Mercaptophenol derivatives as age resisters for polymers

Abstract

Mercaptophenols are reacted with compounds containing olefinic unsaturation, or polycyclic olefins, or dihydroxy compounds to form phenolic antioxidants such as 3,8-bis(4-hydroxyphenylthio)-tricyclo[5.2.1.0. 2 ,6 ] decane; 1,4-bis[2-(4-hydroxyphenylthio)ethyl]benzene and age resistant polymers containing said antioxidants.

I claim: 
     
       1. A polymer subject to oxidative degradation having incorporated therein an antioxidant amount of a composition conforming to the following structural formula: ##STR4## wherein A is selected from the group comprising divalent nonconjugated polycyclic radicals of 7 to 20 carbon atoms or a radical of the formula: ##STR5## wherein n is 0 or 1 and R 2  is a hydrogen radical or a methyl radical. 
     
     
       2. A polymer according to claim 1 wherein the phenolic hydroxyl group is para to the sulfur atom. 
     
     
       3. A composition of matter according to claim .[.19.]. .Iadd.8 .Iaddend.wherein R and R 1  are hydrogen or .[.alkyl.]. .Iadd.aralkyl .Iaddend.radicals of .[.1 to 4.]. .Iadd.8 to 9 .Iaddend.carbon atoms. 
     
     
       4. The polymer according to claim 1 wherein the antioxidant composition is selected from the group consisting of: ##STR6## 
     
     
        2. 5-bis(4-hydroxyphenylthio)bicyclo[2.2.1]heptane .[.5,11 and/or 12- 3,5-(1-phenylethyl)-4-hydroxyphenylthio pentacyclo[8.2.1 4 ,7 0. 2 ,9 0. 3 ,8 ]tetradecane.]. 
     
     
       5. A polymer subject to oxidative degradation having incorporated therein an antioxidant amount of a composition conforming to the following structural formula: ##STR7## wherein R and R 1  are selected from the group comprised of hydrogen radicals and aralkyl radicals of 7 to 9 carbon atoms and R 3  is selected from the group comprised of saturated and unsaturated nonconjugated polycyclic radicals of 7 to 20 carbon atoms. 
     
     
       6. A polymer according to claim 5 wherein R and R 1  are located meta to the sulfur atom and the phenolic hydroxyl group is para to the sulfur atom. 
     
     
       7. A polymer according to claim 5 wherein the antioxidant composition is selected from the group consisting of 1. .[.8-(4-hydroxyphenylthio[5.2.1.0 3 ,6 ]deca-3-ene,.]. .Iadd.8-(4-hydroxyphenylthio)-tricyclo[5.2.1.0 2 ,6 ]dec-3-ene, .Iaddend.   2. 2-(4-hydroxyphenylthio)bicyclo[2.2.1]hepta-5-ene,   3. 5-(4-hydroxyphenylthio)-pentacyclo[8.2.1.1. 4 ,7 0. 2 ,9 0. 3 ,8 ]tetradeca-11-ene.   
     
     
       8. A composition of matter conforming to the following structural formula: ##STR8## wherein R and R 1  are selected from the group comprised of hydrogen radicals and aralkyl radicals of 7 to 9 carbon atoms and R 3  is selected from the group comprised of saturated and unsaturated nonconjugated polycyclic radicals of 7 to 20 carbon atoms. 
     
     
       9. A composition of matter according to claim 8 wherein R and R 1  are located meta to the sulfur atom and the phenolic hydroxyl group is para to the sulfur atom. 
     
     
       10. A composition of matter conforming to the following structural formula: ##STR9## wherein A is selected from the group comprised of divalent nonconjugated polycyclic radicals of 7 to 20 carbon atoms or a radical of the formula: ##STR10## wherein n is 0 to 1 and R 2  is a hydrogen radical or a methyl radical. 
     
     
       11. A composition of matter according to claim 10 wherein the phenolic hydroxyl group is para to the sulfur atom. .Iadd.12. A polymer subject to oxidative degradation having incorporated therein an antioxidant amount of a composition selected from: 5,11 and/or -5,12-bis(3,5-ditertiary butyl-4-hydroxyphenylthio) pentacyclo[8.2.1.1. 4 ,7 0. 2 ,9 0. 3 ,8 ]tetradecane. .Iaddend.