KR910007591B1 - Preparation of substituted phenol - Google Patents

Abstract

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Description

[Name of invention]

Process for preparing substituted phenol

Detailed description of the invention

The present invention relates to a process for the preparation of 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 No. 1,184,533, 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.

Accordingly, the present invention relates to the preparation of a compound of formula (I) comprising reacting 2, 4-bis (dimethylaminomethyl) -6-methylphenol with a mercaptan of formula R ₁ -SH:

Wherein the radicals R ₁ are each independently different and are C ₈ -C unsubstituted or substituted by 1 or 2 hydroxyl groups or -OCO-R ₄ , -CO-OR ₅ or -CO-NR ₅ R _{6 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 the formula (Ia), m is 0, 1 or 2, the radicals R 'are each independently different, C ₁ -C ₈ alkyl or C ₅ -C ₁₂ cyclo alkyl) 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 above.

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-nuclear, 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 , respectively, preferably 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 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-azabentyl, 3-methyl-3-aza-6-oxaheptyl, preferably , 3-oxapentyl or 3-azabutyl.

Especially preferred are radicals R ₁ are different and each independently, 1 or 2 hydroxyl groups, or R ₄ -OCO-, of di-substituted by CO-OR ₅ or -CO-NR ₅ R ₆ or an 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) are 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,

(Note) 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.

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 "Schmiermottel Tashenbuch" (Lubricant Handbook), Huthig Verlag, Heidelberg, 1974.

Accordingly, the present invention also relates to a composition containing a lubricant and at least one compound of general formula (I) in order to stabilize the lubricant against the action of oxygen, heat, light and high energy radiation.

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 can be used in lubricants, 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-tert-butyl-4,6-dimethylphenol

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

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

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

2,6-dicyclopentyl-4-methylphenol

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

2,6-Dioctadecyl-4-methylphenol

2,4,6-tricyclohexylphenol

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

1.2. Alkylated hydroquinones, 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-bis (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-methylphenyl) 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-hydroxybenzyl mercetoacetate

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-hydroxybenzylfonate

Calcium Salts 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 (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -s-triazine

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

1.7 esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols,

Here, 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 polyhydric alcohols, in which 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'-methyl, 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-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylesolecinol, bis (4-tert-butylbenzoyl) resorcinol, benzoylesolecinol, 2,4 -Di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate and nucleodecyl 3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, for example

Ethyl α-cyano-β, β-diphenylacrylate, isooctyl α-cyano-β, β-diphenylacrylate, methylα-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-tetramethyl) with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanol amine Butyl) phenol], for example 1: 1 or 1: 2 complex, nickel dibutyl dithiocarbamate, 4-hydroxy-3, 5-di-tert-butylbenzylphosphonic acid monoalkyl ester ( Eg nickel salts of methyl or ethyl esters), nickel complexes of ketooximes such as 2-hydroxy-4-methylphenylundecyl ketone oxime, 1-phenyl-4-lauroyl-5-hydroxypyrazole Nickel complexes with or without this additional ligand.

2.6. Stericly 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-octanylamino-2, 6 Condensation product 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-butanetetraca carboxylate, 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-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1, 2, 4-triazole, bis (benzylidene) oxalic acid dihydrazide.

4. Phosphites and Phosphonites, for example

Triphenyl phosphite, diphenylalkyl phosphite, phenyldialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioxadecyl phosphite, distearyl pentaerythritol diphosphite, tris ( 2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, trisnearyl sorbitol Triphosphite, 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 divalent manganese salts in combination with iodine and / or phosphorus compounds.

7. 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 palmitate, antimony pyrocatecate or tin pyratecatelate.

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. UV absorbers and light stabilizers

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'-2 -Butyl-5'-tert-butyl, 4'-octoxy, 3 ', 5'-di-tert-amyl and 3', 5'-bis (α, α-dimethylbenzyl) derivatives.

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. Esters of substituted or unsubstituted benzoic acid, for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylsolecinol, bis (4-tert-butylbenzoyl) Resorcinol, benzoylsolecinol, 2,4-di-tert-butylphenyl 3, 5-di-tert-butyl-4-hydroxybenzoate and hexadecyl 3,5-di-tert-butyl -4-hydroxybenzoate.

