Organotin mercapto dicarboxylic acid esters and compositions

Claim 2

An organotin mercapto dicarboxylic acid mixed monohydric and polyhydric alcohol ester having per tin atom one or two alkyl, cycloalkyl or alkylcycloalkyl groups attached to tin through carbon; the alkyl having from 1 to about 12 carbon atoms, the cycloalkyl having from 3 to about 12 carbon atoms, and the alkyl cycloalkyl having from 4 to about 12 carbon atoms; and 2 or 3 mercapto dicarboxylic acid ester groups attached to tin through sulfur, the mercapto dicarboxylic acid having from about four to about 24 carbon atoms, and having at least one esterifying group selected from the group consisting of alkyl, cycloalkyl, and alkylcycloalkyl, the alkyl having from 1 to about 12 carbon atoms, the cycloalkyl having from 3 to about 12 carbon atoms, and the alkyl cycloalkyl having from 4 to about 12 carbon atoms and at least one esterifying group selected from the group consisting of bivalent alkylene, cycloalkylene and alkylenecycloalkyl, the alkylene having from about 2 to about 12 carbon atoms, the cycloalkylene having from 3 to about 12 carbon atoms, and the alkylenecycloalkylene having from 4 to about 12 carbon atoms, each of the two valences of the bivalent alkylene, cycloalkylene and alkylcycloalkylene being linked to groups selected from the group consisting of one hydroxyl and one carboxylic acid group of mercapto dicarboxylic acid; and two carboxylic acid groups of mercapto dicarboxylic acid.

Claim 3

An organotin mercapto dicarboxylic acid mixed monohydric and polyhydric alcohol ester according to claim 1, in which the mercapto dicarboxylic acid is thiomalic acid.

Claim 4

An organotin mercapto dicarboxylic acid mixed monohydric and polyhydric alcohol ester according to claim 2 having per tin atom one alkyl group linked to tin and three mercapto dicarboxylic acid ester groups esterified with alkyl and alkylene groups.

Claim 5

An organotin mercapto dicarboxylic acid mixed monohydric and polyhydric alcohol ester according to claim 3, wherein the alkyl group linked to tin is butyl, the esterifying alkyl group is butyl, and the esterifying alkylene group is ethylene.

Claim 6

An organotin mercapto dicarboxylic acid mixed monohydric and polyhydric alcohol ester according to claim 2, having per tin atom two alkyl groups linked to tin, and two mercapto dicarboxylic acid ester groups esterified with alkyl and alkylene groups.

Claim 7

An organotin mercapto dicarboxylic acid mixed monohydric and polyhydric alcohol ester according to claim 5, wherein the alkyl group linked to tin is methyl, the esterifying alkyl group is butyl, and the esterifying alkylene group is ethylene.

Claim 8

An organotin mercapto dicarboxylic acid mixed monohydric and polyhydric alcohol ester according to claim 5, wherein the alkyl group linked to tin is butyl, the esterifying alkyl group is butyl, and the esterifying alkylene group is ethylene.

Claim 9

An organotin mercapto dicarboxylic acid mixed monohydric and polyhydric alcohol ester according to claim 5, wherein the alkyl group linked to tin is butyl, the esterifying alkyl group is butyl, and the esterifying alkylene group is butylene.

Claim 10

An organotin mercapto dicarboxylic acid mixed monohydric and polyhydric alcohol ester according to claim 5, wherein the alkyl group linked to tin is butyl, the esterifying alkyl group is butyl, and the esterifying alkylene group is neopentylene.

Claim 11

An organotin mercapto dicarboxylic acid mixed monohydric and polyhydric alcohol ester according to claim 5, wherein the alkyl group linked to tin is octyl, the esterifying alkyl group is butyl, and the esterifying alkylene group is ethylene.

Claim 12

An organotin mercapto dicarboxylic acid mixed monohydric and polyhydric alcohol ester according to claim 5, wherein the alkyl group linked to tin is octyl, the esterifying alkyl group is butyl, and the esterifying alkylene group is propylene.

Claim 13

An organotin mercapto dicarboxylic acid mixed monohydric and polyhydric alcohol ester according to claim 5, wherein the alkyl group linked to tin is octyl, the esterifying alkyl group is butyl, and the esterifying alkylene group is butylene.

Claim 14

An organotin mercapto dicarboxylic acid mixed monohydric and polyhydric alcohol ester according to claim 5, wherein the alkyl group linked to tin is methyl, the esterifying alkyl group is butyl, and the esterifying alkylene group is butylene.

