# US 4,391,937 A · Color stable chelated titanate compositions

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 4,391,937 A
- Document ID: US4391937A
- Status: Granted
- Kind: A
- Application number: 06/308,704
- Filed: 1981-10-05
- Granted: 1983-07-05
- Earliest claimed: 1981-10-05
- Assignees: Dow Corning Corporation
- Inventors: James R. Falender; Angelika H. McHale
- Web page: https://patentgrep.com/patent/US4391937A

## CPC

- C08K 5/00: Use of organic ingredients
- C08K 5/0091: {Complexes with metal-heteroatom-bonds}
- C08K 5/04: Oxygen-containing compounds {(C08K5/0091 takes precedence)}
- C08K 5/13: Phenols; Phenolates
- C08K 5/36: Sulfur-, selenium-, or tellurium-containing compounds {(C08K5/0091 takes precedence)}
- C08K 5/52: Phosphorus bound to oxygen only
- C08K 5/54: Silicon-containing compounds {(C08K5/0091 takes precedence)}
- Y10S 502/50: Stabilized
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

## Abstract

A composition containing a chelated titanium compound and an additive selected from the group consisting of (1) esters of thioalkanoic acids, (2) di-tertiary-butyl phenol containing compounds, (3) organic phosphites, and (4) mixtures of (2) and (3), retards the color change of the composition on storage. When this composition is used as the catalyst for one package, room temperature curing silicone elastomeric compositions of the type comprising a hydroxyl endblocked polydiorganosiloxane and a silane having an average of from 2.01 to 4 inclusive alkoxy radicals, the silicone elastomeric composition can be stored without substantial color formation. The improvement in reduced color change is useful in silicone elastomeric compositions which are clear or light colored.

## Claims

### Claim 1

An elastomeric composition comprising (i) a hydroxyl endblocked polydiorganosiloxane, (ii) a silane or mixture of silanes having an average of from 2.01 to 4 inclusive alkoxy radicals, and a sufficient amount of a titanium-containing composition to yield from 0.1 to 10 parts by weight of chelated titanium compound based upon 100 parts by weight of the hydroxyl endblocked polydiorganosiloxane, said elastomeric composition being stable under conditions excluding moisture and curable by exposure to moisture, where said tatanium-containing composition comprise the product obtained by mixing, under conditions which substantially exclude moisture,
(a) a chelated titanium compound having a formula ##STR14## in which R.sup.3 is a monovalent hydrocarbon radical having from 1 to 18 inclusive carbon atoms,
R.sup.4 is a monovalent radical selected from the group consisting of hydrocarbon radicals having from 1 to 18 carbon atoms, and hydrogen,
R.sup.5 is a monovalent radical selected from the group consisting of hydrocarbon radicals and aliphatic hydrocarbonoxy radicals each having from 1 to 18 inclusive carbon atoms, and
Z is a radical selected from the group consisting of monovalent aliphatic hydrocarbonoxy radicals and monovalent acyloxy radicals, each having from 1 to 18 inclusive carbon atoms; hydroxyl radical; divalent oxygen atoms forming a TiOTi linkage; and when taken together form an alkanedioxy radical of the formula ##STR15## in which R.sup.6 is a radical selected from the group consisting of hydrogen atom and monovalent aliphatic hydrocarbon radicals having not more than 8 carbon atoms, the total number of carbon atoms in the alkanedioxy radical is not more than 18, and
(b) from 1 to 100 parts by weight based on 100 parts by weight of (a), of an additive soluble in the chelated titanium compound and being selected from the group consisting of
(1) an ester of thioalkanoic acid of the formula ##STR16## wherein R.sup.8 is an alkyl group containing from 1 to 15 inclusive carbon atoms and a is an integer of from 1 to 4 inclusive,
(2) di-tertiary-butyl phenol containing compounds selected from the group consisting of 2,6-di-tert-butyl-4-methylphenol, tetrakis[methylene-3-(3',5'-di-tert-butyl4'-hydroxyphenyl)propionate]metha ne, octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-tert-butylphenol), 1,6-hexamethylene-bis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), and thiodiethylenebis-(3,5-di-tert-butyl-4-hydroxy hydrocinnamate),
(3) an organic phosphite selected from the group consisting of the formula
(R.sup.10 O).sub.b P(OR.sup.11).sub.3-b
wherein R.sup.10 and R.sup.11 are selected from the group consisting of linear or branched alkyl radicals of from 1 to 18 carbon atoms, and phenyl radical, wherein b is 0 or 1, and the formula ##STR17## wherein R.sup.12 is a linear or branched alkyl radical of from 1 to 18 carbon atoms, and
(4) a mixture of (2) and (3), the composition having a color of less than 13 as determined by the Gardner Color Scale and being stored under conditions substantially excluding moisture.

