Hydrolysable silanes
View Patent ↗This invention relates to hydrolysable silanes useful in the modification of elastomers, and as coupling agents for diene elastomer compositions containing a filler. In particular the invention relates to novel hydrolysable silanes containing a tertiary amine group and an ether or thioether linkage.
1. A hydrolysable silane of the formula
wherein each R represents a hydrolysable group; each R″ represents a hydrocarbyl group having 1 to 8 carbon atoms; n=1 to 3; Y represents a divalent organic spacer linkage having 2 to 20 carbon atoms; X represents —O— or —NH—; m=0 or 1; R 2 represents hydrogen or a hydrocarbyl or substituted hydrocarbyl group having 1 to 8 carbon atoms;
and comprising at least one of the following limitations 1) through 6):
1) Z represents an oxygen atom, R 1 represents a hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, R 3 represents a group of the formula —((CH 2 ) a O) b —R 4 wherein a=1 to 3; b=1 to 6; and R 4 represents hydrogen or a hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms;
2) Z represents a sulphur atom, R 1 represents a hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms and R 3 represents a group of the formula —Y″—SiR p R″ 3-p wherein Y″ represents a divalent organic spacer linkage having 1 to 20 carbon atoms; and p=1 to 3;
3) Z represents an oxygen or a sulphur atom; R 1 represents a group of the formula —Y*—SiR q R″ 3-q wherein Y* represents a divalent organic spacer linkage having 1 to 20 carbon atoms; q =1 to 3; and R 3 represents a hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, provided that when R 3 is CH 3 ;
4) R 1 represents a group of the formula
wherein d =1 to 8; R 8 represents hydrogen or a hydrocarbyl or substituted hydrocarbyl group having 1 to 8 carbon atoms; Z and Z′ independently represent an oxygen or sulphur atom; R 9 represents a hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms; X″ represents —O— or —NH—; m″=0 or 1; Y** represents a divalent organic spacer linkage having 1 to 20 carbon atoms; r =1 to 3; and R 3 represents a hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms;
5) R 1 represents a group of the formula —(CH 2 ) e —C(O)OR 10 wherein e=1 to 8; R 10 represents a hydrocarbyl group having 1 to 8 carbon atoms; and Z represents an oxygen or sulphur atom; R 3 represents a hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms; or
6) Z represents an oxygen atom, R 1 represents a hydrocarbyl group having 1 to 20 carbon atoms, R 3 represents a hydrocarbyl or substituted hydrocarbyl group having from 1 to 20 carbon atoms.
2. A hydrolysable silane according to Claim 1 , comprising limitation 1) wherein R 4 represents hydrogen or a hydrocarbyl group having 1 to 8 carbon atoms.
3. A hydrolysable silane according to Claim 1 , comprising limitation 1) wherein R 4 represents a group of the formula
wherein R6 represents hydrogen or a hydrocarbyl or substituted hydrocarbyl group having 1 to 8 carbon atoms; R 7 represents hydrogen or a hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms; X′ represents —O— or —NH—; m′=0 or 1; Y′ represents a divalent organic spacer linkage having 1 to 20 carbon atoms; each R represents a hydrolysable group; each R″ represents a hydrocarbyl group having 1 to 8 carbon atoms; and n′=1 to 3.
4. A hydrolysable silane according to claim 1 , comprising at least one of limitations 1), 2), or 6) wherein R 1 represents a hydrocarbyl group having 1 to 8 carbon atoms.
5. A hydrolysable silane according to claim 1 , characterised in that R 2 represents hydrogen or each R group is an alkoxy group having 1 to 4 carbon atoms.
6. A hydrolysable silane according to claim 5 , characterised in that each R group is an ethoxy group.
7. A hydrolysable silane according to claim 1 , characterised in that n=3.
8. A hydrolysable silane according to claim 1 , characterised in that Y represents an alkylene group having 2 to 6 carbon atoms.
9. The hydrolysable silane of the formula
10. A hydrolysable silane according to claim 1 , wherein the silane is partially hydrolysed and condensed into oligomers containing siloxane linkages.
11. A process for the preparation of a hydrolysable silane of the formula
wherein each R represents a hydrolysable group; each R″ represents a hydrocarbyl group having 1 to 8 carbon atoms; n=1 to 3; Y represents a divalent organic spacer linkage having 1 to 20 carbon atoms; X represents —O— or —NH—; m=0 or 1; R 1 represents a hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms; R 2 represents hydrogen or a hydrocarbyl or substituted hydrocarbyl group having 1 to 8 carbon atoms; Z represents an oxygen or sulphur atom; and R 3 represents a hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, characterised in that a secondary aminoalkylsilane of the formula R 1 —NH—(CH 2 —C(O)—X) m —Y—SiR n R″ 3-n , wherein R, R″, n, Y, X and R 1 are defined as in claim 1 , is reacted with an aldehyde of the formula R 2 —CHO wherein R 2 represents hydrogen or a hydrocarbyl or substituted hydrocarbyl group having 1 to 8 carbon atoms and an alcohol or thiol of the formula R 3 ZH wherein Z represents an oxygen or sulphur atom; and R 3 represents a hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms.
12. A process according to claim 11 characterised in that the secondary aminoalkylsilane, the aldehyde and the alcohol or thiol are reacted at a temperature in the range 30 to 200° C.