Claim 15

An organotin mercapto dicarboxylic acid mixed monohydric and polyhydric alcohol ester according to claim 5, wherein the alkyl group linked to tin is methyl, the esterifying alkyl group is butyl, and the esterifying alkylene group is neopentylene.

Claim 16

An organotin mercapto dicarboxylic acid ester of claim 1 having per tin atom at least one butyl group linked to tin through carbon.

Claim 17

An organotin mercapto dicarboxylic acid ester of claim 1 having per tin atom at least one octyl group linked to tin through carbon.

Claim 18

An organotin mercapto dicarboxylic acid ester of claim 1 having per tim atom at least one methyl group linked to tin through carbon.

Claim 19

A halogen-containing polymer selected from the group consisting of homopolymers and copolymers of vinyl chloride and chlorinated polymers of vinyl chloride and comprising a stabilizing amount of an organotin mercapto dicarboxylic acid ester of claim 1.

Claim 20

The halogen-containing polymer of claim 17 wherein the organotin mercapto dicarboxylic acid ester is an organotin thiomalic acid ester of claim 2.

Claim 21

The halogen-containing polymer of claim 17 wherein the organotin mercapto dicarboxylic acid ester is an organotin thiomalic acid ester of claim 3.

Claim 22

The halogen-containing polymer of claim 17 wherein the organotin mercapto dicarboxylic acid ester is an organotin thiomalic acid ester of claim 4.

Claim 23

A halogen-containing polymer of claim 18 in which the polymer is polyvinyl chloride homopolymer.

Claim 24

A halogen-containing polymer of claim 18 in which the polymer is a copolymer of a major quantity of vinyl chloride and a minor quantity of another vinyl monomer.

Claim 25

A halogen-containing polymer of claim 18, in which the amount of organotin mercapto dicarboxylic acid ester is within the range from about 0.25% to about 10% by weight of the composition.

Claim 26

A halogen-containing polymer of claim 18, including in addition a polyvalent metal salt of a carboxylic acid or alkyl phenol.

Claim 27

A halogen-containing polymer of claim 18, including in addition an epoxy compound.

Claim 28

A halogen-containing polymer of claim 18, including in addition a plasticizer for the resin in an amount in excess of about 10% by weight.

Claim 29

A rigid halogen-containing polymer of claim 18 comprising a plasticizer in an amount up to about 10% by weight of the composition.

Claim 30

A halogen-containing polymer of claim 18 including in addition a phenolic antioxidant.

Claim 31

A halogen-containing polymer of claim 18 including in addition an impact modifier.

Claim 32

A mixture of organotin mercapto dicarboxylic acid esters useful as a stabilizer for improving the resistance to deterioration of polyvinyl chloride resins when heated at 350° F, and having at least one tin atom to which organic groups are linked only through carbon and sulfur, having linked to tin through sulfur at least one mercapto dicarboxylic acid ester group, each of the organotin mercapto dicarboxylic acid esters having per tin atom one or two alkyl, cycloalkyl or alkylcycloalkyl groups attached to tin through carbon; the alkyl having from 1 to about 12 carbon atoms, the cycloalkyl having from 3 to about 12 carbon atoms, and the alkyl cycloalkyl having from 4 to about 12 carbon atoms; and two or three mercapto dicarboxylic acid ester groups attached to tin through sulfur, the mercapto dicarboxylic acid having from about 4 to about 24 carbon atoms, and having at least one esterifying group selected from the group consisting of alkyl, cycloalkyl, and alkylcycloalkyl, the alkyl having from 1 to about 12 carbon atoms, the cycloalkyl having from 3 to about 12 carbon atoms, and the alkyl cycloalkyl having from 4 to about 12 carbon atoms, and at least one esterifying group selected from the group consisting of bivalent alkylene, cycloalkylene and alkylenecycloalkylene, the alkylene having from about 2 to about 12 carbon atoms, the cycloalkylene having from 3 to about 12 carbon atoms, and the alkylenecycloalkylene having from 4 to about 12 carbon atoms, each of the two valences of the bivalent alkylene, cycloalkylene and alkylcycloalkylene being linked to groups selected from the group consisting of one hydroxyl and one carboxylic group of mercapto dicarboxylic acid; and two carboxylic acid groups of mercapto dicarboxylic acid, one of said organotin mercapto dicarboxylic acid esters having per tin atom one alkyl group linked to tin and three mercapto dicarboxylic acid ester groups esterified with alkyl and alkylene groups; and one of said organotin mercapto dicarboxylic acid esters having per tin atom two alkyl groups linked to tin, and two mercapto dicarboxylic acid ester groups esterified with alkyl and alkylene groups.

