Silane sulfide modified elastomeric polymers
The present invention relates to silane sulfide modifier compounds and methods of making them. The invention also relates to a silane sulfide modified macromolecular compound obtainable by reacting a living anionic elastomeric polymer and a silane sulfide modifier. The silane sulfide modified macromolecular compound may be provided in the form of a polymer composition, and the polymer composition may be vulcanized (cross-linked) by making use of and reaction with at least one vulcanization agent, resulting in a vulcanized polymer composition.
1. A silane sulfide modified elastomeric macromolecular compound obtainable by reacting
i) a living anionic elastomeric polymer and
ii) a silane sulfide modifier represented by the following Formula (5) or Formula (6):
wherein
M is a silicon atom or a tin atom;
R 3 is at least divalent and is (C 8 -C 16 ) alkylarylalkyl, (C 7 -C 16 ) arylalkyl, (C 7 -C 16 ) alkylaryl, or (C 1 -C 16 ) alkyl, and each group may be substituted with one or more of the following groups: tertiary amine group, silyl group, (C 7 -C 18 ) aralkyl group and (C 6 -C 18 ) aryl group;
R 1 , R 12 and R 16 are each independently selected from a hydrogen atom and (C 1 -C 4 ) alkyl;
R 2 , R 13 and R 15 are each independently selected from (C 1 -C 16 ) alkyl, (C 7 -C 16 ) alkylaryl and (C 7 -C 16 ) arylalkyl;
R 4 and R 14 are each independently selected from (C 1 -C 16 ) alkyl and (C 7 -C 16 ) alkylaryl;
b, d and f are each independently selected from an integer of 0, 1 and 2; a, c and e are each independently selected from an integer of 1, 2 and 3; a+b=3; c+d=3; and e+f=3.
2. The silane sulfide modified elastomeric macromolecular compound according to claim 1 , which is represented by the following Formula (P1)
((P) r (R 1 O) x-r (R 2 ) y Si—R 3 —S) s M(R 4 ) t (X) u (Formula P1),
wherein
P is a polymer chain comprising monomer units derived from at least one of the following monomer groups: butadiene, isoprene, styrene and alpha-methylstyrene, the number of monomer units per macromolecule ranging from 10 to 50.000;
M is a silicon atom or a tin atom;
x is an integer selected from 1, 2 and 3; y is an integer selected from 0, 1, and 2; r is an integer selected from 1, 2 and 3; wherein x+y+r=3;
s is an integer selected from 2, 3 and 4; t is an integer selected from 0, 1 and 2; u is an integer selected from 0, 1 and 2; wherein s+t+u=4;
R 1 is independently selected from a hydrogen atom and (C 1 -C 6 ) alkyl;
R 2 is independently selected from (C 1 -C 16 ) alkyl, (C 7 -C 16 ) alkylaryl and (C 7 -C 16 ) arylalkyl;
R 3 is at least divalent and is independently selected from (C 1 -C 16 )alkyl, (C 8 -C 16 ) alkylarylalkyl, (C 7 -C 16 ) arylalkyl and (C 7 -C 16 ) alkylaryl, and each group may be substituted with one or more of the following groups: tertiary amine group, silyl group, (C 7 -C 18 ) aralkyl group and (C 6 -C 18 ) aryl group;
R 4 is independently selected from (C 1 -C 16 ) alkyl and (C 7 -C 16 ) alkylaryl; and X is independently selected from chloride, bromide and —OR 5 ; wherein R 5 is selected from (C 1 -C 16 ) alkyl and (C 7 -C 16 ) arylalkyl.
3. The silane sulfide modified elastomeric macromolecular compound according to claim 2 , wherein R 3 is divalent (C 1 -C 16 ) alkyl.
4. The silane sulfide modified elastomeric macromolecular compound according to claim 2 , wherein X is selected from chloride, bromide and —OR 5 ; wherein R 5 is selected from (C 1 -C 16 ) alkyl.
5. The silane sulfide modified elastomeric macromolecular compound according to claim 2 , wherein R 2 and R 4 are independently selected from (C 1 -C 16 ) alkyl.
6. The silane sulfide modified elastomeric macromolecular compound according to claim 2 , wherein R 1 , R 2 , R 4 and R 5 are independently selected from (C 1 -C 4 ) alkyl.
7. The silane sulfide modified elastomeric macromolecular compound according to claim 2 , wherein s and t are each 2 and u is 0; or s is 3, t is 1 and u is 0.
8. The silane sulfide modified elastomeric macromolecular compound according to claim 2 , wherein r is 1, x is 1 and y is 1; or r is 1, x is 0 and y is 2.
9. A polymer composition comprising at least one silane sulfide modified macromolecular compound as defined in claim 1 and one or more further components selected from components which are added to or formed as a result of the polymerization process used for making the modified macromolecular compound and components which remain after solvent removal from the polymerization process.
10. The polymer composition according to claim 9 , which comprises at least one filler.
11. The polymer composition according to claim 10 , wherein the filler is one or more selected from carbon black, silica, carbon-silica dual-phase-filler, clay, calcium carbonate, magnesium carbonate, lignin, and glass particles.
12. The polymer composition according to claim 11 , wherein the filler comprises silica.
13. The polymer composition according to claim 11 , wherein the filler comprises carbon black.
14. The polymer composition according to claim 9 , which comprises a vulcanization agent.
15. The polymer composition according to claim 9 , which comprises at least one polymer selected from the group consisting of polybutadiene, butadiene-styrene copolymers, butadiene-isoprene copolymers, polyisoprene and butadiene-styrene-isoprene terpolymers.
16. A vulcanized polymer composition comprising the reaction product of at least the following: at least one vulcanization agent; and the polymer composition as defined in claim 9 .
17. A method for making a vulcanized polymer composition comprising reacting at least the following components: at least one vulcanization agent; and the polymer composition as defined in claim 9 .
18. An article comprising at least one component formed from the vulcanized polymer composition as defined in claim 16 .
19. The article according to claim 18 , which is selected from the group consisting of a tire, a tire tread, a tire side wall, a tire carcass, a belt, a hose, a vibration damper, and a footwear component.
20. The silane sulfide modified elastomeric macromolecular compound according to claim 1 , wherein R 3 is a (C 1 -C 16 ) divalent alkyl group or (C 8 -C 16 ) divalent alkylarylalkyl group.
21. The silane sulfide modified elastomeric macromolecular compound according to claim 1 , wherein R 3 is selected from —CH 2 —, —(CH 2 ) 2 —, —(CH 2 ) 3 —, —(CH 2 ) 4 —, —CH 2 —C 6 H 4 —CH 2 — and —C 6 H 4 —C(CH 3 ) 2 —C 6 H 4 —.
22. The silane sulfide modified elastomeric macromolecular compound according to claim 1 , wherein R 2 , R 4 , R 13 and R 15 are each independently selected from (C 1 -C 16 ) alkyl.
23. The silane sulfide modified elastomeric macromolecular compound according to claim 1 , wherein M is a silicon atom; a, c and e are each an integer selected from 2 and 3; and b, d and f are each an integer selected from 0 and 1.