2.4. Acrylates such as ethyl α-cyano-β, β-diphenylacrylate, isooctyl α-cyano-β, β-diphenylacrylate, methyl α-carbomethoxycinnamate, methyl α-cya No-β-methyl-p-methoxycinnamate, butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-methoxycinnamate and N- (β-carbo Methoxy-β-cyanovinyl) -2-methylindolin.

2.5. 2, 2'- complexed with 1 or 1 or 1: 2 with or without additional ligands such as nickel compounds such as n-butylamine, triethanolamine, or N-cyclohexyl diethanolamine Nickel complex of thio-bis [4- (1, 1, 3, 3-tetramethylbutyl) phenol]; Nickel dibutyldithiocarbamate; Nickel salts of 4-hydroxy-3, 5-di-tert-butylbenzylphosphonic acid monoalkyl esters (e.g. methyl or ethyl esters), e.g. 2-hydroxy-4-methylphenylundecyl ketone oxime Nickel complexes of ketoxime; Nickel complex wherein 1-phenyl-4-lauroyl-5-hydroxypyrazole is formed with or without additional ligand.

2.6. Stereo hindered amines such as bis (2, 2, 6, 6-tetramethylpiperidine) 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, Condensation product of 6-tetramethyl-4-hydroxypiperidine and succinic acid, N, N '-(2, 2, 6, 6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-ter-3 Condensation products of -octylamino-2,6-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-tetramethylpiperazinone).

2.7. Oxalic acid diamides such as 4, 4'-dioctyloxyox anilide, 2, 2'-dioctyloxy-5, 5'-di-tert-butyloxyanilide, 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 ortho- and para-methoxy- Mixtures of disubstituted oxanilides and mixtures of ortho- and para-ethoxy-disubstituted oxanilides.

3. Phosphites and phosphites such as triphenyl phosphite, diphenyl alkyl phosphite, phenyldialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distea Reel pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) penta Erythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) 4, 4'-biphenylene diphosphonite, 3,9-bis (2,4 Di-tert-butylenoxy-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro [5.5] untecan.

4. Peroxide scavengers, for example esters of β-thiodipropionic acid, such as lauryl, stearyl, myristyl or tridecyl esters; Zinc salts of mercaptobenzimidazole or 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfite, pentaerythritol tetrakis (β-dodecyl mercapto) propionate.

5. Polyamide stabilizers, for example copper salts and divalent manganese salts in combination with iodine and / or phosphorus compounds

6. basic co-stabilizers such as melamine; Polyvinylpyrrolidone; Dicyandiamide; Triallyl cyanurate; Urea derivatives; Hydrazine derivatives; Amines; Polyamides, polyurethanes; 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, for example 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 and hydroxides, carbon black, graphite.

9. Other additives such as plasticizers, lubricants, emulsifiers, pigments, fluorescent whitening agents, flame retardants, antistatic agents, foaming agents, waxes, oils, organic solvents.

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

Production Example

Example 1

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

Continuous distillation of dimethylamine at 53.2 bar, 160.74 g (0.72 mole) of 2,4-bis- (dimethylaminoethyl) -6-methylphenol and 210.65 g (1.44 mole) of n-octanethiol at 150 ° C ) 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 is 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], s = single line based on TMS = O): Specific signal for Ar—CH ₂ S at 3.77 (s) and 3.6 (s).

In a similar manner to prepare a compound of formula (I)

Application Example

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

Example 2

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 for the Evaluation of Automotive Crankcase 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) in one half of the conventional 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 a catalyst (4% concentration), a nitrate fraction in gasoline, and a liquid metal naphthenate as another catalyst (4% concentration). Test in motor oil as described above [water and two liquid catalysts are carried with certificate of analysis based on National Reference Agency (NBS) standard reference material 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 1

Claims (2)

A process for preparing a compound of formula (I) by reacting 2,4-bis (dimethylaminomethyl) -6-methylphenol with mercaptan of formula R ₁ -SH: Wherein the radicals R ₁ are each independently and substituted with C ₈ -C ₁₈ unsubstituted or substituted by 1 or 2 hydroxyl groups or -OCO-R ₄ , -CO-OR ₅ or -CO-NR ₅ R ₆ 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, the radicals R 'are each independently, C ₁ -C ₈ alkyl or C ₅ -C ₁₂ cyclo alkyl.) 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 above. The process of claim 1, wherein the radicals R ₁ are each independently independent and unsubstituted C ₈ -C ₁₈ alkyl.