DD276086A5 - PREPARATION OF NEW BIS- (ALKYLTHIOMETHYL) PHENOLES AND THEIR USE AS STABILIZERS FOR LUBRICANTS - Google Patents

Abstract

According to the invention, novel bis (alkylthiomethyl) phenols of the formula I are prepared by reacting 2,4-bis (dimethylaminomethyl) -6-methylphenol with a mercaptan R1-SH. In this case, for example: R1 C8-C18-alkyl groups, unsubstituted or substituted by 1 or 2 hydroxyl groups or OCOR2 u. a., phenyl or benzyl, R2 is C1-C17-alkyl, C2-C8-alkenyl and the like. a. Formula (I)

Description

wherein the radicals R ₁ independently of one another represent C 1 -C 4 -alkyl groups which are unsubstituted or substituted by 1 or 2 hydroxyl groups or by -OCO-R ₂ , -CO-OR ₃ or -CO-NR ₃ R ₄ , or phenyl or benzyl, R _{2 is} C ₁ -C ₁₇ -alkyl, C ₂ -C ₈ -alkenyl or a radical of the formula I a

there),

m is 0.1 or 2, and the radicals

R 'independently of one another are C ₁ -C ₈ -alkyl or C 9 -C 12 -cycloalkyl, R _{3 is} a C ₁ -C ₂₀ -alkyl which is optionally interrupted by -O-, -S- or -NR', and R 4 is Is hydrogen or has the meaning given for R ₃ , characterized in that 2,4-bis (dimethylaminomethyl) -6-methyl-phenol is reacted with a mercaptan R ₁ -SH.

2. The method according to claim 1, characterized in that the radicals R _{1 are} independently unsubstituted Ce-C ^ -alkyl.

3. Use of compounds of formula T according to claim 1, characterized in that they are used as stabilizers for lubricants against their damage by the action of oxygen, heat, light and high-energy radiation.

Application blot of the invention

The invention relates to the preparation of novel bis (alkylthlomethyl) phenols and their use as stabilizers for lubricants against their damage by the action of oxygen, heat, light and high-energy radiation.

Characteristic of the known state of the art Alkylthiomethylhaltlge phenols are known as stabilizers. For example, US Pat. No. 3,660,352 discloses the use of

2,4,6-tri-alkyl-bis- (3,5-alkylthlomethyl) phenols described as antioxidants in polymers and elastomers. From the

U.S. Patent No. 3,227,677 also discloses 2, e-bis (alkoxycarbonylalkylenthlomethyl) -4-alkylphenols as antioxidants for polyolefins

known.

According to GB-PS 1184 533 are 2 _< 4-B! S- (alkylthiomethyl) -3,6-dialkylphonols as stabilizers for organic polymers and for

Synthetic oils can be used.

Object of the invention

The object of the invention is to provide novel effective stabilizers for materials which are sensitive to thormic, oxide or solvent degradation.

Explanation of the essence of the invention

Dor invention Not dio object to find neuo compounds that are sensitive as stabilizers for materials that are sensitive to thermal, oxldatlvon or iichtinduziorten degradation, such. As lubricants based on mineral oils or synthetic oils, in particular motor oils, are suitable.

According to the invention, compounds of the formula I are OH

^ _N ^ H ₂ -SR ₁

¹ s )

CH ₂ -S-

₂ -SR,

in which the radicals Rt independently of one another represent Cg-Cia-alkyl groups which are unsubstituted or substituted by 1 or 2 hydroxyl groups or by -OCO-R ₂ , -CO-OR ₃ or -CO ~ NR ₃ R ₄ , or phenyl or phenyl or benzyl,

R _{2 is} C, -C _w -AlkYl, Cj-Ce-alkenyl or a radical of the formula la

- (CH ₂₎ - _<=> -0H ">.

m is 0.1 or 2, and the radicals

R 'independently of one another are C 1 -C -alkyl or C 1 -C -cycloalkyl, R _{1 is} an optionally interrupted by -O-, -S- or -NR'- interrupted dC ^ alkyl, and R _{4 is} hydrogen or has the meaning given for R ₃ ,

by reacting 2,4-bis (dimnthylaminomethyl) -6-methylphenol with a mercaptan Ri-SH.