Claim 33

A mixture of organotin mercapto dicarboxylic acid esters useful as a stabilizer for improving the resistance to deterioration of polyvinyl chloride resins when heated at 350° F, and having at least one tin atom to which organic groups are linked only through carbon and sulfur, having linked to tin through sulfur at least one mercapto dicarboxylic acid ester group, each of the organotin mercapto dicarboxylic acid esters having per tin atom one or two alkyl, cycloalkyl or alkylcycloalkyl groups attached to tin through carbon; the alkyl having from 1 to about 12 carbon atoms, the cycloalkyl having from 3 to about 12 carbon atoms, and the alkyl cycloalkyl having from 4 to about 12 carbon atoms; and two or three mercapto dicarboxylic acid ester groups attached to tin through sulfur, the mercapto dicarboxylic acid having from about 4 to about 24 carbon atoms, and having at least one esterifying group selected from the group consisting of alkyl, cycloalkyl, and alkylcycloalkyl, the alkyl having from 1 to about 12 carbon atoms, the cycloalkyl having from 3 to about 12 carbon atoms, and the alkyl cycloalkyl having from 4 to about 12 carbon atoms, and at least one esterifying group selected from the group consisting of bivalent alkylene, cycloalkylene and alkylenecycloalkylene, the alkylene having from about 2 to about 12 carbon atoms, the cycloalkylene having from 3 to about 12 carbon atoms, and the alkylenecycloalkylene having from 4 to about 12 carbon atoms, each of the two valences of the bivalent alkylene, cycloalkylene and alkylcycloalkylene being linked to groups selected from the group consisting of one hydroxyl and one carboxylic group of mercapto dicarboxylic acid; and two carboxylic acid groups of mercapto dicarboxylic acid, one of said organotin mercapto dicarboxylic acid esters having per tin atom one alkyl group linked to tin and three mercapto dicarboxylic acid ester groups esterified with alkyl and alkylene groups; and one of said organotin mercapto dicarboxylic acid esters having per tin atom two alkyl groups linked to tin, and two mercapto dicarboxylic acid ester groups esterified with alkyl and alkylene groups.

Claim 34

A mixture of organotin mercapto dicarboxylic acid esters in accordance with claim 31, having alkyl groups attached to tin through carbon, and alkyl and alkylene esterifying groups.

Claim 35

A mixture of organotin mercapto dicarboxylic acid esters in accordance with claim 32 wherein the alkyl groups attached to tin through carbon are butyl.

Claim 36

A mixture of organotin mercapto dicarboxylic acid esters in accordance with claim 32, wherein the alkyl groups attached to tin through carbon are octyl.

Claim 37

A mixture of organotin mercapto dicarboxylic acid esters in accordance with claim 32, wherein the alkyl groups attached to tin through carbon are methyl.

Claim 38

A mixture of organotin mercapto dicarboxylic acid esters in accordance with claim 32, wherein the alkyl groups attached to tin through carbon are methyl, and the alkyl esterifying groups are butyl.

Claim 39

A mixture of organotin mercapto dicarboxylic acid esters in accordance with claim 32, wherein the alkyl groups attached to tin through carbon are octyl, and the alkyl esterifying groups are butyl.

Claim 40

A polyvinyl chloride resin composition having an enhanced resistance to deterioration when heated at 350° F, comprising a polyvinyl chloride resin and a mixture of organotin mercapto dicarboxylic esters in accordance with claim 31.

Claim 41

An organotin mercapto dicarboxylic acid mixed monohydric and polyhydric alcohol ester having per tin atom one or two alkyl, cycloalkyl, or alkylcycloalkyl groups attached to tin through carbon, and two or three thiodicarboxylic acid ester groups attached to tin through sulfur, and having the formula: ##STR26## wherein m 1 and m 3 are numbers within the range from 0 to about 7; m 2 is a number within the range from 1 to about 7; n is 1 or 2;

Claim 42

An organotin mercapto dicarboxylic acid mixed monohydric and polyhydric alcohol ester having per tin atom one or two alkyl, cycloalkyl, or alkylcycloalkyl groups attached to tin through carbon, and two or three thiodicarboxylic acid ester groups attached to tin through sulfur, and having the formula: ##STR26## wherein m 1 and m 3 are numbers within the range from 0 to about 7; m 2 is a number within the range from 1 to about 7; n is 1 or 2;