### Claim 2 (depends on 1)

The elastomeric composition according to claim 1 in which the hydroxyl endblocked polydiorganosiloxane, (i), has a viscosity of at least 0.025 Pa.multidot.s at 25.degree. C. and has the average formula ##EQU3## in which z has an average value from 1 to 1.01 inclusive,
y has an average value from 1.99 to 2 inclusive, and the sum of
y+z is 3,
R is selected from the group consisting of monovalent hydrocarbon radicals, halogenated monovalent hydrocarbon radicals, and monovalent cyanoalkyl radicals, all of from 1 to 18 inclusive carbon atoms, and n is an integer, and (ii) is at least one silane or a mixture of silanes of the average formula
R.sub.m Si(OR.sup.1).sub.4-m
in which
R is as defined above,
R.sup.1 is selected from the group consisting of monovalent haloaliphatic hydrocarbon radicals having no halogen alpha to the oxygen and monovalent aliphatic hydrocarbon radicals, both of less than 5 carbon atoms, and m is from 0 to 3 and has an average value of from 0 to 1.99, and (ii) being present in an amount of at least 1.0 mole of silane per mole of silicon-bonded hydroxyl in (i).

### Claim 3 (depends on 2)

The composition of claim 2 in which the chelated titanium compound is diisopropoxy-bis-(ethylacetoacetato)titanium.

### Claim 4 (depends on 2)

The composition of claim 2 in which the chelated titanium compound is 1,3-propanedioxy-bis(ethylacetoacetato)titanium.

### Claim 5 (depends on 3, 4)

The composition of claim 3 or 4 in which (b) is an ester of thioalkanoic acid of (1).

### Claim 6 (depends on 3, 4)

The composition of claim 3 or 4 in which (b) is a di-tertiary-butyl phenol of (2).

### Claim 7 (depends on 3, 4)

The composition of claim 3 or 4 in which (b) is an organic phosphite of (3).

### Claim 8 (depends on 3, 4)

The composition of claim 3 or 4 in which (b) is a mixture of a di-tertiary-butyl phenol of (2) and an organic phosphite of (3).

### Claim 9 (depends on 3, 4)

The composition of claim 3 or 4 in which R is a methyl radical and (ii) is methyltrimethoxysilane.

### Claim 10 (depends on 3)

The composition of claim 3 in which R is a methyl radical, (ii) is methyltrimethoxysilane and the additive is di(stearyl)pentaerythritoldiphosphite.

