Hydrogenated conjugated diene polymer, polymer composition, crosslinked body and tire
A hydrogenated conjugated diene-based polymer which has a structure formed by bonding a nitrogen-containing compound having two or more alkoxysilyl groups and two or more nitrogen atoms with a plurality of conjugated diene-based polymer chains, wherein: when a composition ratio (molar ratio) in the hydrogenated conjugated diene-based polymer of each of a structural unit represented by formula (1), a structural unit represented by formula (2), a structural unit represented by formula (3), and a structural unit represented by formula (4) is p, q, r, and s, respectively, a value a represented by formula (i) is 0.80 or more and 0.97 or less, and an equilibrium storage modulus E′ of the hydrogenated conjugated diene-based polymer is 2.4 MPa or more, α=( p +(0.5× r ))/( p+q +(0.5× r )+ s ) (i)
1. A hydrogenated conjugated diene-based polymer, which has a structure formed by bonding a nitrogen-containing compound having two or more alkoxysilyl groups and two or more nitrogen atoms with a plurality of conjugated diene-based polymer chains,
wherein, when a composition ratio (molar ratio) in the hydrogenated conjugated diene-based polymer of each of a structural unit represented by formula (1), a structural unit represented by formula (2), a structural unit represented by formula (3), and a structural unit represented by formula (4) is p, q, r, and s, respectively, a value α represented by formula (i) is 0.80 or more and 0.97 or less, and an equilibrium storage modulus E′ of the hydrogenated conjugated diene-based polymer is 2.4 MPa or more,
α=( p +(0.5× r ))/( p+q +(0.5× r )+ s ) (i)
2. The hydrogenated conjugated diene-based polymer of claim 1 , wherein the conjugated diene-based polymer chains have a structural unit derived from an aromatic vinyl compound.
3. The hydrogenated conjugated diene-based polymer of claim 1 , wherein the conjugated diene-based polymer chains are random copolymer chains of a conjugated diene compound and an aromatic vinyl compound.
4. The hydrogenated conjugated diene-based polymer of claim 1 , wherein the nitrogen-containing compound is at least one selected from the group consisting of a compound represented by formula (5) and a compound represented by formula (6),
in which: R 1 and R 2 are each independently a hydrocarbyl group having 1 to 20 carbon atoms; R 3 is an alkanediyl group having 1 to 20 carbon atoms; A 1 is a group “*—C(R 5 )═N—” or a group “*—N═C(R 5 )—” (where R 5 is a hydrogen atom or hydrocarbyl group, and “*” represents a bond that binds to R 4 ); R 4 has an m-valent hydrocarbon group having 1 to 20 carbon atoms, or is an m-valent group having 1 to 20 carbon atoms that has at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and in which no active hydrogen is bonded to the at least one atom (where m is an integer of 2 to 10); n is an integer of 1 to 3; and a plurality of R 1 , R 2 , R 3 , A 1 , and n are the same group or different groups from each other,
in which: R 6 , R 7 , R 10 , and R 11 are each independently a hydrocarbyl group having 1 to 20 carbon atoms; R 8 and R 9 are each independently an alkanediyl group having 1 to 20 carbon atoms; A 2 is a group represented by formula (7), a group represented by formula (8), a group represented by formula (9), or a group represented by formula (10); w and p are each independently an integer of 1 to 3; and a plurality of R 6 , R 7 , R 10 , and R 11 are the same group or different groups, respectively,
in which: R 12 , R 13 , and R 15 are each independently a hydrocarbyl group having 1 to 20 carbon atoms; R 14 and R 16 are each independently an alkanediyl group having 1 to 20 carbon atoms; q is an integer of 1 to 3; r is an integer of 0 to 2; a plurality of R 12 to R 15 and q are the same group or different groups, respectively; and “*” represents a bond that binds to the nitrogen atom in formula (6),
in which: R 19 is an alkanediyl group having 3 to 20 carbon atoms; R 19 , the nitrogen atom and the silicon atom form a ring structure of 5 or more members; R 17 and R 18 are each independently a hydrocarbyl group having 1 to 20 carbon atoms; R 20 is an alkanediyl group having 1 to 20 carbon atoms; s is 1 or 2; a plurality of R 17 and R 18 are the same group or different groups, respectively; and “*” represents a bond that binds to the nitrogen atom in formula (6),
in which: R 23 is an alkanediyl group having 1 to 20 carbon atoms; R 21 is a hydrocarbylidene group having 1 to 20 carbon atoms; R 22 is an alkanediyl group or an alkenediyl group having 1 to 20 carbon atoms; R 21 , R 22 and the two nitrogen atoms form a ring structure of 5 or more members; and “*” represents a bond that binds to the nitrogen atom in formula (6), and
in which: R 26 is a hydrocarbylene group having 1 to 20 carbon atoms; R 24 and R 25 are each independently a hydrocarbyl group having 1 to 20 carbon atoms, or R 24 and R 25 together represent a ring structure of 4 to 20 carbon atoms formed together with the nitrogen atom to which R 24 and R 25 are bonded, or R 24 and R 25 together represent a ring structure of 5 or more members formed together with the nitrogen atom shown above in formula (10) and a nitrogen atom different from the nitrogen atom shown above in formula (10) or an oxygen atom; and “*” represents a bond that binds to the nitrogen atom in formula (6).