Claim 43

R is selected from the group consisting of alkyl, cycloalkyl, and alkycycloalkyl, the alkyl having from one to about twelve carbon atoms, the cycloalkyl having from 3 to about 12 carbon atoms, and the alkylcycloalkyl having from 4 to about 12 carbon atoms linked to tin through carbon; and at least one of Z 1 and Z 2 is selected from the group consisting of alkyl, cycloalkyl, and alkylcycloalkyl, the alkyl having from 1 to about 12 carbon atoms, the cycloalkyl having from 3 to about 12 carbon atoms, and the alkylcycloalkyl having from 4 to about 12 carbon atoms; and at least one of Z 1 and Z 2 is selected from the group consisting of i. bivalent alkylene, cycloalkylene and alkylenecycloalkylene taken together with the other of Z 1 and Z 2 of the organotin mercapto dicarboxylic acid ester; the alkylene having from about 2 to about 12 carbon atoms, the cycloalkylene having from 3 to about 12 carbon atoms, and the alkylenecycloalkylene having from 4 to about 12 carbon atoms; ii. hydroxyalkyl, hydroxycycloalkyl and hydroxyalkylcycloalkyl having from 2 to about 12 carbon atoms; the alkyl having from 1 to about 12 carbon atoms, the cycloalkyl having from 3 to about 12 carbon atoms, and the alkylcycloalkyl having from 4 to about 12 carbon atoms linked to tin through carbon; and iii. bivalent alkylene, cycloalkylene and alkylenecycloalkylene having from about 2 to about 12 carbon atoms and linked to a carboxylic acid ester group of a second organotin mercapto dicarboxylic acid ester; the alkylene having from about 2 to about 12 carbon atoms, the cycloalkylene having from 3 to about 12 carbon atoms, and the alkylenecycloalkylene having from 4 to about 12 carbon atoms.

Claim 44

R is selected from the group consisting of alkyl, cycloalkyl, and alkycycloalkyl, the alkyl having from one to about twelve carbon atoms, the cycloalkyl having from 3 to about 12 carbon atoms, and the alkylcycloalkyl having from 4 to about 12 carbon atoms linked to tin through carbon; and at least one of Z 1 and Z 2 is selected from the group consisting of alkyl, cycloalkyl, and alkylcycloalkyl, the alkyl having from 1 to about 12 carbon atoms, the cycloalkyl having from 3 to about 12 carbon atoms, and the alkylcycloalkyl having from 4 to about 12 carbon atoms; and at least one of Z 1 and Z 2 is selected from the group consisting of i. bivalent alkylene, cycloalkylene and alkylenecycloalkylene taken together with the other of Z 1 and Z 2 of the organotin mercapto dicarboxylic acid ester; the alkylene having from about 2 to about 12 carbon atoms, the cycloalkylene having from 3 to about 12 carbon atoms, and the alkylenecycloalkylene having from 4 to about 12 carbon atoms; ii. hydroxyalkyl, hydroxycycloalkyl and hydroxyalkylcycloalkyl having from 2 to about 12 carbon atoms; the alkyl having from 1 to about 12 carbon atoms, the cycloalkyl having from 3 to about 12 carbon atoms, and the alkylcycloalkyl having from 4 to about 12 carbon atoms linked to tin through carbon; and iii. bivalent alkylene, cycloalkylene and alkylenecycloalkylene having from about 2 to about 12 carbon atoms and linked to a carboxylic acid ester group of a second organotin mercapto dicarboxylic acid ester; the alkylene having from about 2 to about 12 carbon atoms, the cycloalkylene having from 3 to about 12 carbon atoms, and the alkylenecycloalkylene having from 4 to about 12 carbon atoms.

Claim 45

An organotin mercapto dicarboxylic acid ester of claim 39 in which n is 1.

Claim 46

An organotin mercapto dicarboxylic acid ester of claim 39, in which n is 2.

Claim 47

An organotin thiomalic acid ester of claim 39, in which m 1 and m 3 are 0, and n is 1.

Claim 48

An organotin thiomalic acid ester of claim 39, in which m 1 and m 3 are 0, and n is 2.

Claim 49

An organotin thiomalic acid ester of claim 39, in which at least one of Z 1 and Z 2 is alkylene.

Claim 50

An organotin thiomalic acid ester of claim 39, in which at least one of Z 1 and Z 2 is methyl and at least one of Z 1 and Z 2 is ethylene.

Claim 51

An organotin thiomalic acid ester of claim 39, in which at least one of Z 1 and Z 2 is butyl and at least one of Z 1 and Z 2 is ethylene.

Claim 52

An organotin thiomalic acid ester of claim 39, in which at least one of Z 1 and Z 2 is octyl and at least one of Z 1 and Z 2 is ethylene.