KR910005430B1 - Substituted phenol as stabilizer - Google Patents

Abstract

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Description

[Name of invention]

Substituted phenols useful as stabilizers

Detailed description of the invention

The present invention relates to novel bis (alkylthiomethyl) phenols useful as stabilizers.

Phenols containing alkylthiomethyl are known as stabilizers. For example, US Pat. No. 3,660,352 describes 2, 4, 6-trialkyl-bis (3, 5, -alkylthiomethyl) phenols useful as antioxidants for polymers and elastomers. . Moreover, 2, 6-bis (alkoxycarbonylalkylenethiomethyl) -4-alkylphenols are known from US Pat. No. 3 227 677 as antioxidants for polyolefins.

According to British Patent 1184 533, 2, 4-bis (alkylthiomethyl) -3, 6-dialkylphenols can be used as stabilizers for organic polymers and synthetic oils.

There remains a need for effective stabilizers for materials that are sensitive to thermal, oxidative or photoinductive degradation.

Therefore, this invention relates to the compound of the following general formula (I).

Here, the radicals R ₁ are each independently different, or substituted by one or two hydroxyl group or _{-OCO-R 4, -CO-OR} 5 or -CO-NR ₅ R ₆ unsubstituted, C ₈ - Or a C ₁₈ alkyl group, or phenyl or benzyl: R ₄ is C ₁ -C ₁₇ alkyl, C ₂ -C ₈ alkenyl or a radical of the general formula (Ia);

(In Formula (Ia), m is 0.1 or 2, and the radicals R 'are each independently different and are C ₁ -C ₈ alkyl or C ₅ -C ₁₂ cycloalkyl.) R ₅ is —O —,- C ₁ -C ₂₀ alkyl which may be interrupted by S-or-NR'-; R ₆ is hydrogen or has the meaning of one of those shown for R ₅ .

R 'as C ₁ -C ₈ alkyl is for example methyl, ethyl, n-propyl, isopropyl, n-butyl, secondary-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, 1 , 1-dimethylbutyl, n-heptyl, n-octyl or 2-ethylhexyl. Preferably, R 'is C ₁ -C ₄ alkyl, in particular methyl, ethyl isopropyl or tert-butyl, particularly preferably methyl or tert-butyl.

R ′ as C ₅ -C ₁₂ cycloalkyl is for example cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl or cyclododecyl. Preferably R 'is C ₅ -C ₈ cycloalkyl, more preferably cyclohexyl.

R ₁ as C ₈ -C ₁₈ alkyl is, for example, in addition to the radicals indicated for R ′ and also 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 ₁ is n-octyl or n-dodecyl.

R ₁ as C ₁ -C ₁₈ alkyl may be substituted with 1 or 2 hydroxyl groups. Examples of such radicals are 2-hydroxydodecyl, 2-hydroxyhexadecyl or 2-hydroxyoctadecyl.

R ₄ as C ₁ -C ₁₇ alkyl is for example radicals represented for R ′ and R ₁ , for example methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl , C ₁ -C ₁₂ alkyl, such as n-hexyl, n-octyl, 2-ethylhexyl or n-dodecyl.

R ₄ as C ₂ -C ₈ alkenyl is for example vinyl, allyl, metalyl, but-3-enyl, pent-4-enyl, hex-5-enyl, oct-7-enyl, des-9-enyl Or dodes-11-enyl, preferably R ₄ is vinyl or allyl.

R ₄ as a radical of formula (Ia) is for example 4-hydroxy-3, 5-dimethylphenyl, 4-hydroxy-3, 5-di-tert-butylphenyl, 4-hydroxy-3, 5-dimethylbenzyl, 4-hydroxy-3, 5-di-tert-butylbenzyl or 4-hydroxy-3, 5-dimethylphenylethyl, preferably 4-hydroxy-3, 5- Di-tert-butylbenzyl.

R ₅ or R ₆ as C ₁ -C ₂₀ alkyl is for example _one of the radicals shown for R ′ and R ₁ , respectively, or is 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′— is, for example, 3-oxabutyl, 3-oxapentyl, 3, 6-dioxaheptyl, 3, 6, 9-trioxadecyl, 3, 6, 9, 12-tetraoxatridecyl, 3, 6, 9, 12, 15-pentahexahexadecyl, 3, 6, 9, 12, 15, 18- Hexaoxanonadecyl, 3-thiabutyl, 3-azabutyl, 3-methyl-3-azapentyl, 3-ethyl-3-azapentyl, 3-methyl-3-aza-6-oxaheptyl, preferably , 3-oxapentyl or 3-azabutyl.

