylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane.

263 O S

4. Peroxide-destroying compounds , for example esters of β-thio-dipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole, the zinc salt of 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis ( ß-dodecylmercapto) propionate.

5. Polyamide stabilizers, such as copper salts in combination with iodides and / or phosphorus compounds and salts of divalent manganese.

6. Basic co-stabilizers , such as melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali and alkaline earth salts of higher fatty acids, for example, Ca stearate, Zn stearate, Mg stearate , Na ricinoleate, K-palmitate, antimony catechinate or tin catechinate.

7. Nucleating agents , such as 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid.

8. Fillers and reinforcing agents , such as calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.

9. Other additives , such as plasticizers, lubricants, emulsifiers, pigments, optical brighteners, flame retardants, antistatic agents, blowing agents, waxes, oils, organic solvents.

embodiment

The following examples further illustrate the invention. In the examples, the remainder of the description and the claims mentioned percents and parts are weight percentages and parts by weight.

2 63 06s

PREPARATION

Example 1: Preparation of Z 1 -BisCn-octylthiomethyl-o-methylphenol (Compound No. 1)

? ^H A / CH ₂ -S-Ti-C ₈ HI ₇

160.74 g (0.72 mol) of 2,4-bis (dimethylaminomethyl) -6-methylphenol and 210.65 g (1.44 mol) of n-octanethiol be in an apparatus equipped with stirrer and intensive cooler long 36 hours at 150 ⁰ C., whereby dimethylamine is continuously withdrawn at 53.2 bar. This gives 291.6 g (95%) of a yellow oil. Pure 2,4-bis (n-octylthiomethyl) -6-methyl-phenol is obtained by column chromatography of the crude product on silica gel as a colorless oil.

Analysis:

Calculated 70.69% C Found 70.85% C

10.44% H 10.42% H

15.09% S 15.11% S

¹ H-NMR (CDCl ₃ , 100 MHz, data in δ [ppm] relative to TMS = 0, s = singlet): Characteristic signals for Ar-CH ₂ S at 3.77 (s) and 3.6 (s) ,

Analogously, the following compounds of formula I are prepared:

OH

i π (D

• ·

I Il

• ·

-sr ₂

Connection no. Ri R ₂ R ₃ Characteristics Connection 2 CH ₃ n-Ci ₂ H ₂₅ H Mp .: 28 ° C Connection 3 CH ₃ n ~ Cι2 "2 5 CH ₃ Mp .: 43 ° C Connection 4 C (CH ₃ ) ₃ Tl-C ι 2 ** 2 5 CH ₃ Mp .: 40 ° C Connection 5 CH ₃ nC ₈ Hi7 CH ₃ liquid Connection 6 CH ₃ ~ '\ -. ^{/ Φ} H _: Mp: 99-100 ° C Connection 7 CH ₃ H liquid Connection 8 CH ₃ -CH ₂ -COO-CH ₂ CH- (CH ₂ ) ₃ -CH ₃ CH ₂ CH ₃ H liquid Connection 9 CH ₃ -CH ₂ CH ₂ -OH H liquid Connection 10 CH ₃ -C (CH ₃₎ 2 -CH ₂ -C (CH _{3) 2} -CH ₂ -C (CH _{3) 3} H liquid Connection 11 CH ₃ -C (CH ₃ ) ₂ -CH ₂ -C (CH ₃ ) ₃ H liquid APPLICATIONS

The compounds 1-4 from Example 1 are tested for their stabilizing effect.

Example 2 Stabilization of Polybutadiene Rubber (Oven Aging) 100 g of polybutadiene, which is prestabilized with 0.4% of 2,6-di-t-butyl-p-cresol, are homogeneously co-extruded on a mixing mill at 50 ° C. for 6 minutes 0.25% of the compound to be tested mixed. The rolled sheets are pressed at 80 ° C plates of 10 mm thickness. Another plate is made without stabilizer in the same way.

The testing of the novel compositions is carried out by heat aging in a convection oven at 80 ° C. The criterion used is the unwanted gel content that occurs during oven aging. This is determined as follows:

1 gram of polybutadiene is dissolved overnight at room temperature in 100 ml of toluene. The solution is filtered through a sintered glass funnel (pore size 00) and the filtered solution is evaporated to dryness.

The gel content results from

gel

χ 100 (%)

E · »weight (1 gram)

A = weight of the evaporation residue

The gel content increases rapidly after an induction period. The arbitrary definition of the induction period is the time after which a gel content of 2% is reached. This induction time is determined by periodic gel content determinations.