R 'as Ct-Cs-alkyl is, for example, methyl, ethyl, n-propyl, isopropyl, η-butyl, sec-butyl, t-butyl, ii-pentyl, isopentyl,

n-hexyl, 1,1-dimethylbutyl, n-heptyl, n-octyl or 2-ethylhexyl.

Preferably, R 'is C ₁ -C ₄ alkyl, especially methyl, ethyl, isopropyl or t-butyl, and most preferably methyl or t-butyl. R 'as C ₅ -C ₁₂ -CyClOalkyl means, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl or cyclododecyl. Prefers

R 'is Ce-Cs'cycloalkyl, in particular cyclohexyl.

R 1 as C 1 -C 6 -alkyl is, for example, n-orthyl, 2-ethylhoxyl, nonyl, n-decyl, 1,1,3,3-tetramethylbutyl, 1,1,3,3- Tetramethylhexyl, n-undecyl, n-dodecyl, 1,1,3, U, 5,5-hexamethylhexyl, n-tetradecyl, n-hexadecyl or n-octadecyl. Prefers

Rt is C ₁ -C ₁ S-alkyl, for example n-octyl or n-dodecyl.

Ri as the Cr-Cia alkyl may be substituted by one or two hydroxyl groups. As such radicals are, for example

2-hydroxydodecyl, 2-hydroxyhexadecyl or 2-hydroxyoctadecyl in question.

R ₂ as Ci-CirAlkyl means, for example, the radicals mentioned for Rt and methyl, ethyl, n-propyl, isopropyl, n-butyl,

sec.Butyi, t-butyl, n-pentyl, isopentyl, n-hexyl, 1,1-dimethylbutyl or n-heptyl, preferably C ₁ -C ₂ -alkyl, such as

Methyl, ethyl, n-propyl, isopropyl, η-butyl, t-butyl, n-hexyl, n-octyl, 2-ethylhexyl or n-dodecyl. If R _{2 is} C 1 -C -alkenyl, then the radicals vinyl, allyl, methallyl, but-3-enyl, pent-4-enyl, hox-5-enyl, for example, Oct-7-enyl, Dec-9-enyl or Dodec-11-enyi in question. Preferably, R _{2 is} vinyl or allyl. R ₂ as a rust for formula la can be, for example, 4-hydroxy-3,5-dimethylphenyl, 4-hydroxy-3,5-di-t-butylphenyl, 4-hydroxy

3,5-dimethylbenzyl, 4-hydroxy-3,6-di-t-butylbenzyl or 4-hydroxy-3,5-dimethylphenylethyl, preferably 4-hydroxy-3,5-di-t-butylbenzyl.

I ₁ or R ₄ as Ci-C ₂₀ alkyl means, for example, the radicals mentioned for R ₁ or R ₂ and eicosyl, preferably methyl, ethyl,

n-hexyl, n-octyl or n-dodecyl.

R < ^v , rv ^{v 1} U as Ci-C ₂₀ -alkyl interrupted by -O-, -S- or -N'- means, for example, 3-oxabutyl, 3-oxapentyl,

3,6-4V, oxaheptyl, 3,6,9-trioxadecyl, 3,6,9,12-tetraoxatridecyl, 3,6,9,12,15-pentaoxahexadecyl, 3,6,9,12,15,18- Hexaoxanonadecyl,

3-Tl.labutyl. 3-azabutyl, 3-methyl-3azapentyl, 3-ethyl-3-azapentyl, 3-methyl-3-aza-6-oxaheptyl, preferably 3-oxapentyl or 3-azabutyl.

In formula I, the radicals Ri are preferably, independently of one another, Cg-Cu-alkyl groups which are unsubstituted or

are substituted by 1 or 2 hydroxyl groups or by -OCO-R ₂₁ -CO-OR ₁ or -CO-NR ₃ R ₄ , wherein R ₂ , R ₁ and R _{4 have} the abovementioned meaning.