5. The hydrogenated conjugated diene-based polymer of claim 1 , which has a molecular weight distribution measured by gel permeation chromatography (GPC) of 1.1 or more and 2.0 or less, and has a peak top molecular weight of a peak having a smallest molecular weight in the hydrogenated conjugated diene-based polymer in a range of 1.0×10 5 to 2.0×10 6 .
6. The hydrogenated conjugated diene-based polymer of claim 1 , wherein the value α is 0.88 or more and 0.97 or less.
7. A polymer composition, comprising the hydrogenated conjugated diene-based polymer of claim 1 and an inorganic filler.
8. A crosslinked body, obtained by a process comprising crosslinking the polymer composition of claim 7 .
9. A tire, wherein one or both of a tread and a sidewall are formed using the polymer composition of claim 7 .
10. The hydrogenated conjugated diene-based polymer of claim 2 , wherein the conjugated diene-based polymer chains are random copolymer chains of a conjugated diene compound and an aromatic vinyl compound.
11. The hydrogenated conjugated diene-based polymer of claim 2 , wherein the nitrogen-containing compound is at least one selected from the group consisting of a compound represented by formula (5) and a compound represented by formula (6),
in which: R 1 and R 2 are each independently a hydrocarbyl group having 1 to 20 carbon atoms; R 3 is an alkanediyl group having 1 to 20 carbon atoms; A 1 is a group “*—C(R 5 )═N—” or a group “*—N═C(R 5 )—” (where R 5 is a hydrogen atom or hydrocarbyl group, and “*” represents a bond that binds to R 4 ); R 4 has an m-valent hydrocarbon group having 1 to 20 carbon atoms, or is an m-valent group having 1 to 20 carbon atoms that has at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and in which no active hydrogen is bonded to the at least one atom (where m is an integer of 2 to 10); n is an integer of 1 to 3; and a plurality of R 1 , R 2 , R 3 , A 1 , and n are the same group or different groups from each other,
in which: R 6 , R 7 , R 10 , and R 11 are each independently a hydrocarbyl group having 1 to 20 carbon atoms; R 8 and R 9 are each independently an alkanediyl group having 1 to 20 carbon atoms; A 2 is a group represented by formula (7), a group represented by formula (8), a group represented by formula (9), or a group represented by formula (10); w and p are each independently an integer of 1 to 3; and a plurality of R 6 , R 7 , R 10 , and R 11 are the same group or different groups, respectively,
in which: R 12 , R 13 , and R 15 are each independently a hydrocarbyl group having 1 to 20 carbon atoms; R 14 and R 16 are each independently an alkanediyl group having 1 to 20 carbon atoms; q is an integer of 1 to 3; r is an integer of 0 to 2; a plurality of R 12 to R 15 and q are the same group or different groups, respectively; and “*” represents a bond that binds to the nitrogen atom in formula (6),
in which: R 19 is an alkanediyl group having 3 to 20 carbon atoms; R 19 , the nitrogen atom and the silicon atom form a ring structure of 5 or more members; R 17 and R 18 are each independently a hydrocarbyl group having 1 to 20 carbon atoms; R 20 is an alkanediyl group having 1 to 20 carbon atoms; s is 1 or 2; a plurality of R 17 and R 18 are the same group or different groups, respectively; and “*” represents a bond that binds to the nitrogen atom in formula (6),
in which: R 23 is an alkanediyl group having 1 to 20 carbon atoms; R 21 is a hydrocarbylidene group having 1 to 20 carbon atoms; R 22 is an alkanediyl group or an alkenediyl group having 1 to 20 carbon atoms; R 21 , R 22 and the two nitrogen atoms form a ring structure of 5 or more members; and “*” represents a bond that binds to the nitrogen atom in formula (6), and
in which: R 26 is a hydrocarbylene group having 1 to 20 carbon atoms; R 24 and R 25 are each independently a hydrocarbyl group having 1 to 20 carbon atoms, or R 24 and R 25 together represent a ring structure of 4 to 20 carbon atoms formed together with the nitrogen atom to which R 24 and R 25 are bonded, or R 24 and R 25 together represent a ring structure of 5 or more members formed together with the nitrogen atom shown above in formula (10) and a nitrogen atom different from the nitrogen atom shown above in formula (10) or an oxygen atom; and “*” represents a bond that binds to the nitrogen atom in formula (6).
