# US 10,766,972 B2 · Modified conjugated diene-based polymer and method for producing the same, and modified conjugated diene-based polymer composition

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- Number: US 10,766,972 B2
- Document ID: US10766972B2
- Status: Granted
- Kind: B2
- Application number: 15/551,548
- Filed: 2016-02-19
- Published: 2018-02-08
- Granted: 2020-09-08
- Earliest claimed: 2015-02-19
- Assignees: Asahi Kasei Kabushiki Kaisha
- Applicants: Asahi Kasei Kabushiki Kaisha
- Inventors: Chigusa Yamada; Yukio Yamaura; Kenta Hisamura; Junichi Yoshida
- Web page: https://patentgrep.com/patent/US10766972B2

## CPC

- C08C 19/25: Incorporating silicon atoms into the molecule
- C08F 8/00: Chemical modification by after-treatment (graft polymers, block polymers, crosslinking with unsaturated monomers or with polymers C08F251/00 - C08F299/00; of conjugated diene rubbers C08C)
- C08F 236/06: Butadiene
- C08K 3/36: Silica
- C08L 9/06: Copolymers with styrene
- C08L 15/00: Compositions of rubber derivatives (C08L11/00, C08L13/00 take precedence)
- C08C: TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)

## Abstract

The present invention provides a modified conjugated diene-based polymer, wherein the Mooney stress-relaxation rate measured at 110° C. is 0.45 or less, and the modification percentage is 75% by mass or more.

## Claims

### Claim 1

A modified conjugated diene-based polymer comprising a nitrogen atom,
wherein a content of the nitrogen atom is 40 ppm by mass or more based on a total amount of the modified conjugated diene-based polymer,
a Mooney stress-relaxation rate measured at 110° C. is 0.45 or less,
a modification percentage is 84.8% by mass or more, and
a ratio of a first weight-average molecular weight to a first number-average molecular weight is 1.50 or more and 3.50 or less.

### Claim 2 (depends on 1)

The modified conjugated diene-based polymer according to claim 1, comprising a nitrogen atom at one or more terminal, and a star-shaped polymer structure having a nitrogen atom-containing alkoxysilane substituent positioned at a center thereof.

### Claim 3 (depends on 1)

The modified conjugated diene-based polymer according to claim 1, wherein a shrinkage factor (g′) determined by gel permeation chromatography (GPC)-light scattering measurement with a viscosity detector is 0.86 or less.

### Claim 4 (depends on 1)

The modified conjugated diene-based polymer according to claim 1, wherein a ratio of a second number-average molecular weight determined by GPC-light scattering measurement to the first number-average molecular weight determined by measurement with GPC is 1.00 or more.

### Claim 5 (depends on 1)

The modified conjugated diene-based polymer according to claim 1, wherein a ratio of a second weight-average molecular weight determined by GPC-light scattering measurement to the first weight-average molecular weight determined by measurement with GPC is 1.00 or more.

### Claim 6 (depends on 1)

The modified conjugated diene-based polymer according to claim 1, wherein the first number-average molecular weight is 200000 or more and 2000000 or less.