Especially preferred are radicals R _1, each a different and independently, substituted by one or two hydroxyl group or _{-OCO-R 4, -CO-OR} 5 or -CO-NR ₅ R ₆ or a unsubstituted C ₈ - A C ₁₈ alkyl group, and R ₄ , R ₅ and R ₆ are compounds of formula (I) as defined above.

Particularly preferred compounds of formula (I) are those in which the radicals R ₁ are the same and C ₈ -C ₁₂ alkyl.

Representative examples of the compound of formula (I) include the following substances.

2, 4-bis (n-octylthiomethyl) -6-methylphenol, 2, 4-bis (tert-octylthiomethyl) -6-methylphenol ¹ , 2, 4-bis (tert-dodecylthio Methyl) -6-methylphenol ² , 2, 4-bis (benzylthiomethyl) -6-methylphenol, 2, 4-bis (2'-ethylhexyloxycarbonylmethylthiomethyl) -6-methylphenol.

1 tert-octyl is 1, 1, 3, 3-tetramethylbutyl.

2 tert-dodecyl is a mixture consisting of 1, 1, 3, 3, 5, 5-hexamethylhexyl and 1, 1, 4, 6, 6-pentamethylhept-4-yl.

Compounds of general formula (I) are suitable for stabilizing compositions containing elastomers or tacky resins, examples of which are as follows.

1. Polydienes, for example polybutadiene, polyisoprene or polychloroprene—block polymers such as styrene / butadiene / styrene, styrene / isoprene / styrene or acrylonitrile / butadiene copolymers.

2. Copolymers between monoolefin and diolefin olefins such as, for example, ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers or Copolymers of other vinyl monomers and terpolymers of ethylene with propylene and dienes such as hexadiene, dicyclopentadiene or ethylidene-norbornene.

3. Halogen-containing polymers such as polychloroprene, chlorinated rubber, chlorinated or sulfochlorinated polyethylene, epichlorohydrin homopolymers and copolymers chlorotrifluoroethylene copolymers, for example polyvinylidene chloride Polymers made from halogen-containing vinyl compounds such as polyvinylidene fluoride, as well as copolymers thereof, such as, for example, vinyl chloride / vinylidene chloride, vinyl / vinyl acetate or vinylidene chloride / vinyl acetate.

4. Precursors, as well as polyurethanes, one of which is derived from polyethers, polyesters and polybutadienes having terminal hydroxyl groups, and the other of which is derived from aliphatic or aromatic polyisocyanates.

5. Natural rubber.

6. Mixtures of the above polymers (polyblends).

7. Aqueous emulsions of natural or synthetic rubber, such as, for example, natural rubber latex or latex of carboxylated styrene / butadiene copolymers.

Such elastomers may be in the form of latex and stabilized in such form.

Preferred elastomers are polydienes such as polybutadiene rubber, halogen-containing polymers such as polyvinylidene fluoride or polyurethanes.

The elastomer composition contains, for convenience, 0.01 to 10% by weight, preferably 0.05 to 5.0% by weight of a stabilizer of formula (I). Mixtures of stabilizers of formula (I) may also be used.

Incorporation into the elastomer is, for example, prior to or during molding, mixing the material of formula (I) and any other additives according to methods conventionally used in the art, or leaving the solvent intact or subsequent This can be achieved by adding the dissolved or dispersed compound to the polymer while evaporating the solvent. The compounds of formula (I) may also be added to the plastic to be stabilized, for example in the form of a master batch containing the abovementioned compounds at a concentration of 2.5 to 25% by weight.