12. The hydrogenated conjugated diene-based polymer of claim 3 , wherein the nitrogen-containing compound is at least one selected from the group consisting of a compound represented by formula (5) and a compound represented by formula (6),
in which: R 1 and R 2 are each independently a hydrocarbyl group having 1 to 20 carbon atoms; R 3 is an alkanediyl group having 1 to 20 carbon atoms; A 1 is a group “*—C(R 5 )═N—” or a group “*—N═C(R 5 )—” (where R 5 is a hydrogen atom or hydrocarbyl group, and “*” represents a bond that binds to R 4 ); R 4 has an m-valent hydrocarbon group having 1 to 20 carbon atoms, or is an m-valent group having 1 to 20 carbon atoms that has at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and in which no active hydrogen is bonded to the at least one atom (where m is an integer of 2 to 10); n is an integer of 1 to 3; and a plurality of R 1 , R 2 , R 3 , A 1 , and n are the same group or different groups from each other,
in which: R 6 , R 7 , R 10 , and R 11 are each independently a hydrocarbyl group having 1 to 20 carbon atoms; R 8 and R 9 are each independently an alkanediyl group having 1 to 20 carbon atoms; A 2 is a group represented by formula (7), a group represented by formula (8), a group represented by formula (9), or a group represented by formula (10); w and p are each independently an integer of 1 to 3; and a plurality of R 6 , R 7 , R 10 , and R 11 are the same group or different groups, respectively,
in which: R 12 , R 13 , and R 15 are each independently a hydrocarbyl group having 1 to 20 carbon atoms; R 14 and R 16 are each independently an alkanediyl group having 1 to 20 carbon atoms; q is an integer of 1 to 3; r is an integer of 0 to 2; a plurality of R 12 to R 15 and q are the same group or different groups, respectively; and “*” represents a bond that binds to the nitrogen atom in formula (6),
in which: R 19 is an alkanediyl group having 3 to 20 carbon atoms; R 19 , the nitrogen atom and the silicon atom form a ring structure of 5 or more members; R 17 and R 18 are each independently a hydrocarbyl group having 1 to 20 carbon atoms; R 20 is an alkanediyl group having 1 to 20 carbon atoms; s is 1 or 2; a plurality of R 17 and R 18 are the same group or different groups, respectively; and “*” represents a bond that binds to the nitrogen atom in formula (6),
in which: R 23 is an alkanediyl group having 1 to 20 carbon atoms; R 21 is a hydrocarbylidene group having 1 to 20 carbon atoms; R 22 is an alkanediyl group or an alkenediyl group having 1 to 20 carbon atoms; R 21 , R 22 and the two nitrogen atoms form a ring structure of 5 or more members; and “*” represents a bond that binds to the nitrogen atom in formula (6), and
in which: R 26 is a hydrocarbylene group having 1 to 20 carbon atoms; R 24 and R 25 are each independently a hydrocarbyl group having 1 to 20 carbon atoms, or R 24 and R 25 together represent a ring structure of 4 to 20 carbon atoms formed together with the nitrogen atom to which R 24 and R 25 are bonded, or R 24 and R 25 together represent a ring structure of 5 or more members formed together with the nitrogen atom shown above in formula (10) and a nitrogen atom different from the nitrogen atom shown above in formula (10) or an oxygen atom; and “*” represents a bond that binds to the nitrogen atom in formula (6).
13. The hydrogenated conjugated diene-based polymer of claim 2 , which has a molecular weight distribution measured by gel permeation chromatography (GPC) of 1.1 or more and 2.0 or less, and has a peak top molecular weight of a peak having a smallest molecular weight in the hydrogenated conjugated diene-based polymer in a range of 1.0×10 5 to 2.0×10 6 .
14. The hydrogenated conjugated diene-based polymer of claim 3 , which has a molecular weight distribution measured by gel permeation chromatography (GPC) of 1.1 or more and 2.0 or less, and has a peak top molecular weight of a peak having a smallest molecular weight in the hydrogenated conjugated diene-based polymer in a range of 1.0×10 5 to 2.0×10 6 .
15. The hydrogenated conjugated diene-based polymer of claim 4 , which has a molecular weight distribution measured by gel permeation chromatography (GPC) of 1.1 or more and 2.0 or less, and has a peak top molecular weight of a peak having a smallest molecular weight in the hydrogenated conjugated diene-based polymer in a range of 1.0×10 5 to 2.0×10 6 .
16. The hydrogenated conjugated diene-based polymer of claim 2 , wherein the value α is 0.88 or more and 0.97 or less.
17. The hydrogenated conjugated diene-based polymer of claim 3 , wherein the value α is 0.88 or more and 0.97 or less.
18. The hydrogenated conjugated diene-based polymer of claim 4 , wherein the value α is 0.88 or more and 0.97 or less.
19. The hydrogenated conjugated diene-based polymer of claim 5 , wherein the value α is 0.88 or more and 0.97 or less.
20. A polymer composition, comprising the hydrogenated conjugated diene-based polymer of claim 2 and an inorganic filler.