Polyorganosiloxane composition, and associated method
View Patent ↗A composition is provided that may include a sulfur-functional linear polyorganosiloxane. The sulfur-functional linear polyorganosiloxane may include a chemically protected sulfur group. Under certain conditions, the sulfur group may react with an unsaturated elastomer. The invention may include embodiments that relate to method of making and using the sulfur-functional linear polyorganosiloxane.
1. A composition comprising: a sulfur-functional linear polyorganosiloxane comprising a chemically-protected sulfur group capable of reacting with an unsaturated elastomer, wherein the sulfur-functional linear polyorganosiloxane has a formula of (I), (II) or (III):
wherein A is a ((R 27 OC(═O)) t -(L) j ) k -(Q) z J(=E)- group;
R 1 -R 27 is independently at each occurrence a hydrogen atom, an aliphatic radical, a cycloaliphatic radical, or an aromatic radical;
G is a divalent aliphatic radical, a divalent cycloaliphatic radical, or a divalent aromatic radical;
R 28 is a hydroxyl group, an alkoxy group, or an aryloxy group;
S is one or more sulfur atoms;
L is independently at each occurrence a monovalent or a polyvalent group derived by substitution of an aliphatic radical, a cycloaliphatic radical, or an aromatic radical;
Q is oxygen, sulfur or an NR 29 group, R 29 is an aliphatic radical, a cycloaliphatic radical, or an aromatic radical;
J is carbon, sulfur, phosphorus, or a sulfonyl group;
E is oxygen or sulfur;
“m” is independently an integer greater than 0;
“n” is independently equal to 0 or is an integer greater than 0;
“p” is greater than 0;
“t” is an integer that is equal to 0, 1, 2, 3, 4, or 5;
“j” is equal to 0 or 1;
“k” is equal to 1 if J is carbon, sulfur or sulfonyl, “k” is 2 if J is phosphorus; and
“z” is an integer that is equal to 0, 1, or 2.
2. The composition as defined in claim 1 , wherein the sulfur-functional linear polyorganosiloxane further comprises a functional group capable of coupling with a filler surface.
3. The composition as defined in claim 1 , wherein the sulfur-functional linear polyorganosiloxane has a formula of (I):
wherein A is a ((R 27 OC(═O)) t -(L) j ) k -(Q) z J(=E) group;
R 1 -R 27 are independently at each occurrence a hydrogen atom, an aliphatic radical, a cycloaliphatic radical, or an aromatic radical;
G is a divalent aliphatic radical, a divalent cycloaliphatic radical, or a divalent aromatic radical;
R 28 is a hydroxyl group, an alkoxy group, or an aryloxy group;
S is one or more sulfur atoms;
L is independently at each occurrence a monovalent or a polyvalent group derived by substitution of an aliphatic radical, a cycloaliphatic radical, or an aromatic radical;
Q is oxygen, sulfur or an NR 29 group, R 29 is an aliphatic radical, a cycloaliphatic radical, or an aromatic radical;
J is carbon, sulfur, phosphorus, or a sulfonyl group;
E is oxygen or sulfur;
“m” is independently an integer greater than 0;
“n” is independently an integer greater than 0;
“p” is greater than 0;
“t” is an integer that is equal to 0, 1, 2, 3, 4, or 5;
“j” is equal to 0 or 1;
“k” is equal to 1 if J is carbon, sulfur or sulfonyl, “k” is 2 if J is phosphorus; and
“z” is an integer that is equal to 0, 1, or 2.
4. The composition as defined in claim 1 , wherein the sulfur-functional linear polyorganosiloxane has a formula of(II):
wherein A is a ((R 27 OC(═O)) t -(L) j ) k -(Q) z J(=E)- group;
R 1 -R 27 is independently at each occurrence a hydrogen atom, an aliphatic radical, a cycloaliphatic radical, or an aromatic radical;
G is a divalent aliphatic radical, a divalent cycloaliphatic radical, or a divalent aromatic radical;
R 28 is a hydroxyl group, an alkoxy group, or an alkoxy group;
S is one or more sulfur atoms;
L is independently at each occurrence a monovalent or a polyvalent group derived by substitution of an aliphatic radical, a cycloaliphatic radical, or an aromatic radical;
Q is oxygen, sulfur or an NR 29 group, R 29 is an aliphatic radical, a cycloaliphatic radical, or an aromatic radical;
J is carbon, sulfur, phosphorus, or a sulfonyl group;
E is oxygen or sulfur;
“m” is independently an integer greater than 0;
“n” is independently an integer greater than 0;
“p” is greater than 0;
“t” is an integer that is equal to 0, 1, 2, 3, 4, or 5;
“j” is equal to 0 or 1;
“k” is equal to 1 if J is carbon, sulfur or sulfonyl, “k” is 2 if J is phosphorus; and
“z” is an integer that is equal to 0, 1, or 2.