Examples of adhesive resins are as follows:

Natural rosin resins such as elastomeric rosin, tree rosin, and tall oil rosin

Derivatives of rosin resins, for example glycerol esters, pentaerythritol esters, each of which may or may not be hydrogenated, unbalanced or unbalanced

-Synthetic C ₅ -or C ₉ -Hydrocarbon Resin

Indene resin, methyl indene resin, coumarone-indene resin

Terpene resin

-Methylstyrene resin

Phenolic Resin

Another tackifier such as asphalt or bitumen

A mixture of the above resins

Aqueous emulsion of the resin

Preferred adhesive compositions are those containing synthetic C ₅ -or C ₉ -hydrocarbon resins, rosin resins or derivatives of rosin resins.

The adhesive resin composition contains the stabilizer of the general formula (I) at 0.01 to 10% by weight, preferably 0.03 to 3.0% by weight, based on the adhesive resin. Mixtures of stabilizers of formula (I) may also be used.

The incorporation of the compound of general formula (I) into the tackifying resin can be achieved by a method conventionally used in the art during or before or after manufacture or modification.

Stabilized compositions can be used in a wide variety of forms, such as, for example, films, filaments, ribbons, molding compositions, profiles, or varnishes, binders for adhesives or putties.

Compounds of formula (I) are prepared by known methods, for example by reacting 2,4-bis (dimethylaminomethyl) -6-methylphenol with mercaptans of formula R ₁ -SH.

The phenols of general formula (I) of the invention are not only suitable for stabilizing elastomers and sticky resins, but also for stabilizing lubricants, in particular motor oils, based on mineral oils and synthetic oils.

Suitable lubricants are known to those skilled in the art and are described, for example, in Schmiermiittel Taschenbush (Lubricant Handbook), Huthig Verlag, Heidelberg, 1974.

Phenol of the general formula (I) of the present invention is added in an amount of 0.01 to 10% by weight based on the lubricant. On the basis of the lubricant, it is preferable to use 0.05 to 5.0% by weight of phenol, particularly preferably 0.1 to 2.0% by weight.

It is also possible to use mixtures of phenols of general formula (I).

Lubricant formulations of the invention containing phenols of formula (I) are added to improve certain performance properties, for example antioxidants, metal surface stabilizers, rust preventive additives, viscosity index enhancers, pour point depressants, dispersants / It may further contain other additives such as surfactants and wear resistant additives.

Examples of other additives that may be used in the lubricant, along with phenols of formula (I), are as follows:

1. Antioxidant

1.1. Alkylated monophenols, for example

2,6-di-tert-butyl-4-methylphenol

2-3-butyl-4, 6-dimethylphenol

2, 6-di-tert-butyl-4-ethylphenol

2,6-di-tert-butyl-4-n-butylphenol

2,6-di-tert-butyl-4-isobutylphenol

2, 6-dicyclopentyl-4-methylphenol

2- (α-methylcyclohexyl) -4, 6-dimethylphenol

2, 6-Dioctadecyl-4-methylphenol

2, 4, 6-tricyclohexylphenol

2,6-di-tert-butyl-4-methoxyphenol

1.2. 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

1.3. Hydroxylated thiophenyl ethers, for example

2, 2'-thiobis (6-tert-butyl-4-methylphenol)

2, 2'-thiobis (4-octylphenol)

4, 4'-thiobis (6-tert-butyl-3-methylphenol)

4, 4'-thiobis (6-tert-butyl-2-methylphenol)

1.4. Alkylidenebisphenols, for example

2, 2'-methylenebis (6-tert-butyl-4-methylphenol)

2, 2'-methylenebis (6-tert-butyl-4-ethylphenol)

2, 2'-methylenebis [4-methyl-6- (α-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'-ethylidenebis (4, 6-di-tert-butylphenol)

2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol)

2, 2'-methylenebis [6- (α-methylbenzyl) -4-nonylphenol]

2, 2'-methylenebis [6- (α, α-dimethylbenzyl) -4-nonylphenol]

4, 4'-methylenebis (2, 6-di-tert-butylphenol)

4, 4'-methylenebis (6-tert-butyl-2-methylphenol)

1, 1- (5-tert-butyl-4-hydroxy-2-methylphenyl) butane

2, 6-bis (tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol

1, 1, 3-tris (5-tert-butyl-4-hydroxy-2-methylphenol) butane

1, 1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmercapto butane

Ethylene glycol bis [3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate]

Bis (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene

Bis [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate

1.5. Benzyl compounds, for example

1, 3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -2, 4, 6-trimethylbenzene

