Process for production of modified conjugated diene polymers, modified conjugated diene polymers produced by the process, rubber compositions, and tires
A process for producing a modified conjugated diene based polymer includes a step (a) of reacting a silicon compound with a conjugated diene based polymer having an active end so that the reaction takes place at the active end, the silicon compound having a protected primary amino group in the molecule thereof and a silicon atom to which a hydrocarbyloxy group and a reactive group are bonded, to thereby modify the active end, and a step (b) of performing condensation reaction, in the presence of a titanium compound serving as a titanium-based condensation-accelerating agent. A rubber composition contains the modified diene polymer, and a tire is produced from the rubber composition.
1. A process for producing a modified conjugated diene based polymer, the process comprising
a step (a) of reacting a silicon compound with a conjugated diene based polymer having an active end so that the reaction takes places at the active end, the silicon compound having a protected primary amino group in the molecule thereof and a silicon atom to which a hydrocarbyloxy group and a reactive group are bonded, to thereby modify the active end, and
a step (b) of performing condensation reaction which involves the group derived from the silicon compound and bonded to the active end of the conjugated diene based polymer, in the presence of a titanium compound serving as a titanium-based condensation-accelerating agent,
wherein the protected amino group is capable of being deprotected by hydrolysis to be a primary amino group, and
wherein the titanium compound is at least one selected from the group consisting of tetrakis(2-ethyl-1,3-hexanediolato)titanium and titanium di-n-butoxide bis(2,4-pentanedionate).
2. A process for producing a modified conjugated diene based polymer as described in claim 1 , which further includes a deprotection step (c) of hydrolyzing the group derived from the silicon compound and bonded to the active end of the conjugated diene based polymer, whereby the protected primary amino group contained in the group bonded to the active end is converted to a free amino group.
3. A process for producing a modified conjugated diene based polymer as described in claim 1 , wherein the silicon compound employed in the step (a) is a silicon compound represented by formula (I):
wherein each of R 1 and R 2 represents a hydrocarbon group having 1 to 20 carbon atoms, each of R 3 to R 5 represents a hydrocarbon group having 1 to 20 carbon atoms, R 6 represents a divalent hydrocarbon group having 1 to 12 carbon atoms, A represents a reactive group, and f is an integer of 1 to 10; or
a silicon compound represented by formula (III):
wherein each of R 1 and R 2 represents a hydrocarbon group having 1 to 20 carbon atoms, each of R 3 to R 5 represents a hydrocarbon group having 1 to 20 carbon atoms, R 6 represents a divalent hydrocarbon group having 1 to 12 carbon atoms, R 13 represents a divalent hydrocarbon group having 1 to 12 carbon atoms, A represents a reactive group, and f is an integer of 1 to 10.
4. A process for producing a modified conjugated diene based polymer as described in claim 3 , wherein the group A in formula (I) is a halogen atom or a hydrocarbyloxy group having 1 to 20 carbon atoms.
5. A process for producing a modified conjugated diene based polymer as described in claims 1 , wherein the conjugated diene based polymer having an active end is produced through anionic polymerization, in the presence of an organic alkali metal compound serving as a polymerization initiator, of a conjugated diene compound singly or of a conjugated diene compound and an aromatic vinyl compound in combination.
6. A process for producing a modified conjugated diene based polymer as described in claim 5 , wherein the conjugated diene compound is at least one selected from the group consisting of 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene.
7. A process for producing a modified conjugated diene based polymer as described in claim 5 , wherein the aromatic vinyl compound is styrene.
8. A process for producing a modified conjugated diene based polymer as described in claim 5 , wherein the conjugated diene based polymer has a repeating unit derived from the aromatic vinyl compound in an amount of 0 to 55 mass % based on the total repeating unit present in the conjugated diene based polymer and a vinyl bond content of 7 to 65 mass % based on the total conjugated diene portion.
