Modified elastomeric polymers
View Patent ↗This disclosure generally relates to chain end modified elastomeric polymers and branched modified elastomeric polymers, their use in the preparation of elastomeric compositions, and articles prepared from chain end modified elastomeric polymers and branched modified elastomeric polymers. An elastomeric polymer composition is provided including the reaction product of at least a living anionic elastomeric polymer, a silane modifier compound, and a modifier compound.
1. An elastomeric polymer composition comprising the reaction product of at least the following:
i) a living anionic elastomeric polymer;
ii) a silane modifier compound represented by the Formula 1 or Formula 2:
(R 1 O) 3 Si—R 4 —S—SiR 3 3 , Formula 1
(R 13 O) 3 Si—R 9 —N(SiR 10 R 11 R 12 ) 2 Formula 2
wherein:
Si is silicon; S is sulfur; O is oxygen; N is nitrogen;
R 4 and R 9 are the same or different, and each is independently a group selected from a (C 7 -C 100 ) aralkyl, a (C 6 -C 100 ) aryl, a (C 1 -C 100 ) alkyl, or a (C 2 -C 100 ) dialkylether (alkyl-O-alkyl); and wherein each alkyl may be linear or branched, and saturated or unsaturated;
R 1 , R 3 , R 10 , R 11 , R 12 and R 13 are the same or different, and are each, independently, selected from hydrogen (H), a (C 1 -C 16 ) alkyl, a (C 6 -C 16 ) aryl, a (C 7 -C 16 ) aralkyl or a (C 3 -C 30 ) tri(hydrocarbyl)silyl, and wherein the hydrocarbyl groups are each, independently, selected from a (C 1 -C 16 ) alkyl, a (C 6 -C 16 ) aryl, or a (C 7 -C 16 ) aralkyl;
iii) a modifier compound represented by one of the following Formulas 3 to 6:
wherein:
Si is silicon; S is sulfur; O is oxygen; N is nitrogen,
x and p are an integer selected from 1, and 2;
y and q are an integer selected from 1, and 2;
x+y=3; p+q=3;
R 4 , R 9 and R 15 are the same or different, and each is independently a group selected from a (C 7 -C 100 ) aralkyl, a (C 6 -C 100 ) aryl, a (C 1 -C 100 ) alkyl, or a (C 2 -C 100 ) dialkylether (alkyl-O-alkyl); and wherein each alkyl may be linear or branched, and saturated or unsaturated;
R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 10 , R 11 , R 12 , R 13 , R 14 , R 16 , R 17 , R 18 , R 19 , R 20 , and R 21 are the same or different, and are each, independently, selected from hydrogen (H), a (C 1 -C 16 ) alkyl, a (C 6 -C 16 ) aryl, a (C 7 -C 16 ) aralkyl, or a (C 3 -C 30 ) tri(hydrocarbyl)silyl, and wherein
the hydrocarbyl groups are each independently selected from a (C 1 -C 16 ) alkyl, a (C 6 -C 16 ) aryl, or a (C 7 -C 16 ) aralkyl.
2. The composition of claim 1 , wherein the living anionic elastomeric polymer (Component i) and the silane modifier compound (Component ii) are first reacted to form a modified polymer, and the modified polymer is then reacted with the modifier compound (Component iii).
3. The composition of claim 1 , wherein the silane modifier (Component ii) is the compound of Formula 1.
4. The composition of claim 1 , wherein the silane modifier (Component ii) is the compound of Formula 2.
5. The composition of claim 1 , wherein the elastomeric polymer is selected from the group consisting of styrene-butadiene copolymers, polybutadiene, butadiene-isoprene copolymers, polyisoprene and butadiene-styrene-isoprene terpolymers.
6. The composition of claim 1 , further comprising a filler.
7. The composition of claim 1 , further comprising a vulcanization agent.
8. The composition of claim 6 , further comprising at least one polymer is selected from the group consisting of styrene-butadiene copolymers, polybutadiene, butadiene-isoprene copolymers, polyisoprene, butadiene-styrene-isoprene terpolymers, and combinations thereof.