Bis (3,5-tert-butyl-4-hydroxybenzyl) sulfide

Isooctyl 3,5-di-tert-butyl-4-hydroxybenzylmercetoacetate

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-hydroxybenzylphosphonate

Calcium salt of monoethyl 3, 5-di-tert-butyl-4-hydroxybenzylphosphonate

1.6. Acylaminophenols, for example

Anilide of 4-hydroxylauric acid

Anilide of 4-hydroxystearic acid

2,4-bis (octylmerceto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -s-triazineoctyl

N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate

1.7. esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols, wherein the alcohol is for example

Methanol diethylene glycol

Octadecanol triethylene glycol

1,6-hexanediol pentaerythritol

Neopentyl Glycol Tris (hydroxyethyl) isocyanurate

Thiodiethylene glycol bis (hydroxyethyl) oxalic acid diamide

1.8. esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono- or polyalcohols, wherein the alcohol is for example

Methanol Diethylene Glycol

Octadecanol triethylene glycol

1,6-hexanediol pentaerythritol

Neopentyl Glycol Tris (hydroxyethyl) isocyanurate

Thiodiethylene glycol bis (hydroxyethyl) oxalic acid diamide

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

N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine

N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine

N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine

2. ＵＶ absorber and light stabilizer

2.1. 2- (2'-hydroxyphenyl) benzotriazole, for example

5'-methyl, 3 ', 5'-di-tert-butyl, 5'-tert-butyl, 5'-(1, 1, 3, 3-tetramethylbutyl), 5-chloro-3 ', 5'-di-tert-butyl, 5-chloro-3'-tert-butyl-5'-methyl, 3'-tert-butyl-5'-tert-butyl, 4'-octoxy, 3 ', 5'-di-tert-amyl and 3', 5'-bis (α, α-dimethylbenzyl) derivatives.

2.2. 2-hydroxybenzophenone, for example

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

2.3. Esters of substituted and unsubstituted benzoic acids, for example

4-tert-butyl phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylesolecinol, bis (4-tert-butylbenzoyl) resolecinol, benzoylesolecinol, 2, 4 -Di-tert-butylphenyl-3, 5-di-tert-butyl-4-hydroxybenzoate and hexadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, for example

Ethyl α-cyano-β, β-diphenylacrylate, isooctyl α-cyano-β, β-diphenylacrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl- ｐ-methoxycinnamate, butyl α-cyano-β-methyl-ｐ-methoxycinnamate, methyl-α-carbomethoxy-ｐ-methoxycinnamate and N- (β-carbomethoxy-β- Cyanovinyl) -2-methylindolin.

2.5. Nickel compounds, for example

2,2'-thiobis [4- (1, 1, 3, 3-tetramethylbutyl) with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyl diethanol amine ) Phenol, for example 1: 1 or 1: 2 complex, nickel dibutyl dithiocarbamate, 4-hydroxy-3, 5-di-tert-butylbenzylphosphonic acid monoalkylester (eg Nickel salts of methyl or ethyl esters), for example nickel complexes of ketooximes such as 2-hydroxy-4-methylphenylundecyl ketone oxime, 1-phenyl-4-lauroyl-5-hydroxypyrazole Nickel complexes with or without additional ligands.

2.6. Sterically hindered amines, for example

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-hydroxybenzylmalonate, 1-hydroxyethyl-2, 2, 6, 6-tetramethyl-4- Condensation product of hydroxypiperidine and succinic acid, N, N '-(2, 2, 6, 6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2, 6 Condensation products of dichloro-1, 3, 5-s-triazine, tris (2, 2, 6, 6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis (2,2, 6, 6-tetramethyl-4-piperidyl) -1, 2, 3, 4-butanetetracarboxylate, 1, 1 '-(1, 2, -ethanediyl) bis (3, 3, 5, 5-tetra Methylpiperazinone).

2.7. Oxalic acid diamides, for example

4, 4'-dioctyloxyoxanilide, 2, 2'-dioctyloxy-5, 5'-di-tert-butyloxanilide, 2, 2'-didodecyloxy-5, 5'-di -Tert-butyloxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxalamide, 2-ethoxy-5-tert-butyl-2 Ortho- and para-methoxy-disubstituted oxanilides and mixtures with '-ethyloxanilides and their 2-ethoxy-2'-ethyl-5, 4'-di-tert-butyloxanilides And mixtures of para-ethoxy-disubstituted oxanilides.