The results are summarized in Table 1. Table 1

stabilizer Induction time to gel content «2% (in days) none 21 Connection 2 77 Connection 3 84 Connection 4 56

Example 3: Stabilization of polybutadiene rubber (Brabender) 100 parts of polybutadiene, which is prestabilized with 0.4% of 2,6-di-t-butyl-p-cresol, is additionally mixed with 0.25% of the stabilizer to be tested in a Brabender Plastograph kneaded at 160 ⁰ C and 60 revolutions per minute for 30 minutes. From the course of the torque curve, the induction time is determined, ie the kneading time in minutes until the torque increases by 100 rap after the torque minimum.

263 ES 8

The results are summarized in Table 2.

Table 2

stabilizer Induction time (in minutes) none 8th Connection 1 > 30 Connection 2 23 Connection 3 23.5 Connection 4 26

Example 4: Stabilization of a hydrogenated Cg hydrocarbon resin

(Oven aging)

50 g of resin, which is pre-stabilized with 0.15% of 2,6-di-t-butyl-p-cresol are melted in a glass flask at 170 ⁰ C and 0.1% of compound 1 for 15 minutes mixed with stirring. The hot melt is then filled into aluminum dishes or Petri dishes. The layer thickness of the solidified resin mass is about 15 ram in the aluminum dishes and 1 mm in the petri dishes. The examination of the inventive composition is made by heat aging in a convection oven at 170 ⁰ C. The criterion used is the unwanted discoloration occurring during oven aging. This is determined as follows:

a) for the 1 mm samples: yellowness index according to ASTM D 1925-70 and

b) for the 15 mm samples: Gardner color according to DIN 6161. Higher numbers mean stronger discoloration. The results are summarized in Table 3.

Table 3

Stabilizer no.

Yellowness index after hours at 170 ⁰ C 0 12 30 Gardner color after hours at 170 ⁰ C 0 12

no connection 1

3 3

86 6

126 12 5 1-2

3-4

FO 7.3 / HO / ac *

Claims (9)

ζ. u ο u ο claims 1. Use of substituted phenols of the formula I. OH } CD. · Γ} CH ₂ -SR ₂ in which. ^R l ^c ± ~ ^C Q ~ ^A ^ ^k y ⁱ · ^or C ₅ -C _l2 -C.ycloalkyl, the radicals R ₂ are independently Cl-Cg-alkyl groups which are unsubstituted or substituted by 1 or 2 Hydroxyl groups or by -OCO-R ₄ , -CO-OR or -CO-NR R are substituted, or phenyl or benzyl, R _{3 is} hydrogen or methyl, under the condition that when R _{1 is} different from methyl, R is methyl, R _{4 is} C ₁ -C ₁₇ -aryl, C ₂ -Cg -alkenyl or a radical of formula Ia - (CH ₂ ) _m (/ ^ -OH (Ia), R ¹ . m is O, 1 or 2, and the radicals R * independently of one another have the meaning given for R ₁ , R _{5 is} an optionally interrupted by -0-, -S- or -NR'- interrupted C ₁ -C ₂₀ -AlRyI , and R ^ is hydrogen or one for R ₁ . in that it is used for stabilizing elastomers or tackifying resins. 2. Use according to claim 1, characterized in that they are used for stabilizing elastomers. 2 6 1 O 6 p 3. Use according to claim 2, characterized in that the radicals R ₂ independently of one another represent C ₂ -C 18 -alkyl groups which are unsubstituted, or by 1 or 2 hydroxyl groups or by -OCO-Rit, -CO-OR 5 or -CO- NR5R6 are substituted, or benzyl or phenyl, wherein Ri ₁ , R5 and Re have the meaning given in claim 1. 4. Use according to claim 1, characterized -characterized in that Ri Ci-Cij-alkyl. 5. Use according to claim 2, characterized in that Ri is methyl or t-butyl. 6. Use according to claim 1, characterized in that R ₂ Ci »-Ci8-alkyl, -CH ₂ CH ₂ -OH, -CH ₂ CH ₂ -OCO-Ri ,, -CH ₂ -COO-R ₅ or -CH ₂ CH ₂ -COO-Rs, benzyl or phenyl, wherein Ri ^ and R5 have the meaning given in claim 1. 7. Use according to claim 6, characterized in that Ra is Cu-Ci8-alkyl. 8. Use according to claim 1, characterized in that the elastomer is a polydiene, a halogen-containing polymer or a polyurethane. 9. Use according to claim 1, characterized in that 0.05-5.0 wt .-% of the stabilizer of formula I, based on the elastomer or on the tackifying resin.