Preference is given to compounds of the formula I in which the radicals R 1 independently of one another are unsubstituted C ₁ -C 5 -alkyl!

stand.

Particular preference is given to compounds of the formula I in which the radicals R ₁ have the same meaning and C ₁ -C ₁₂ -alkyl

stand.

As examples of representatives vo. A. Indunctions of the formula I are to be regarded as the substances listed below:

2,4-BLS (n-octylthlomethyl) -e-metnylphanol,

2,4-Bls- (t-octylthiomothyl) -6-methylphonol [t-octyl is 1,1,3,3-tetramethylbutyl), 2,4-bis (t-dodecylthiomethyl) -6-methylphenol (t-dodecyl is a mixture of 1,1,3,3,5,6-hexamethylhexyl and 1,1,4,6,6-

Pontamothylhopt- (4 -) - yl] and 2,4-Bl8- (bonzylthiomethyl) -e-methylphonol. Dio implementation of dos-2,4-Bir dimothylaminomethyl) -6-mothylphenols with the mercaptan R _t -SH is carried out according to known Methods, for example, are described in GB-A-1184 633 and in US-A-3227677. All starting products are

Bokannto compounds and kön'.en be prepared by bekannton method. They are also partially commercially available.

The erglndungsgomäßon phenols of formula I are - in addition dam stabilizing elastomers and tackifying Resins - also for stabilizing lubricants on the bed of mineral oils or synthetic oils, in particular of Engine oils. The lubricants in question are familiar to the person skilled in the art and are used, for example. in the "Schmiermittel Taschenbuch iHüthig Verlag, Heidelberg, 1974) *. Another object of the invention is therefore the use of compounds of formula I as stabilizers for Lubricants against damage caused by exposure to oxygen, heat, light and high-energy radiation. The phenols of the formula I according to the invention are expediently used in a concentration of 0.01-10% by weight,

calculated on the lubricant, added. Preference is given to using from 0.05 to 5.0% by weight, particularly preferably from 0.1 to 2.0% by weight, of the phenols, calculated as the amount of lubricant.

Mixtures of phenols of formula I can also be used. Inventive lubricant formulations containing phenols of the formula I may additionally contain other additives

included, which are added to improve certain performance characteristics, such. B. more antioxidants,

Metal passivators, rust inhibitors, viscosity index improvers, pour point depressants, dispersants / surfactants and Anti-wear additives. As further additives ", with which together the phenols of the formula I according to the invention are used in lubricants

can, for example, be mentioned:

1. Antioxidants

1.1. Alkyllated monophenols, e.g. 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- (c-methylcyclohexylMe-dimethyl-phenol, 2 , 6-di-octadecyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol.

1.2. Alkyllated hydroquinones, e.g. 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-di-phenyl-4-octadecyloxyphenol.

1.3. Hydroxylated thiodiphenyl ethers, e.g. As 2,2'-thio-bis (6-th.-butyl-4-methylphenol), 2,2'-thlo-bis (4-octylphenol), 4,4'-thiobis- (6-tert Butyl-3-methylphenol), 4,4'-thio-bls- (6-tert-butyl-2-methyl-phenol).

1.4. Alkyllaene-Blsphenols, z. For example, 2,2'-methylene-bis (6-tert-butyl-4-methyl-phenol), 2,2'-methylene-bis (6-tert-butyl <1-ethylphenol), 2 _l 2 'Methylene-bis- [4-methyl-6- (a-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, i'-ethylidene-bis- (4,6-di-tert-butylph (inol ), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2 _{l of} 2'-methylenebis [6- (a-methylbenzyl) -4-nonylphenol), 2,2 ' -Mi) thylene-bis- (6 · (a, a-dimethylbenzyl) -4-nonylphenol), 4,4'-methylenebis (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-yydroxy-2-methylphenyl) -3-ndodecylmercaptobutane, ethylene glycol bis [3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate], di- '.S-tert-butyl ^ -hydroxy-S-methylphenyl-dicyclopentadiene, di- | 2 - (3'-tert-butyl-2'-hydroxy-5'-methyl-benzyl) -6-tert-butyl-4-methyl-phenyl] 'terephthalate.