3. Metal surface stabilizers, eg

N, N'-diphenyloxalic acid diamide, N-salicyl-N'-salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3, 5-di- Tert-butyl-4-hydroxy phenylpropionyl) hydrazine, 3-salicyloylamino-1, 2, 4-triazole, bis (benzylidene) oxalic acid dihydrazide.

4. Phosphites and Phosphonites, eg

Triphenyl phosphite, diphenylalkyl phosphite, phenyldialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2 , 4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol tri Phosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonite, 3, 9-bis (2,4-di-tert-butylphenoxy)- 2, 4, 8, 10-tetra-oxa-3, 9-diphosphaspiro [5.5] undecane.

5. Peroxide scavengers, eg

esters of β-thiodipropionic acid (eg lauryl, stearyl, myristyl or tridecyl esters) zinc salts of mercaptobenzimidazole or 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, diocta Decyl disulfide, pentaerythritol, tetrakis (β-dodecylmercapto) propionate.

6. Polyamide stabilizers, eg

Copper salts and two manganese salts in combination with iodine and / or phosphorus compounds.

7. Basic co-stabiliser, eg

Melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivative, hydrazine derivative, amine, polyamide, polyurethane, for example calcium stearate, zinc stearate, magnesium stearate, sodium ricinol Alkali metal salts and alkaline earth metal salts of fatty acids such as late and potassium palmidate, antimony pyrocatecholate or tin pyrocatecholate.

8. Nucleating agents, eg

4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid.

9. Fillers and reinforcing agents, eg

Calcium carbonate, silicate, fiberglass, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.

10. Other additives, for example

Plasticizers, lubricants, emulsifiers, pigments, fluorescent whitening agents, flame retardants, antistatic agents, foaming agents.

As a practical matter, the compositions of the present invention containing rubber or tackifying resins and phenols of general formula (I) may also contain other additives.

Examples of such additives are as follows:

1. Antioxidant

Examples of antioxidants can be found in the list of additional additives for the lubricants.

2. absorber and light stabilizer

2.1. 2- (2'-hydroxyphenyl) benzotriazole, for example

5'-methyl, 3 ', 5'-di-tert-butyl, 5'-tert-butyl, 5'-(1, 1, 3, 3-tetramethylbutyl), 5; Chloro-3 ', 5'-di-tert-butyl, 5-chloro-3'-tert-butyl-5'-methyl, 3'-tert-butyl-5'-tert-butyl, 4' -Octoxy, 3 ', 5'-di-tert-amyl and 3', 5'-bis (α, α-dimethylbenzyl) derivatives.

2.2. 2-hydroxybenzophenone, for example

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 or unsubstituted esters of benzoic acid, for example

4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylesolecinol, bis (4-tert-butylbenzoyl) resolecinol, benzoylesolecinol, 2, 4 -Di-tert-butylphenyl-3, 5-di-tert-butyl-4-hydroxybenzoate and hexadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, for example

Ethyl α-cyano-β, β-diphenylacrylate, isooctyl α-cyano-β, β-diphenylacrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl- ｐ-methoxycinnamate, butyl-α-cyano-β-methyl-ｐ-methoxycinnamate, methyl α-carbomethoxy-ｐ-methoxycinnamate and N- (β-carbomethoxy-β- Cyanovinyl) -2-methylindolin.

2.5. Nickel compounds, eg

2, 2′-thio-bis [4- () complexed with 1: 1 or 1: 2 with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine 1, 1, 3, 3-tetramethylbutyl) phenol] nickel complex; Nickel dibutyldithiocarbamate; Nickel salts of 4-hydroxy-3, 5-di-tert-butylbenzylphosphonic acid monoalkyl esters (e.g., methyl or ethyl esters); Nickel complexes of ketoximes such as, for example, 2-hydroxy-4-methylphenylundecyl ketone oxime; Nickel complex formed by 1-phenyl-4-lauroyl-5-hydroxypyrazole with or without additional ligand.

