Synergistic antioxidant mixtures, compounds and process for their production

Claim 2

A composition comprising (A) organic material selected from the group of oxidizable polymers, oils, resins, waxes and fuels; containing an effective amount of a mixture of (B) a phenolic antioxidant and (C) a compound of the formula: wherein R is selected from the group comprised of (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; (3) or aralkyl radicals having 7 to 12 carbon atoms, and wherein R l is selected from the group comprised of (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 3 -R 2 -(R 4 ) n , wherein R 2 is a cycloalkylene radical having 5 to 12 carbon atoms and R 3 and R 4 are alkylene radicals having 1 to 6 carbon atoms, and n equals 1 or 0; (4) or a group of the formula R 5 YR 6 , wherein R 5 and R 6 are alkylene radicals having 2 to 6 carbon atoms and Y is oxygen, sulfur or a 1,4-phenylene radical; the ratio of C to B ranging from 1:4 to 4:1.

Claim 3

A composition according to claim 1 wherein R is an ethylene radical of the formula -CH 2 -CH 2 - and R is a dodecyl radical.

Claim 4

A composition according to claim 1 wherein R is a propylene radical of the formula and R is a dodecyl radical.

Claim 5

A composition according to claim 1 wherein the phenolic antioxidant (B) is selected from the group comprising 2,6-di-tert.butyl-4-methylphenol 2,4,6-tri-tert.butylphenol 2,2'-methylene-bis-(4-methyl-6-tert.butylphenol) 2,2'-thio-bis-(4-methyl-6-tert.butylphenol) 4,4'-thio-bis-(3-methyl-6-tert.butylphenol) 4,4'-butylidene-bis-(6-tert.butyl-3-methylphenol) Styrenated phenol Butylated octylated phenol Butylated α-methylstyrenated phenol Styrenated butylated m, p-cresol 4,4'-methylenebis(2,6-di-tert.butylphenol) 2,2'-methylenebis[4-methyl-6-(1-methylcyclohexyl) phenol] Butylated reaction product of p-cresol and dicyclopentadiene Tetrakis [methylene 3-(3,5-di-tert.butyl-4-hydroxyphenyl)propionate]methane 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert.butyl-4-hydroxybenzyl)benzene Thiodiethylene bis [3-(3,5-di-tert.butyl-4-hydroxyphenyl)propionate] Octadecyl 3-(3,5-di-tert.butyl-4-hydroxyphenyl) propionate

Claim 6

An antioxidant composition comprised of a phenolic antioxidant (B); and a compound (C) of general formula wherein R is selected from the group comprised of (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; (3) or aralkyl radicals having 7 to 12 carbon atoms, and wherein R 1 is selected from the group comprised of (1) alkylene radicals having 2 to 6 carbon atoms; (2) cycloalkylene radicals having 5 to 12 carbon atoms; (3) alkylcycloalkylene radicals of the formula -R3-R2-(R4)n, wherein R 2 is a cycloakylene radical having 5 to 12 carbon atoms and R 3 and R 4 are alkylene radicals having 1 to 6 carbon atoms, and n equals 1 or 0; (4) or a group of the formula R 5 YR 6 , wherein R 5 and R 6 are alkylene radicals having 2 to 6 carbon atoms and Y is oxygen, sulfur or a 1,4-phenylene radical; the amount of(C) being from 20 to 80% of the total antioxidant composition.

Claim 7

An antioxidant composition comprised of a phenolic antioxidant (B); and a compound (C) of general formula wherein R is selected from the group comprised of (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; (3) or aralkyl radicals having 7 to 12 carbon atoms, and wherein R 1 is selected from the group comprised of (1) alkylene radicals having 2 to 6 carbon atoms; (2) cycloalkylene radicals having 5 to 12 carbon atoms; (3) alkylcycloalkylene radicals of the formula -R3-R2-(R4)n, wherein R 2 is a cycloakylene radical having 5 to 12 carbon atoms and R 3 and R 4 are alkylene radicals having 1 to 6 carbon atoms, and n equals 1 or 0; (4) or a group of the formula R 5 YR 6 , wherein R 5 and R 6 are alkylene radicals having 2 to 6 carbon atoms and Y is oxygen, sulfur or a 1,4-phenylene radical; the amount of(C) being from 20 to 80% of the total antioxidant composition.

Claim 8

An antioxidant composition according to claim 5 wherein R 1 is an ethylene radical of the formula -CH 2 -CH 2 - and R is dodecyl radical.

Claim 9

An antioxidant composition according to claim 5 wherein R 1 is a propylene radical of the formula and R is dodecyl radical.

Claim 10

An antioxidant composition according to claim 5 wherein the phenolic antioxidant (B) is selected from the group 2,6-di-tert.butyl-4-methylphenol 2,4,6-tri-tert.butylphenol 2,2'-methylene-bis-(4-methyl-6-tert.butylphenol) 2,2'-thio-bis-(4-methyl-6-tert.butylphenol) 4,4'-thio-bis-(3-methyl-6-tert.butylphenol) 4,4'-butylidene-bis-(6-tert.butyl-3-methylphenol) Styrenated phenol Butylated octylated phenol Butylated α-methylstyrenated phenol Styrenated butylated m, p-cresol 4,4'-methylenebis(2,6-di-tert,butylphenol) 2,2'-methylenebis[4-methyl-6-(1-methylcyclohexyl) phenol] Butylated reaction product of p-cresol and dicyclopentadiene Tetrakis [methylene 3-(3,5-di-tert.butyl-4-hydroxyphenyl)propionate]methane 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert.butyl-4-hydroxybenzyl)benzene Thiodiethylene bis [3-(3,5-di-tert.butyl-4-hydroxyphenyl)propionate] Octadecyl 3-(3,5-di-tert.butyl-4-hydroxyphenyl) propionate

Claim 11

A compound of the formula: wherein R is selected from the group comprised of (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; (3) or aralkyl radicals having 7 to 12 carbon atoms, and wherein R is selected from the group comprised of (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 3 -R 2 -(R 4 ) n , wherein R 2 is a cycloakylene radical having 5 to 12 carbon atoms and R3 and R 4 are alkylene radicals having 1 to 6 carbon atoms, and n equals 1 or 0; (4) or a group of the formula R 5 YR 6 , wherein R 5 and R 6 are alkylene radicals having 2 to 6 carbon atoms and Y is oxygen, sulfur or a 1,4-phenylene radical.