### Claim 11

A method of producing a silicone elastomeric composition which is stable under conditions excluding moisture but which will cure upon exposure to moisture comprising mixing under conditions which substantially exclude moisture
(i) a hydroxyl endblocked polydiorganosiloxane having a viscosity of at least 0.025 Pa.multidot.s at 25.degree. C. having the average formula ##EQU4## in which z has an average value from 1 to 1.01 inclusive,
y has an average value from 1.99 to 2 inclusive, and the sum of
y+z is 3,
R is selected from the group consisting of monovalent hydrocarbon radicals, halogenated monovalent hydrocarbon radicals, and monovalent cyanoalkyl radicals, all of from 1 to 18 inclusive carbon atoms, and n is an integer,
(ii) at least one silane or silane mixture of the average formula
R.sub.m Si(OR.sup.1).sub.4-m
in which
R is as defined above,
R.sup.1 is selected from the group consisting of monovalent haloaliphatic hydrocarbon radicals having no halogen alpha to the oxygen and monovalent aliphatic hydrocarbon radicals, both of less than 5 carbon atoms,
m is from 0 to 3 and has an average value of from 0 to 1.99, and (ii) being present in an amount of at least 1.0 mole of silane per mole of silicon-bonded hydroxyl in (i), and
(iii) a sufficient amount of a titanium-containing composition, to yield from 0.1 to 10 parts by weight of chelated titanium compound based on 100 parts by weight of (i) and
placing said silicone elastomerc composition into a moisture impermeable container where said titanium-containing composition comprises the product obtained by mixing, under conditions which substantially exclude moisture,
(a) a chelated titanium compound having a formula ##STR18## in which R.sup.3 is a monovalent hydrocarbon radical having from 1 to 18 inclusive carbon atoms,
R.sup.4 is a monovalent radical selected from the group consisting of hydrocarbon radicals having from 1 to 18 carbon atoms, and hydrogen,
R.sup.5 is a monovalent radical selected from the group consisting of hydrocarbon radicals and aliphatic hydrocarbonoxy radicals each having from 1 to 18 inclusive carbon atoms, and
Z is a radical selected from the group consisting of monovalent aliphatic hydrocarbonoxy radicals and monovalent acyloxy radicals, each having from 1 to 18 inclusive carbon atoms; hydroxyl radical; divalent oxygen atoms forming a TiOTi linkage; and when taken together form an alkanedioxy radical of the formula ##STR19## in which R.sup.6 is a radical selected from the group consisting of hydrogen atom and monovalent aliphatic hydrocarbon radicals having not more than 8 carbon atoms, the total number of carbon atoms in the alkanedioxy radical is not more than 18, and
(b) from 1 to 100 parts by weight based on 100 parts by weight of (a), of an additive soluble in the chelated titanium compound and being selected from the group consisting of
(1) an ester of thioalkanoic acid of the formula ##STR20## wherein R.sup.8 is an alkyl group containing from 1 to 15 inclusive carbon atoms and a is an integer of from 1 to 4 inclusive,
(2) di-tertiary-butyl phenol containing compounds selected from the group consisting of 2,6-di-tert-butyl-4-methylphenol, tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]meth ane, octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-tert-butylphenol), 1,6-hexamethylene-bis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), and thiodiethylenebis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),
(3) an organic phosphite selected from the group consisting of the formula
(R.sup.10 O).sub.b P(OR.sup.11).sub.3-b
wherein R.sup.10 and R.sup.11 are selected from the group consisting of linear or branched alkyl radicals of from 1 to 18 carbon atoms, and phenyl radical, wherein b is 0 or 1, and the formula ##STR21## wherein R.sup.12 is a linear or branched alkyl radical of from 1 to 18 carbon atoms, and
(4) a mixture of (2) and (3), the composition having a color of less than 13 as determined by the Gardner Color Scale.

### Claim 12

A method of producing a silicone elastomeric composition which is stable under conditions excluding moisture but which will cure upon exposure to moisture comprising mixing under conditions which substantially exclude moisture
(i) 100 parts by weight of a hydroxyl endblocked polydiorganosiloxane having a viscosity of at least 0.025 Pa.s at 25.degree. C. and having the average formula ##EQU5## in which z has an average value from 1 to 1.01 inclusive,
y has an average value from 1.99 to 2 inclusive, and the sum of
y+z is 3,
R is selected from the group consisting of monovalent hydrocarbon radicals, halogenated monovalent hydrocarbon radicals, and monovalent cyanoalkyl radicals, all of from 1 to 18 inclusive carbon atoms, and n is an integer,
(ii) at least one silane or silane mixture of the average formula
R.sub.m Si(OR.sup.1).sub.4-m
in which
R is as defined above,
R.sup.1 is selected from the group consisting of monovalent haloaliphatic hydrocarbon radicals having no halogen alpha to the oxygen and monovalent aliphatic hydrocarbon radicals, both of less than 5 carbon atoms,
m is from 0 to 3 and has an average value of from 0 to 1.99, and (ii) being present in an amount of at least 1.0 mole of silane per mole of silicon-bonded hydroxyl in (i), and
(a) at least 0.1 part by weight based on the weight of (i) of a chelated titanium compound having a formula ##STR22## in which R.sup.3 is a monovalent hydrocarbon radical having from 1 to 18 inclusive carbon atoms,
R.sup.4 is a monovalent radical selected from the group consisting of hydrocarbon radicals having from 1 to 18 carbon atoms, and hydrogen,
R.sup.5 is a monovalent radical selected from the group consisting of hydrocarbon radicals and aliphatic hydrocarbonoxy radicals each having from 1 to 18 inclusive carbon atoms, and
Z is a radical selected from the group consisting of monovalent aliphatic hydrocarbonoxy radicals and monovalent acyloxy radicals, each having from 1 to 18 inclusive carbon atoms; hydroxyl radical; divalent oxygen atoms forming a TiOTi linkage; and when taken together form an alkanedioxy radical of the formula ##STR23## in which R.sup.6 is a radical selected from the group consisting of hydrogen atom and monovalent aliphatic hydrocarbn radicals having not more than 8 carbon atoms, the total number of carbon atoms in the alkanedioxy radical is not more than 18, and
(b) an additive selected from the group consisting of
(1) at least 0.05 part by weight of an ester of thioalkanoic acid of the formula ##STR24## wherein R.sup.8 is an alkyl group containing from 1 to 15 inclusive carbon atoms and a is an integer of from 1 to 4 inclusive,
(2) from 0.015 part to 5 parts by weight of di-tertiary-butyl phenol containing compounds selected from the group consisting of 2,6-di-tert-butyl-4-methylphenol, tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)-propionate[met hane, octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, 4,4'-methylene-bis(2,6-di-tert-butylphenol), 1,6-hexamethylene-bis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), and thiodiethylenebis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),
(3) from 0.001 part to 1 part by weight of an organic phosphite selected from the group consisting of the formula
(R.sup.10 O).sub.b P(OR.sup.11).sub.3-b
wherein R.sup.10 and R.sup.11 are selected from the group consisting of linear or branched alkyl radicals of from 1 to 18 carbon atoms, and phenyl radical, wherein b is 0 or 1, and the formula ##STR25## wherein R.sup.12 is a linear or branched alkyl radical of from 1 to 18 carbon atoms; and
(4) a mixture of di-tertiary-butyl phenol of (2) and an organic phosphite of (3), the composition having a color of 5 or less as determined by the Gardner Color Scale.