1.5. Benzyl blends, e.g. B. 1, 3,5-Trl- (3,5-dl-tert-butyl-4-hydroxy-benzyl) -2,4,6-tri-methylbenzene, DI- (3,5-di-tert-butyl-4 -hydroxybenzyl-sulfide.dS-di-tert-butyl-hydroxybenzyl-mercaptoacetic acid isooctyl-bis, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyldithiol-terephthalate, 1H, S-Tris-OS) di-tert-butyl-m-hydroxvbenzyl-isocyanurate, 1,3,5-tris - <4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl-isocyanurate, di-tert-butyl-m-hydroxybenzyl-phosphonic acid dioctadecyl ester, 3, 5-Di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, calcium salt.

1.6. Acylamino phenols, e.g. 0.4-Hydroxy-laurinoic anilide, 4-hydroxystearic anilide, 2,4-bis-octylmercapto-6- (3,5-di-tert-butyl-4-hydroxy-anilino) -s-triazine, NO.S-di-tert-butyl ^ -hydroxyphenyll-carbamic acid octyl ester.

1.7. Esters of ß- (3,5-DI-tert-butyl-4-hydroxyphenyl) -proplonsiure with mono- or muhrwertigen alcohols such. With methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris-hydroxyethyl isocyanurate, di-hydroxyethyl-oxalic acid diamide.

1.8. Esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) -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, di-hydroxyethyl-oxy-acid diamide.

1.9. Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) -proplonic acid, such as. N, N'-di- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl-hexamethylenediamine, N, N'-di- (3,5-di-tert-butyl-4-hydroxyphenyl-propionyl) -trimethylene-end-amine , N, N'-di- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hydrazine.

2. UV absorber and sunscreen

2.1.2- (2'-hydroxyphenyl) benzotriazoles, such as. B. the 5'-methyl, 3 ', 5'-di-tert-butyl, 5'-tert-butyl, 5' - (1,1,3,3-Totramethylbutyl! -, 5-chloro 3 ', 6'-di-tert-butyl, 5-chloro-3'-tert-butyl-5'-methyl, 3'-sec-butyl-5'-tert-butyl, 4'-octoxy, 3 ', 5'-di-tert-amyl, 3', 5'-bis (a, adimethylbenzyl derivative.

T.2. 2-Hydroxybenzophonone, 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-tert-butylphenyl salicylate, phenyl salicylate, octylphenylsylcate, dibcnzoylresorcinol, bis (4-tert-butylbenzoyl) -resorcln, benzoylresorcln, 3, B-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert. butylphonyl ester, SB-DI-tert-butyl-hydroxybenzoic acid hexoxadocyl ester.

2.4. Acrylic & te, such. A-cyano-β, -β-diphenylacrylic acid ethyl ester or isooctyl ester, α-carbomethoxy cinnamic acid methyl ester, α-cyano-β-methyl-p-methoxy-cinnamic acid methyl ester or the like. -butylestor.a-carbomethoxy-p-methoxy-cinnamic acid methyl ester, N-lß-carbomothoxy-cyanovinyld ^ -mothyl-indole.

2.5. Nickel compounds, e.g. Nickel complexes of 2,2'-thio-bis- [4-1,1,3,3-tetrametbylbutyl) -phenol], such as the 1: 1 or the 1: 2 complex, optionally with additional ligands such as n Butylamine, triethanolamine or N-cyclohexyl-diethanolamine, Nictaldibutyldithiocarbamat, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonsäure monoalkyl esters, such as methyl or ethyl esters, nickel complexes of ketoximes, such as 2-hydroxy-4- Methyl-phenyl undecyl ketone oxime, nickel complexes of i-phenyl-4-lauroyl-S-hydroxy-pyrazole, optionally with additional ligands.