9. An article comprising at least one component formed from the composition of claim 1 .
10. The article of claim 9 , wherein the article is a tire.
11. An elastomeric polymer composition comprising the reaction product of at least the following: 1) a filler; 2) the elastomeric polymer composition of claim 1 .
12. The composition of claim 11 , wherein the living anionic elastomeric polymer (Component i) and the silane modifier (Component ii) are first reacted to form a modified polymer, and the modified polymer is then reacted with the modifier (Component iii).
13. The composition of claim 11 , wherein the silane modifier (Component ii) is the compound of Formula 1.
14. The composition of claim 11 , wherein the silane modifier (Component ii) is the compound of Formula 2.
15. The composition of claim 11 , wherein the elastomeric polymer is selected from the group consisting of styrene-butadiene copolymers, polybutadiene, butadiene-isoprene copolymers, polyisoprene and butadiene-styrene-isoprene terpolymers.
16. An article comprising at least one component formed from the composition of claim 11 .
17. A vulcanized elastomeric polymer composition comprising the reaction product of at least the following:
1) a filler;
2) a vulcanization agent; and
3) the elastomeric polymer composition of claim 1 .
18. The vulcanized composition of claim 17 , wherein the living anionic elastomeric polymer (Component i) and the silane modifier (Component ii) are first reacted to form a modified polymer, and the modified polymer is then reacted with the modifier (Component iii).
19. The vulcanization composition of claim 17 , wherein the silane modifier (Component ii) is the compound of Formula 1.
20. The vulcanization composition of claim 17 , wherein the silane modifier (Component ii) is the compound of Formula 2.
21. An article comprising at least one component formed from the composition of claim 17 .
22. A composition comprising at least the following:
i) a living anionic elastomeric polymer;
ii) a silane modifier compound represented by the Formula 1 or Formula 2:
(R 1 O) 3 Si—R 4 —S—SiR 3 3 , Formula 1
(R 13 O) 3 Si—R 9 —N(SiR 10 R 11 R 12 ) 2 Formula 2
wherein:
Si is silicon; S is sulfur; O is oxygen; N is nitrogen;
R 4 and R 9 are the same or different, and each is independently a group selected from a (C 7 -C 100 ) aralkyl, a (C 6 -C 100 ) aryl, a (C 1 -C 100 ) alkyl, or a (C 2 -C 100 ) dialkylether (alkyl-O-alkyl); and wherein each alkyl may be linear or branched, and saturated or unsaturated;
R 1 , R 3 , R 10 , R 11 , R 12 and R 13 are the same or different, and are each, independently, selected from hydrogen (H), a (C 1 -C 16 ) alkyl, a (C 6 -C 16 ) aryl, a (C 7 -C 16 ) aralkyl or a (C 3 -C 30 ) tri(hydrocarbyl)silyl, and wherein the hydrocarbyl groups are each, independently, selected from a (C 1 -C 16 ) alkyl, a (C 6 -C 16 ) an aryl, or a (C 7 -C 16 ) aralkyl; and
iii) a modifier compound represented by one of the following Formulas 3 to 6:
wherein:
Si is silicon; S is sulfur; O is oxygen; N is nitrogen,
x and p are an integer selected from 1, and 2;
y and q are an integer selected from 1, and 2;
x+y=3; p+q=3;
R 4 , R 9 and R 15 are the same or different, and each is independently a group selected from a (C 7 -C 100 ) aralkyl, a (C 6 -C 100 ) aryl, a (C 1 -C 100 ) alkyl, or a (C 2 -C 100 ) dialkylether (alkyl-O-alkyl); and wherein each alkyl may be linear or branched, and saturated or unsaturated;
R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 10 , R 11 , R 12 , R 13 , R 14 , R 16 , R 17 , R 18 , R 19 , R 20 , and R 21 are the same or different, and are each, independently, selected from hydrogen (H), a (C 1 -C 16 ) alkyl, a (C 6 -C 16 ) aryl, a (C 7 -C 16 ) aralkyl, or a (C 3 -C 30 ) tri(hydrocarbyl)silyl, and wherein
the hydrocarbyl groups are each independently selected from a (C 1 -C 16 ) alkyl, a (C 6 -C 16 ) aryl, or a (C 7 -C 16 ) aralkyl.