### Claim 13 (depends on 1)

The elastomeric composition of claim 1 in which (b) is an ester of thioalkanoic acid of (1).

### Claim 14 (depends on 1)

The elastomeric composition of claim 1 in which (b) is a di-tertiary-butyl phenol of (2).

### Claim 15 (depends on 1)

The elastomeric composition of claim 1 in which (b) is an organic phosphite of (3).

### Claim 16 (depends on 1)

The elastomeric composition of claim 1 in which (b) is a mixture of the di-tertiary-butyl phenol of (2) and the organic phosphite of (3).

### Claim 17 (depends on 2)

The elastomeric composition of claim 2 in which (b) is an ester of thioalkanoic acid of (1).

### Claim 18 (depends on 2)

The elastomeric composition of claim 2 in which (b) is a di-tertiary-butyl phenol of (2).

### Claim 19 (depends on 2)

The elastomeric composition of claim 2 in which (b) is an organic phosphite of (3).

### Claim 20 (depends on 2)

The elastomeric composition of claim 2 in which (b) is a mixture of the di-tertiary-butyl phenol of (2) and the organic phosphite of (3).

### Claim 21 (depends on 17, 18, 19)

The composition of claim 17, 18, 19, or 20 in which R is a methyl radical and (ii) is methyltrimethoxysilane.

### Claim 22 (depends on 11)

The method of claim 11 in which (b) is an ester of thioalkanoic acid of (1).

### Claim 23 (depends on 11)

The method of claim 11 in which (b) is a di-tertiary-butyl phenol of (2).

### Claim 24 (depends on 11)

The method of claim 11 in which (b) is an organic phosphite of (3).

### Claim 25 (depends on 11)

The method of claim 11 in which (b) is a mixture of the di-tertiary-butyl phenol of (2) and the organic phosphite of (3).

### Claim 26 (depends on 12)

The method of claim 12 in which (b) is an ester of thioalkanoic acid of (1).

### Claim 27 (depends on 12)

The method of claim 12 in which (b) is a di-tertiary-butyl phenol of (2).

### Claim 28 (depends on 12)

The method of claim 12 in which (b) is an organic phosphite of (3).

### Claim 29 (depends on 12)

The method of claim 12 in which (b) is a mixture of the di-tertiary-butyl phenol of (2) and the organic phosphite of (3).

### Claim 30 (depends on 50, 51)

The product obtained by exposing the composition of claim 50 or 51 to moisture.

### Claim 31 (depends on 5)

The product obtained by exposing the composition of claim 5 to moisture.

### Claim 32 (depends on 6)

The product obtained by exposing the composition of claim 6 to moisture.

### Claim 33 (depends on 7)

The product obtained by exposing the composition of claim 7 to moisture.

### Claim 34 (depends on 8)

The product obtained by exposing the composition of claim 8 to moisture.