2.6. Sterlsch hindered amines, such as. Bis (2,2,6,6-tetramethylpiperidyl) sebacate, bis (1,2,2,6,6-pentamethylpiperidyl) sebacate, n-butyl-3,5-di-tert. butyl-4-hydroxybenzyl malonic acid bis (1,2,2,6,6-pentamethylplperidyl) 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-tert-octylamino-2,6-dir.-chloro-1,3,5-s-triazine, tris- (2,2, 6,6-tetramethylm-piperidyl-N-nitrilotriacetate, tetrakis- (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylic acid, 1,1 '- (1,2-ethanediyl) bis (3,3,5, S-tetramethyl-piperazinone).

2.7. Oxalic acid diamonds, such as 4,4'-di-octyloxy-oxanilide. 2,2'-dioctyl-oxy-5,5'-di-tert-butyl-oxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert-butyl-oxanilld, 2-ethoxy-2'-dichloroethane ethyl oxanilide, N, N'-bis- (3-dimethylaminopropyl) -oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with 2-ethoxy-2 ^l -ethyl-5,4 ' di-tert-butyl-oxanilide, mixtures of o- and p-methoxy- as well as o- and p-ethoxy-di-substituted oxanilides.

3. Metalldesaktlvatoren, such as. B. Ν, Ν'-Diphenyloxalsäurediamid, N-salicylate-N'-salicyloylhydrazin, N, N'-bis-salicyloylhydrazine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) - hydrazine, S-salicyloylamino-i-triazole, bis-benzylidenoxa IsMu redi hydrazide.

4. 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-tert-butylphenyl) phosphite, diisodecylpenta-he, ^s rit diphosphite, di- (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, 3,9-bis (2,4-di-tert-butyl-phenoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane.

5. peroxide-destroying compounds, such as. 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 disulphide, pentaerythritol tetrakis-dodecylmercepto-J-propylate.

6. Polyamide stabilizers, e.g. Copper salts in combination with iodides and / or phosphorus compounds and salts of divalent manganese.

7. Basic Co-Stablllsatoren, such as. As melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine Derlvate, amines, polyamides, polyurethanes, alkali and alkaline earth salts of higher fatty acids, for example, Ca stearate, Zn stearate, Mg stearate, Na riclnoleate, K- Palmlatate, antimony catenate or tin catechinate.

8. i'Jukllerungsmlttel, such. B. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid.

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

10. Other additives, such as. As plasticizers, lubricants, emulsifiers, pigments, optical brighteners, flame retardants, antistatic agents, blowing agents.

Ausführungsbeisplel

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

Herstellungsbelsplel Example 1: Preparation of 2,4-bis (n-octylthylmethyl) -6-methylphenol (Compound No. 1)

OH

CH κ. · .CH ₂ -S-Ii-CoH ₁₇ V ^N /

I Il

CHi-S-Ji-C ₀ Hi ₇

160.7.ig (0.72 mol) of 2,4-Bls (dimethylamnomethyl) -e-methylphenol and 210.65 g (1.44 mol) of n-Ottanthlol are in an apparatus with stirrer and intensive condenser for 36 hours on 150 ⁰ C heated, while boi 63,2bar is continuously drawn off diethylamine. This gives 291.6 g (ö5%) of oily yellow oil. Pure 2,4-Bls (n-octyl-thiomothyl) -6-methyl-5-phanol is obtained by column chromatography on crude 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 = single "): Characteristic signals for Ar-CH ₂ S at

3.77 (s) and 3.6 (s).

Analogwelwelse the following compounds of formula I are prepared:

CH ₂ -S-

2-S-Rj

Connection no. Ri Characteristics Compound 2 Compound 3 n-CI ₂ H ₂₅ \ / I = * M.p .: 28 ° C .: mp 99-100 ⁰ C. Connection 4 • SS liquid Compound 5 Compound 6 -C (CHj) ₂ -CH ₂ -C (CHj) ₂ -CH ₂ -C (CH ₁ ) J -C (CHj) ₂ -CH ₂ -C (CH ₃ ) J liquid liquid

applications The compounds 1 and 2 from Example 1 are tested for their stabilizing effect. Example 2 Stabilization of Polybutadiene Rubber (Oven Aging)

100g polybutadiene, which is pre-stabilized with 0.4% 2,6-Di-t-butyl-p-cresol, are homogeneously mixed on a roll mill at 5O ⁰ C for 6 minutes mixed with 0.25% of the test compound. The sheets are pressed at 80 ^c C plates of 10mm thickness. Another plate is made without stabilizer in the same way.