2.6. Sterically hindered amines, for example

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-hydroxy benzylmalonate, 1-hydroxyethyl-2, 2, 6, 6-tetramethyl-4- Condensation product of hydroxypiperidine and succinic acid, N, N '-(2, 2, 6, 6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2, 6 Condensation products of dichloro-1, 3, 5-s-triazine, tris (2, 2, 6, 6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis (2, 2, 6, 6-tetramethyl-4-piperidyl) -1, 2, 3, 4-butanetetracarboxylate, 1, 1 '-(1, 2, -ethanediyl) bis (3, 3, 5, 5-tetra Methylpiperazinone).

2.7. Oxalic acid diamide, for example

4, 4'-dioctyloxyox anilide, 2, 2'-dioctyloxy-5, 5'-di-tert-butyloxanilide, 2, 2'-didodecyloxy-5, 5'-di -Tert-butyloxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxalamide, 2-ethoxy-5-tert-butyl-2 '-Ethyloxanilide and mixtures thereof with 2-ethoxy-2'-ethyl-5, 4'-di-tert-butyloxanilide and mixtures of ortho- and para-methoxy-disubstituted oxanilides and Mixtures of ortho- and para-ethoxy-disubstituted oxanilides.

3. phosphites and phosphonites, eg

Triphenyl phosphite, diphenyl alkyl phosphite, phenyldialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2 , 4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol tri Phosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonite, 3,9-bis (2,4-di-tert-butylphenoxy)- 2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane.

4. Peroxide scavenger, eg

Esters of β-thiodipropionic acid such as lauryl, stearyl, myristyl or tridecyl esters; Zinc salts of mercaptobenzimidazole or 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis (β-dodecyl mercapto) propionate.

5. polyamide stabilizers, eg

Copper salts and divalent manganese salts in combination with iodine and / or phosphorus compounds.

6. Basic ball stabilizer, eg

Melamine; Polyvinylpyrrolidone; Dicyandiamide; Triallyl cyanurate; Urea derivatives; Hydrazine derivatives; Amines; Polyamides; Polyurethane; Alkali metal salts and alkaline earth metal salts of high fatty acids such as calcium stearate, zinc stearate, magnesium stearate, sodium ricinolate and potassium palmitate, antimony pyrocatecholate or tin pyrocatecholate.

7. Nucleating agents, eg

4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid.

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

9.0 other additives, for example

Plasticizers, lubricants, emulsifiers, pigments, fluorescent whitening agents, flame retardants, antistatic agents, blowing agents, waxes, oils, organic solvents.

The following examples illustrate the present invention in more detail. In the following description and claims,% is by weight.

(Production Example)

Example 1

Preparation of 2, 4-bis (n-octylthiomethyl) -6-methylphenol (Compound 1)

Dimethylamine was continuously distilled off at 53.2 bar, at 150 ° C., 160.74 g (0.72 mol) of 2,4-bis (dimethylaminoethyl) -6-methylphenol and 210.65 g (1.44 mol) of n-octanthiol ) Is mixed for 36 hours in a reactor equipped with a stirrer and a multiple coil cooler. 291.6 g (yield-95%) of yellow oil are obtained. The crude product is column chromatographed through silica gel to give pure 2, 4-bis (n-octylthiomethyl) -6-methylphenol in the form of a colorless oil.

Analysis value:

Theoretical value: C: 70.69% H: 10.44% S: 15.09%

Found: C: 70.85% H: 10.42% S: 15.11%

¹ H-NMR (CDCl ₃ ; 100 MHz; data δ [ppm] based on TMS = 0, s = single line); Specific signal for Ar-CH ₂ S appears at 3.77 (s) and 3.6 (s).

In a similar manner, the compounds of formula (I) are prepared.

Application Example

The test for the stabilizing activity of the compounds 1 and 2 of Example 1 is carried out.

Example 2

Stabilization of Polybutadiene Rubber

[Oven ageing]

100 g of polybutadiene pre-stabilized with 0.4% of 2, 6-di-tert-butyl-P-cresol are homogeneously mixed with 0.25% of the stabilizer to be tested on a mill at 50 ° C. for 6 minutes. A 10 mm thick sample is pressed from a rolled sheet at 80 ° C. Another sample is prepared in the same way without a stabilizer.

