The Goodyear & Tire Rubber Company

Richard H Kline

Dane Kenton Parker

Max H Keck

Compounds of the formula: ##STR1## wherein R, R' and R.sup.2 are alkyl radicals having 1 to 20 carbon atoms, phenyl radicals which may be substituted by 1 or 2 alkyl groups having 1 to 8 carbon atoms, aralkyl radicals having 7 to 12 carbon atoms, or cycloalkyl radicals having 5 to 12 carbon atoms; and wherein R.sup.3 is hydrogen or an alkyl radical having from 1 to 4 carbon atoms. These compounds have utility as synergistic stabilizers with phenolic type antioxidants for the stabilization of organic materials such as natural and synthetic polymers, rubbers, lubricants and oils, etc.

Mercapto acid ester antioxidants for polymers

Synergistic antioxidant mixtures

There is disclosed a process comprising reacting a compound having the general structural Formula II: ##STR1## with a compound having the general Formula III: ##STR2## in the presence of a basic catalyst while dissolved in an organic solvent to yield an aldehyde having the structural Formula I: ##STR3## wherein R.sub.1 and R.sub.2 are the same or different radicals selected from the group consisting of tertiary alkyl radicals having from 4 to 12 carbon atoms, R.sub.3 and R.sub.4 are the same or different radicals selected from the group consisting of alkyl radicals containing from 1 to 12 carbon atoms, cycloalkyl radicals containing from 5 to 12 carbon atoms, phenyl and substituted phenyl radicals or R.sub.3 and R.sub.4 with the carbon atom to which they are joined may form a cycloalkyl ring of from 5 to 12 carbon atoms, R.sub.5 is selected from the group consisting of hydrogen, alkyl radicals containing from 1 to 12 carbon atoms, or a cycloalkyl radical containing 5 or 6 carbon atoms.

Process for preparing

There is a process disclosed for alkylating the nucleus of a phenol, said process comprising reacting an .alpha., .omega.alkanediol containing from 3 to 8 carbon atoms with a phenol having an unsubstituted nuclear position para to the phenolic hydroxyl group; said phenol being selected from the group of alkylated phenols having tertiary alkyl groups of 4 to 8 carbon atoms in both positions ortho to the phenolic hydroxyl group, in the presence of an alkali metal hydroxide or alkoxide or alkali metal at a temperature from 200.degree. to 300.degree. C. while continuously removing the water by-product as it forms and obtaining as a product said phenol having a primary hydroxy terminated alkyl group of 3 to 8 carbon atoms in said para position.

Alkylation of 2,6-di-tert-alkylphenols with alkanediols

Compounds of the formula: ##STR1## wherein R is selected from (1) alkyl radicals having 6 to 20 carbon atoms; (2) phenyl radicals which may be substituted by 1 or 2 alkyl groups having 1 to 8 carbon atoms; or (3) aralkyl radicals having 7 to 12 carbon atoms; and wherein R.sup.1 is selected from (1) alkylene radicals having 2 to 6 carbon atoms; (2) cycloalkylene radicals having 5 to 12 carbon atoms; (3) alkylcycloalkylene radicals of the formula --R.sub.3 --R.sub.2 (R.sub.4).sub.n, wherein R.sub.2 is a cycloalkylene radical having 5 to 12 carbon and R.sub.3 and R.sub.4 are alkylene radicals having 1 to 6 carbon atoms, and n equals 1 or 0; (4) or a group of the formula --R.sub.5 --YR.sub.6, wherein R.sub.5 and R.sub.6 are alkylene radicals having 2 to 6 carbon atoms and Y is oxygen, sulfur, or a 1,4-phenylene radical. These compounds have utility as synergistic stabilizers with phenolic type antioxidants in the stabilization of organic materials such as natural and synthetic polymers, rubbers, lubricants and oils, etc.