The test of the compositions according to the invention by heat aging in a convection oven at 60 ⁹ C.

performed. 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 in 100 ml of toluene at room temperature. The solution is by a

Filtered glass filter (pore size 00) and the filtered solution was evaporated to dryness. The gel content results from

Gel·

E-A

x 100 (%)

E = weight (1 gram) A = weight of the evaporation residue The gel content increases rapidly after an induction bead. As an arbitrary definition of the induction period, the time, after

which achieves a gel content of 2%. This induction time is determined by periodic Geigehaitsbestimmungen.

The results are summarized in Table 1. Table 1 stabilizer

Induction time to gel content = 2% (In days)

Kolner connection 2

21 77

Bolsplol 3: stabilization of polybutadiene rubber (Brabendor)

100 parts of polybutadiene, which is vorstabilisiert with 0.4% of 2,6-di-t-butyl-p-cresol, is additionally 0.25% of the tested

Stabilizer in a Brabender Piastographen kneaded at 16O ⁰ C and 60 revolutions per minute for 30 minutes. Out

the course of the torque curve, the induction time is determined, d. H. the kneading time in minutes until the rise of the

Torque around 100mp after the torque minimum. The results are summarized in Table 2. Table 2 Stabilizer induction time (in minutes)

none 8

Connection 1> 30 Connection 2 23 Example 4: TFOUT Test (Thin Film Oxygen Uptake Test) This test is a modified version of the "Rotary Bomb Oxidation Test for Mineral Oils" (ASTM D 2272)

described in »C. S. Ku and S.M. Hsu, A Thin-Film Oxygen Uptake Test for the Automotive Evaluation Crankcase Lubricants,

Lubrication Engineering, Vol. 40 (2), 75-83 (1984). As Tectöl serves a motor oil based on mineral oil, which helps the »

usual amount of zinc dithiophosphate (0.75%, zinc content 0.06%, based on the motor oil) contains; this change is made so that a potential effect of the stabilizer to be tested can be shown.

Compound 1 from Example 1 is oxidized in the motor oil described in the presence of 2% water, a liquid,

nitrated fraction of a motor gasoline as catalyst (4% use concentration), of a liquid metal naphthenate as further catalyst (4% use concentration; water and the two liquid catalyst substances are under the no.

Standard Reference Material was supplied in 1817 by the National Bureau of Standards [NBS] with Analytical Certificate). The experiment is finished with a significant bend of the pressure / time diagram. Those given in the table below Results mean the time (in minutes) to the break of the pressure / time diagram. Long times correspond to good stabilizer effectiveness. Concentration of the stabilizer: 0.5%, based on the oil. Table 3 Stabilizer minutes to significant pressure drop

none 85

Compound 1 134 Example R: Stabilization of a Hydrogenated Cy Hydrocarbon Resin (Oven Aging)

50 g Herz, which is vorstabilisiert with 0.15% 2,6-di-t-butyl-p-cresol are melted in a glass flask at 17O 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 composition is about 15 mm in the aluminum dishes and 1 mm in the petri dishes. The test of the composition according to the invention is carried out by heat aging in a convection oven at 170 ° C. The criterion used is the unwanted discoloration occurring during oven aging. This is determined as follows:

a) in the case of 1 mm samples: Yollowness Index according to ASTM D 1925-70 and

b) both 15mm samples: Gardner color according to DIN 6161

 Higher numbers each mean stronger discoloration. ' The results are summarized in Table 4.

Table 4 Stabilizer No Yellowness Index Gardner Color

after hours at 170 ° C after hours at 170'C 0 12 30 0 12 30

none 3 86 126 1 5 9

Compound 1 3 6 12 11-2 3-4

Claims (1)

-1- 276 036 Claims: 1. Process for the preparation of compounds of the formula I. ? ^H
^ _s / H ₂ -SR, CH ₂ -SR ₁