Method for producing denatured conjugated diene polymer
A method for producing a modified conjugated diene polymer usable as a raw material of a crosslinked polymer which is used for use in tires and the like of automobiles and can enhance low fuel consumption performance of automobiles and the like is provided. A method for producing a modified conjugated diene polymer comprising a polymerization step in which a monomer including a conjugated diene compound or a monomer including a conjugated diene compound and an aromatic vinyl compound is polymerized in the presence of at least one compound selected from the group consisting of the following formulae (1) and (2) and an alkali metal compound or an alkaline earth metal compound to obtain a modified conjugated diene polymer. (In the formulae, A 1 is a hydrocarbylsilyl group in which three H's (hydrogen atoms) in a “—SiH 3 ” structure are each substituted by a hydrocarbyl group, and R 1 and R 2 are hydrocarbylene groups.)
1. A method for producing a modified conjugated diene polymer, the method comprising:
polymerizing a monomer comprising a conjugated diene compound or a monomer comprising a conjugated diene compound and an aromatic vinyl compound in the presence of at least one compound selected from the group consisting of the following formulae (1) and (2) and an alkali metal compound or an alkaline earth metal compound, to obtain a first modified conjugated diene polymer:
wherein, in formulae (1) and (2):
A 1 is independently a hydrocarbylsilyl group in which the three hydrogen atoms of a SiH 3 structure are each substituted by a hydrocarbyl group; and
R 1 and R 2 are independently hydrocarbylene groups.
2. The method according to claim 1 , further comprising:
reacting the first modified conjugated diene polymer with a compound represented by formula (3), to obtain a second modified conjugated diene polymer having a structure represented by the following formula (6):
wherein, in formula (3):
A 2 is a functional group having at least one atom selected from the group consisting of N, P and S, having no active hydrogen and being bound to R 6 by any one atom of the above N, P and S, such that in a part or all of the at least one atom selected from the group consisting of the above N, P and S of A 2 is protected by a protecting group, wherein the protecting group is optionally a hydrocarbylsilyl group in which the three hydrogen atoms of a SiH 3 structure are each substituted by a hydrocarbyl group;
R 4 and R 5 are independently hydrocarbyl groups;
R 6 is a hydrocarbylene group; and
n is an integer of 0 to 2, and
wherein, in formula (6):
A 4 is a functional group having at least one atom selected from the group consisting of N, P and S and being bound to R 8 by any one atom of the above N, P and S, such that a part or all of the at least one atom selected from the group consisting of the above N, P and S of A 4 is protected by a protecting group, wherein the protecting group is optionally a hydrocarbylsilyl group in which the three hydrogen atoms of a SiH 3 structure are each substituted by a hydrocarbyl group;
R 6 is independently a hydrocarbyl group;
R 7 is independently a hydrogen atom or a hydrocarbyl group;
n is an integer of 0 to 2; and
R 8 is a hydrocarbylene group.
3. The method of claim 1 , wherein the first modified conjugated diene polymer is reacted with an onium-forming agent.
4. The method of claim 2 , wherein the first modified conjugated diene polymer is reacted with an onium-forming agent.
5. A modified conjugated diene polymer having a structure of formula (4) or a structure of formula (5) at one end and a structure of formula (6) at the other end:
wherein, in formulae (4) and (5):
A 3 is independently a hydrogen atom or a hydrocarbylsilyl group; and
R 1 and R 2 are independently hydrocarbylene groups, and
wherein, in formula (6):
A 4 is a functional group having at least one atom selected from the group consisting of N, P and S and being bound to R 8 by any one atom of the above N, P and S, such that a part or all of the at least one atom selected from the group consisting of the above N, P and S of A 4 is protected by a protecting group, wherein the protecting group is optionally a hydrocarbylsilyl group in which the three hydrogen atoms of a SiH 3 structure are each substituted by a hydrocarbyl group;
R 6 is independently a hydrocarbyl group;
R 7 is independently a hydrogen atom or a hydrocarbyl group;
n is an integer of 0 to 2; and
R 8 is a hydrocarbylene group.
6. A polymer composition, comprising:
the modified conjugated diene polymer according to claim 5 ;
carbon black and/or silica; and
a crosslinking agent.
7. A crosslinked polymer obtained by crosslinking the polymer composition according to claim 6 .
8. A tire, comprising the crosslinked polymer according to claim 7 as a material of a tread or a side wall.
9. A modified conjugated diene polymer having a structure of formula (4) or a structure of formula (5) at one end and a structure of formula (7) at the other end:
wherein, in formulae (4) and (5):
A 3 is independently a hydrogen atom or a hydrocarbylsilyl group; and
R 1 and R 2 are independently hydrocarbylene groups,
wherein, in formula (7):
A 5 is a group in which a functional group having at least one atom selected from the group consisting of N, P and S and bound to R 8 by any one atom of the above N, P and S is converted into an onium, such that a part or all of the at least one atom selected from the group consisting of the above N, P and S of A 5 is protected by a protecting group, wherein the protecting group is optionally a hydrocarbylsilyl group in which the three hydrogen atoms of a SiH 3 structure are each substituted by a hydrocarbyl group;
R 6 is independently a hydrocarbyl group;
R 7 is independently a hydrogen atom or a hydrocarbyl group;
n is an integer of 0 to 2; and
R 8 is a hydrocarbylene group.
10. A polymer composition, comprising:
the modified conjugated diene polymer according to claim 9 ;
carbon black and/or silica; and
a crosslinking agent.
11. A crosslinked polymer obtained by crosslinking the polymer composition according to claim 10 .
12. A tire, comprising the crosslinked polymer according to claim 11 as a material of a tread or a side wall.