Claim 12

A compound of the formula: wherein R is selected from the group comprised of (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; (3) or aralkyl radicals having 7 to 12 carbon atoms, and wherein R is selected from the group comprised of (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 3 -R 2 -(R 4 ) n , wherein R 2 is a cycloakylene radical having 5 to 12 carbon atoms and R3 and R 4 are alkylene radicals having 1 to 6 carbon atoms, and n equals 1 or 0; (4) or a group of the formula R 5 YR 6 , wherein R 5 and R 6 are alkylene radicals having 2 to 6 carbon atoms and Y is oxygen, sulfur or a 1,4-phenylene radical.

Claim 13

A compound according to claim 9 wherein R 1 is an ethylene radical of the formula -CH 2 -CH 2 - and R is a dodecyl radical.

Claim 14

A compound according to claim 9 wherein R 1 is a propylene radical of the formula and R is a dodecylradical.

Claim 15

A compound according to claim 9 which is 2,9-dihydroxy-4, 7-dithiadecamethylene bis[3-dodecylthio)propionate].

Claim 16

13 A compound according to claim 9 which is 2,9-dihydroxy-4,7-dithia-5-methyldecamethylene bis [3-(dodecylthio) propionate].

Claim 17

A process for the production of a compound of the structural formula: wherein R is selected from the group comprised of (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; (3) or aralkyl radicals having 7 to 12 carbon atoms, and wherein R is selected from the group comprised of (1) alkylene radicals having 2 to 6 carbon atoms; (2) cycloakylene radicals having 5 to 12 carbon atoms; (3) alkylcycloalkylene radicals of the formula -R 3 -R 2 -(R 4 ) n , wherein R 2 is a cycloalkylene radical having 5 to 12 carbon atoms and R 3 and R 4 are alkylene radicals having 1 to 6 carbon atoms, and n equals 1 or 0; (4) or a group of the formula R 5 YR 6 , wherein R 5 and R 6 are alkylene radicals having 2 to 6 carbon atoms and Y is oxygen, sulfur or a 1,4-phenylene radical; wherein a compound of the general formula wherein R is selected from the group comprised of (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; (3) or aralkyl radicals having 7 to 12 carbon atoms is reacted with 2,3-epoxypropyl acrylate to yield an intermediate 2,3-epoxypropyl 3-(R-thio)propionate; this intermediate is reacted with a compound of the formula HSR 1 SH, wherein R is selected from the group comprised of (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 3 R 2 -(R 4 ) n wherein R 2 is a cycloalkylene radical having 5 to 12 carbon atoms and R 3 and R 4 are alkylene radicals having 1 to 6 carbon atoms, and n equals 1 or 0; (4) or a group of the formula R 5 YR 6 , wherein R 5 and R 6 are alkylene radicals having 2 to 6 carbon atoms and Y is oxygen, sulfur, or a 1,4-phenylene radical, to yield the compounds of this invention; both reactions being base catalyzed.

Claim 18

A process for the production of a compound of the structural formula: wherein R is selected from the group comprised of (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; (3) or aralkyl radicals having 7 to 12 carbon atoms, and wherein R is selected from the group comprised of (1) alkylene radicals having 2 to 6 carbon atoms; (2) cycloakylene radicals having 5 to 12 carbon atoms; (3) alkylcycloalkylene radicals of the formula -R 3 -R 2 -(R 4 ) n , wherein R 2 is a cycloalkylene radical having 5 to 12 carbon atoms and R 3 and R 4 are alkylene radicals having 1 to 6 carbon atoms, and n equals 1 or 0; (4) or a group of the formula R 5 YR 6 , wherein R 5 and R 6 are alkylene radicals having 2 to 6 carbon atoms and Y is oxygen, sulfur or a 1,4-phenylene radical; wherein a compound of the general formula wherein R is selected from the group comprised of (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; (3) or aralkyl radicals having 7 to 12 carbon atoms is reacted with 2,3-epoxypropyl acrylate to yield an intermediate 2,3-epoxypropyl 3-(R-thio)propionate; this intermediate is reacted with a compound of the formula HSR 1 SH, wherein R is selected from the group comprised of (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 3 R 2 -(R 4 ) n wherein R 2 is a cycloalkylene radical having 5 to 12 carbon atoms and R 3 and R 4 are alkylene radicals having 1 to 6 carbon atoms, and n equals 1 or 0; (4) or a group of the formula R 5 YR 6 , wherein R 5 and R 6 are alkylene radicals having 2 to 6 carbon atoms and Y is oxygen, sulfur, or a 1,4-phenylene radical, to yield the compounds of this invention; both reactions being base catalyzed.

Claim 19

A process according to claim 14 wherein dodecanethiol is reacted with 2,3-epoxypropyl acrylate at ambient temperature in ethanol or 2-propanol; 1,2-ethanedithiol is added to the reaction mixture at room temperature and the product, 2,9-dihydroxy-4,7-dithiadecamethylene bis[3-(dodecylthio)propionate] is isolated.