9. A modified conjugated diene based polymer produced by the process as recited in claim 1 .
10. A rubber composition comprising a modified conjugated diene based polymer produced by a process comprising
a step (a) of reacting a silicon compound with a conjugated diene based polymer having an active end so that the reaction takes place at the active end, the silicon compound having a protected primary amino group in the molecule thereof and a silicon atom to which a hydrocarbyloxy group and a reactive group are bonded, to thereby modify the active end, and
a step (b) of performing condensation reaction which involves the group derived from the silicon compound and bonded to the active end of the conjugated diene based polymer, in the presence of a titanium compound serving as a titanium-based condensation-accelerating agent,
wherein the protected amino group is capable of being deprotected by hydrolysis to be a primary amino group, and
wherein the titanium compound is at least one selected from the group consisting of tetrakis(2-ethyl-1,3-hexanediolato)titanium and titanium di-n-butoxide bis(2,4-pentanedionate).
11. A rubber composition as described in claim 10 , which comprises a rubber component containing 15 mass % or more of the modified conjugated diene based polymer in an amount of 100 parts by mass and silica and/or carbon black in the total amount of 20 to 120 parts by mass.
12. A rubber composition as described in claim 11 , wherein the rubber component comprises the modified conjugated diene based polymer in an amount of 15 to 100 mass % and at least one selected from the group consisting of a natural rubber, a synthetic isoprene rubber, a butadiene rubber, a styrene-butadiene rubber, an ethylene-α-olefin copolymer rubber, an ethylene-α-olefin-diene copolymer rubber, a chloroprene rubber, a halogenated butyl rubber, and a styrene-isobutylene copolymer having a halomethyl group, in an amount of 85 to 0 mass %.
13. A rubber composition as described in claim 10 , wherein the process further includes a deprotection step (c) of hydrolyzing the group derived from the silicon compound and bonded to the active end of the conjugated diene based polymer, whereby the protected primary amino group contained in the group bonded to the active end is converted to a free amino group.
14. A rubber composition as described in claim 10 , wherein wherein the silicon compound employed in the step (a) is a silicon compound represented by formula (I):
wherein each of R 1 and R 2 represents a hydrocarbon group having 1 to 20 carbon atoms, each of R 3 to R 5 represents a hydrocarbon group having 1 to 20 carbon atoms, R 6 represents a divalent hydrocarbon group having 1 to 12 carbon atoms, A represents a reactive group, and f is an integer of 1 to 10; or
a silicon compound represented by formula (III):
wherein each of R 1 and R 2 represents a hydrocarbon group having 1 to 20 carbon atoms, each of R 3 to R 5 represents a hydrocarbon group having 1 to 20 carbon atoms, R 6 represents a divalent hydrocarbon group having 1 to 12 carbon atoms, R 13 represents a divalent hydrocarbon group having 1 to 12 carbon atoms, A represents a reactive group, and f is an integer of 1 to 10.
15. A rubber composition as described in claim 14 , wherein the group A in formula (I) is a halogen atom or a hydrocarbyloxy group having 1 to 20 carbon atoms.
16. A rubber composition as described in claim 10 , wherein the conjugated diene based polymer having an active end is produced through anionic polymerization, in the presence of an organic alkali metal compound serving as a polymerization initiator, of a conjugated diene compound singly or of a conjugated diene compound and an aromatic vinyl compound in combination.
17. A rubber composition as described in claim 16 , wherein the conjugated diene compound is at least one selected from the group consisting of 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene.
18. A rubber composition as described in claim 16 , wherein the aromatic vinyl compound is styrene.
19. A rubber composition as described in claim 10 , wherein the conjugated diene based polymer has a repeating unit derived from an aromatic vinyl compound in an amount of 0 to 55 mass % based on the total repeating unit present in the conjugated diene based polymer and a vinyl bond content of 7 to 65 mass % based on the total conjugated diene portion.
20. A pneumatic tire employing the rubber composition as recited in claim 10 .
21. A pneumatic tire comprising a tread, a base tread, or a sidewall, wherein the tread, the base tread, or the sidewall employs the rubber composition as recited in claim 10 .