The compositions of the invention are tested by thermal aging of the samples in an air circulation oven at 80 ° C. The criterion to confirm the stability of the sample is the gel content unnecessarily produced during oven soaking. Gel content is measured as follows:

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

The gel content is calculated using the following equation.

E = weight [expressed as a quantity (1g)]

A = weight of residual oil after evaporation

The gel content increases rapidly after the induction period. The time at which the gel content of the sample represents 2% is arbitrarily defined as the induction period. The gel content is measured periodically to determine this triggering period.

The results are shown in Table 1.

TABLE 1

Example 3

Stabilization of Polybutadiene Rubber [Brabender]

In a Brabender plastograph at 160 ° C., 60 rpm, 100 parts of polybutadiene pre-stabilized with 0.4% of 2, 6-di-tert-butyl-ｐ-cresol at 0.25% and 30% to be tested. Mix for minutes.

The induction time is measured from the flow of torque, i.e., the mixing time (minutes) until the torque increases after a minimum torque of 100mp.

The results are shown in Table 2.

TABLE 2

Example 4

TFOUT Test [Thin-film oxygen uptake test]

This test is a variation of the rotary explosive oxidation test on mineral oil (ASTM D 2272). The TFOUT test was conducted by C.S.Ku and S.M. Hsu, A Thin-Film Oxygen Uptake Test fo the Evaluation of Automotive Cramkcase Lubricants, Lubrication Engineering, Vol. 40 (2), PP. 75-83 (1984). The test oil is a motor oil based on mineral oil. The motor oil contains zinc dithiophosphate (0.75% -zinc content 0.06%, based on the motor oil) 1/2 of the usual amount; This change is made to reveal the potential effect of the stabilizer being tested. Compound 1 of Example 1 was prepared in the presence of a liquid oxidized as 2% water and catalyst (4% concentration), a nitrate fraction in gasoline, and in the presence of a liquid metal naphthenate as another catalyst (4% concentration). Test in the motor oil described above (water and both liquid catalysts are carried with a certificate of analysis based on National Reference Standards (NBS) No. 1817). The test ends when the dip appears in the pressure / time plot.

The results shown in the table below represent the time in minutes until the dip is displayed in the pressure / time plot.

Long periods of time correspond to good stabilizing activity.

Stabilizer Concentration: 0.5% based on oil.

TABLE 3

Example 5

Stabilization of hydrogenated C ₅ -hydrocarbon resins

50 g of a resin pre-stabilized with 0.15% of 2, 6-di-tert-butyl-ｐ-cresol was dissolved in a glass flask at 170 ° C, and 0.1% of compound 1 was mixed over 15 minutes while stirring. Hot melt is poured into an aluminum dish and a petri dish. The layer thickness of the solidified resinous material is about 15 mm in aluminum dishes and 1 mm in petri dishes. The composition of the present invention is tested by thermal aging in a 170 ° C. air circulation oven. The criterion for confirming the stability of the sample is discoloration which appears undesirably during oven soaking. Discoloration is determined as follows.

(a) For 1 mm samples: Yellowness Index according to ASTDM 1925-70

(b) For 15 mm specimens: Gardner color value according to DIN 6161.

Higher values indicate more discoloration (this applies to both the push index and the Gardner color grade).

The results are shown in Table 4.

TABLE 4

Claims (2)

Compounds of the general formula (I) Wherein radicals R ₁ are each independently, and one or two of the hydroxyl group or _{-OCO-R 4, -CO-OR} 5 or -CO-NR ₅ R ₆ optionally substituted by unsubstituted C ₈ -C ₁₈ An alkyl group, or phenyl or benzyl; R ₄ is C ₁ -C ₁₇ alkyl, C ₂ -C ₈ alkenyl or a radical of the general formula (Ia); (In the formula (Ia), m is 0.1 or 2, and the radicals R 'are each independently and C ₁ -C ₈ alkyl or C ₅ -C ₁₂ cycloalkyl.) R ₅ is —O —,-S C ₁ -C ₂₀ alkyl which may be interrupted by -or-NR'-; R ₅ is hydrogen or has the meaning of one of those shown for R ₅ above. The compound of claim 1, wherein the radicals R ₁ are each independently independent and unsubstituted C ₈ -C ₁₈ alkal.