5. The composition as defined in claim 1 , wherein the sulfur-functional linear polyorganosiloxane has a formula of (III):
wherein A is a ((R 27 OC(═O)) t -(L) j ) k -(Q) z J(=E)- group;
R 1 -R 27 is independently at each occurrence a hydrogen atom, an aliphatic radical, a cycloaliphatic radical, or an aromatic radical;
G is a divalent aliphatic radical, a divalent cycloaliphatic radical, or a divalent aromatic radical;
R 28 is a hydroxyl group, an alkoxy group, or an aryloxy group;
S is one or more sulfur atoms;
L is independently at each occurrence a monovalent or a polyvalent group derived by substitution of an aliphatic radical, a cycloaliphatic radical, or an aromatic radical;
Q is oxygen, sulfur or an NR 29 group, R 29 is an aliphatic radical, a cycloaliphatic radical, or an aromatic radical;
J is carbon, sulfur, phosphorus, or a sulfonyl group;
E is oxygen or sulfur;
“m” is independently an integer greater than 0;
“n” is independently an integer greater than 0;
“p” is greater than 0;
“t” is an integer that is equal to 0, 1, 2, 3, 4, or 5;
“j” is equal to 0 or 1;
“k” is equal to 1 if J is carbon, sulfur or sulfonyl, “k” is 2 if J is phosphorus; and
“z” is an integer that is equal to 0, 1, or 2.
6. The composition as defined in claim 1 , wherein A-S— is one or more of a thiocarboxylate ester; dithiocarboxylate; thiocarbonate ester; dithiocarbonate ester; trithiocarbonate ester; thiosulfonate ester; thiosulfate ester; thiosulfamate ester; trithiosulfinate ester; thiosulfite ester; thiosulfimate ester; thiophosphate ester; dithiophosphate ester; trithiophosphate ester; thiophosphamate ester; dithiophosphamate ester; thiophosphoramidate ester; dithiophosphoramidate ester; or trithiophosphoramidate ester.
7. The composition as defined in claim 1 , wherein R 28 is one or more of a hydroxyl group, a methoxy group, an ethoxy group, an isopropyloxy group, an isobutoxy group, or an acetoxy group.
8. The composition as defined in claim 1 , wherein the sulfur-functional linear polyorganosiloxane has a molecular weight in a range greater than about 250 grams per mole.
9. The composition as defined in claim 1 , wherein G is one or more of (—CH 2 CH 2 —), (—CH 2 CH 2 CH 2 —), (—CH 2 CH 2 CH 2 CH 2 —), (—CH(CH 3 )—), (—CH 2 CH(CH 3 )—), (—C(CH 3 ) 2 —), (—CH(C 2 H 5 )—), (—CH 2 CH 2 CH(CH 3 )—), (—CH 2 CH(CH 3 )CH 2 —),(—CH 2 CH 2 (C 6 H 4 )CH 2 CH 2 —), diethylene cyclohexane, or 1,2,4-triethylene cyclohexane.
10. A composition comprising the reaction product of a linear polyorganosiloxane comprising an alkene group and a —R 28 group bonded to the linear polyorganosiloxane through a divalent aliphatic radical, a divalent cycloaliphatic radical, or a divalent aromatic radical, and a thio acid having a structure defined by formula (IV):
((R 27 OC(═O)) t -(L) j ) k -(Q) z J(=E)SH (IV)
wherein R 27 is an aliphatic radical, a cycloaliphatic radical, or an aromatic radical;
L is independently at each occurrence a monovalent group or a polyvalent group that is derived by substitution of an aliphatic radical, a cycloaliphatic radical, or an aromatic radical;
Q is oxygen, sulfur, or an NR 29 group, wherein R 29 is an aliphatic radical, a cycloaliphatic radical, or an aromatic radical;
J is carbon, sulfur, phosphorus, or a sulfonyl group;
E is oxygen or sulfur;
S comprises one or more sulfur atoms;
R 28 is a hydroxyl group, an alkoxy group, or an aryloxy group;
“t” is an integer that is equal to 0, 1, 2, 3, 4, or 5;
“j” is equal to 0 or 1;
“k” is equal to 1 if J is carbon, sulfur or sulfonyl;
“k” is 2 if J is phosphorus; and
“z” is equal to 0, 1, or 2.
11. The composition as defined in claim 10 , wherein the reaction product comprises one or more of a thiocarboxylate ester; dithiocarboxylate; thiocarbonate ester; dithiocarbonate ester; trithiocarbonate ester; thiosulfonate ester; thiosulfate ester; thiosulfamate ester; thiosulfinate ester; thiosulfite ester; thiosulfimate ester; thiophosphate ester; dithiophosphate ester; trithiophosphate ester; thiophosphamate ester; dithiophosphamate ester; thiophosphoramidate ester; dithiophosphoramidate ester; or trithiophosphoramidate ester.
12. The composition as defined in claim 10 , wherein the reaction product further comprises one or more of a hydroxyl group, a methoxy group, an ethoxy group, an isopropyloxy group, an isobutoxy group, or an acetoxy group.