23. The composition of claim 22 , wherein the silane modifier (Component ii) is the compound of Formula 1.
24. The composition of claim 22 , wherein the silane modifier (Component ii) is the compound of Formula 2.
25. The composition of claim 22 , wherein the elastomeric polymer is selected from the group consisting of styrene-butadiene copolymers, polybutadiene, butadiene-isoprene copolymers, polyisoprene, and butadiene-styrene-isoprene terpolymers.
26. An article comprising at least one component formed from the composition of claim 22 .
27. A method for making an elastomeric polymer composition, comprising the following:
A) reacting at least the following constituents to form a modified polymer:
i) a living anionic elastomeric polymer, and
ii) a silane modifier compound represented by the Formula 1 or Formula 2:
(R 1 O) 3 Si—R 4 —S—SiR 3 3 , Formula 1
(R 13 O) 3 Si—R 9 —N(SiR 10 R 11 R 12 ) 2 Formula 2
wherein:
Si is silicon; S is sulfur; O is oxygen; N is nitrogen;
R 4 and R 9 are the same or different, and each is independently a group selected from a (C 7 -C 100 ) aralkyl, a (C 6 -C 100 ) aryl, a (C 1 -C 100 ) alkyl, or a (C 2 -C 100 ) dialkylether (alkyl-O-alkyl); and wherein each alkyl may be linear or branched, and saturated or unsaturated;
R 1 , R 3 , R 10 , R 11 , R 12 and R 13 are the same or different, and are each, independently, selected from hydrogen (H), a (C 1 -C 16 ) alkyl, a (C 6 -C 16 ) an aryl, a (C 7 -C 16 ) aralkyl or a (C 3 -C 30 ) tri(hydrocarbyl)silyl, and wherein the hydrocarbyl groups are each independently, selected from a (C 1 -C 16 ) alkyl, a (C 6 -C 16 ) an aryl, or a (C 7 -C 16 ) aralkyl;
B) reacting the modified polymer with at least the following to form the elastomeric polymer:
iii) a modifier compound represented by one of the following Formulas 3 to 6:
wherein:
Si is silicon; S is sulfur; O is oxygen; N is nitrogen,
x and p are an integer selected from 1, and 2;
y and q are an integer selected from 1, and 2;
x+y=3; p+q=3;
R 4 , R 9 and R 15 are the same or different, and each is independently a group selected from a (C 7 -C 100 ) aralkyl, a (C 6 -C 100 ) aryl, a (C 1 -C 100 ) alkyl, or a (C 2 -C 100 ) dialkylether (alkyl-O-alkyl); and wherein each alkyl may be linear or branched, and saturated or unsaturated;
R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 10 , R 11 , R 12 , R 13 , R 14 , R 16 , R 17 , R 18 , R 19 , R 20 , and R 21 are the same or different, and are each, independently, selected from hydrogen (H), a (C 1 -C 16 ) alkyl, a (C 6 -C 16 ) aryl, a (C 7 -C 16 ) aralkyl, or a (C 3 -C 30 ) tri(hydrocarbyl)silyl, and wherein the hydrocarbyl groups are each independently selected from a (C 1 -C 16 ) alkyl, a (C 6 -C 16 ) aryl, or a (C 7 -C 16 ) aralkyl.
28. A method for making a vulcanized elastomeric polymer composition comprising the steps of reacting at least the following constituents: 1) a filler; 2) a vulcanization agent; and 3) the elastomeric polymer composition of claim 1 .
29. The composition of claim 1 , wherein the silane modifier (Component ii) is the compound of Formula 1 and modifier compound (Component iii) is the compound of Formula 3.
30. The composition of claim 11 , wherein the silane modifier (Component ii) is the compound of Formula 1 and modifier compound (Component iii) is the compound of Formula 3.
31. The composition of claim 17 , wherein the silane modifier (Component ii) is the compound of Formula 1 and modifier compound (Component iii) is the compound of Formula 3.
32. The composition of claim 17 , wherein the silane modifier (Component ii) is the compound of Formula 2 and modifier (Component iii) is the compound of Formula 3.