A combination of a phenolic antioxidant, such as the butylated reaction product of p-cresol and dicyclopentadiene and an ester such as 3,6,9-trioxaundecamethylene bis [3-(dodecylthio)propionate] is used to stabilize polymers against oxidative degradation.

Phenolic/ester antioxidant system

Phenolic age resistors such as 4-(3,5-ditertiary butyl-4-hydroxyphenyl)-2-butyl 2-methyl-4-thia-6-octanoyloxyhexanoate are used as antioxidants in diene rubbers, such as butadiene-styrene types and in polyolefins, such as polypropylene.

3,5-Ditertiary alkyl-4-hydroxyphenyl (alkyl) 6-acyloxy-4-thia hexanoates

Antioxidants such as S-[3-(3,5-ditert.-butyl-4-hydroxyphenyl) propyl] thiomethacrylate are used to stabilize polymers either by being physically incorporated therein or by being polymerized in combination with other monomer to form polymers with built-in antioxidant protection.

Antioxidants

Amide and imide age resistors such as N-(3,5-di tert.butyl-4-hydroxyphenyl) acrylamide and N-(3,5-di tert.butyl-4-hydroxyphenyl) itaconimide, age resistant polymers having amide and imide age resistors physically combined therewith and age resistant polymeric compositions prepared by free radical polymerization techniques involving the use of said amides and imides as monomers.

Age resistors and age resistant polymeric compositions

Ester age resisters such as 4-anilinophenyl acrylate and 4-anilinophenyl methacrylate, age resistant polymers having ester age resisters physically combined therewith and age resistant polymeric compositions prepared by free radical polymerization techniques involving the use of said esters as monomers.

Age resisters and age resistant polymeric compositions

Antioxidants such as 2-(3,5-di tert.butyl-4-hydroxybenzyloxy) ethyl acrylate and 2-(3,5-di tert.butyl-4-hydroxybenzyloxy) ethyl methacrylate, age resistant polymers having age resistors physically combined therewith and age resistant polymeric compositions prepared by emulsion free radical polymerization techniques involving the use of said age resistors as monomers.

Stabilized polymeric compositions

Phenolic antioxidants such as bis(3,5-di tert.butyl-4-hydroxyphenyl) 2,9-dimethyl-4,7-dithiadecanedioate are used to stabilize diene rubbers such as butadiene-styrene copolymers (SBR) and polyolefins such as polypropylene.

Sulfur-containing phenolic antioxidants

2,6-Di tert alkyl-4-vinylphenols are copolymerized in free radical emulsion polymerization systems to form self-stabilizing polymers. Such polymers have the advantage that the antioxidant cannot be extracted or volatilized from the polymer.

2,6-Di-tert-alkyl-4-vinylphenols as polymerizable antioxidants

Phenolic antioxidants such as 1,1-dimethyl-2-(3,5-di tert.butyl-4-hydroxyphenyl) ethyl amine and a method of preparing said antioxidants involving the reaction between a 3,5-di tert.alkyl-4-hydroxybenzyl halide; N,N-dialkyl amine or dithiocarbamate such as 3,5-di tert.butyl-4-hydroxybenzyl chloride; 2,6-di tert.butyl-4-dimethylaminomethylphenol or 3,5-di tert.butyl-4-hydroxybenzyl N,N-dimethyldithiocarbamate and a nitroalkane such as 2-nitropropane to produce a nitro compound such as 1,1-dimethyl-2-(3,5-di tert.butyl-4-hydroxyphenyl)-1-nitroethane which can be catalytically reduced to form the aminoalkyl phenol.

Antioxidants and process of preparing said antioxidants

Phenolic age resistors such as 4-(3,5-ditertiary butyl-4-hydroxyphenyl)-2-butyl 2-methyl-4-thia-6-octanoyloxy-hexanoate are used as antioxidants in diene rubbers, such as butadiene-styrene types and in polyolefins, such as polypropylene.

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Cuyahoga Falls, OH, United States of America

Richard H Kline