### Claim 7 (depends on 1)

The modified conjugated diene-based polymer according to claim 1, represented by following general formula (A) or (B):
wherein
R21 to R24 each independently denote an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms;
R25 and R26 each independently denote an alkylene group having 1 to 20 carbon atoms;
R27 denotes a hydrogen atom, a silyl group substituted with a hydrocarbon, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms;
a and c each independently denote an integer of 1 or 2;
b and d each independently denote an integer of 0 or 1;
(a+b) and (c+d) each independently denote an integer of 2 or less;
(Polym) denotes a conjugated diene-based polymer derived by polymerization of a conjugated diene compound or copolymerization of a conjugated diene compound and an aromatic vinyl compound,
wherein at least one terminal thereof is a functional group represented by any of general formulas (4) to (7) below; in a case that a plurality of moieties is present as R21, R23, or (Polym) they are independent of each other;
wherein
R28 to R33 each independently denote an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms;
R34 to R36 each independently denote an alkylene group having 1 to 20 carbon atoms;
a, c, and e each independently denote an integer of 1 or 2;
b, d, and f each independently denote an integer of 0 or 1;
(a+b), (c+d), and (e+f) each independently denote an integer of 2 or less;
(Polym) denotes a conjugated diene-based polymer derived by polymerization of a conjugated diene compound or copolymerization of a conjugated diene compound and an aromatic vinyl compound,
wherein at least one terminal thereof is a functional group represented by any of following general formulas (4) to (7); in a case that a plurality of moieties is present as R28, R30, R32, or (Polym) they are independent of each other;
wherein
R10 and R11 are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms;
R10 and R11 may be attached together to form a cyclic structure together with an adjacent nitrogen atom, and in this case, R10 and R11 denote an alkylene group having 5 to 12 carbon atoms, and may have an unsaturated bond or a branched structure in a part thereof;
wherein
R15 and R16 are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aralkyl group having 6 to 20 carbon;
R15 and R16 may be attached together to form a cyclic structure together with an adjacent nitrogen atom, and in this case, RB and RB denote an alkylene group having 5 to 12 carbon atoms, and may have an unsaturated bond or a branched structure in a part thereof;
R14 denotes an alkylene group having 1 to 20 carbon atoms or a conjugated diene-based polymer having 1 to 20 carbon atoms;
wherein
R15 and R16 are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aryl group having 6 to 20 carbon atoms; and
R15 and R16 may be attached together to form a cyclic structure together with an adjacent nitrogen atom, and in this case, R15 and R16 denote an alkylene group having 5 to 12 carbon atoms, and may have a branched structure in a part thereof;
wherein
R17 denotes a hydrocarbon group having 2 to 10 carbon atoms, and may have an unsaturated bond or a branched structure in a part thereof; and
R18 denotes an alkyl group having 1 to 12 carbon atoms, and may have a branched structure in a part thereof.

### Claim 8 (depends on 1)

A method for producing the modified conjugated diene-based polymer according to claim 1, comprising steps of:
polymerizing at least a conjugated diene compound in a presence of an organolithium compound having at least one nitrogen atom in a molecule to obtain a conjugated diene-based polymer; and
modifying the conjugated diene-based polymer with a modifier having four or more alkoxy groups bonding to a silyl group and a tertiary amino group in one molecule.

### Claim 9 (depends on 8)

The method for producing the modified conjugated diene-based polymer according to claim 8, wherein the modifier comprises a modifier represented by any of following general formulas (1) to (3):
wherein R1 to R4 each independently denote an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms; R5 denotes an alkylene group having 1 to 10 carbon atoms; R6 denotes an alkylene group having 1 to 20 carbon atoms; m denotes an integer of 1 or 2; n denotes an integer of 2 or 3; (m+n) denotes an integer of 4 or more; and in a case that a plurality of moieties is present as any of R1 to R4, they are independent of each other;
wherein R1 to R6 each independently denote an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms; R7 to R9 each independently denote an alkylene group having 1 to 20 carbon atoms; m, n, and I each independently denote an integer of 1 to 3; (m+n+1) denotes an integer of 4 or more; and in a case that a plurality of moieties is present as any of R1 to R6, they are independent of each other;
wherein R1 to R4 each independently denote an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms; R5 and R6 each independently denote an alkylene group having 1 to 20 carbon atoms; m and n each independently denote an integer of 1 to 3; (m+n) denotes an integer of 4 or more; R7 denotes an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a silyl group substituted with a hydrocarbon group; and in a case that a plurality of moieties is present as any of R1 to R4, they are independent of each other.

### Claim 10 (depends on 9)

The method for producing the modified conjugated diene-based polymer according to claim 9, wherein the modifier comprises a modifier represented by the formula (1) with m and n therein being 2 and 3, respectively, or the modifier comprises a modifier represented by the formula (2) with each of m, n, and I therein being 3.

### Claim 11 (depends on 8)

The method for producing the modified conjugated diene-based polymer according to claim 8, wherein the organolithium compound comprises an organolithium compound represented by any of following general formulas (14) to (17):
wherein R10 and R11 are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms; R10 and R11 may be attached together to form a cyclic structure together with an adjacent nitrogen atom, and in this case, R10 and R11 denote an alkylene group having 5 to 12 carbon atoms, and may have an unsaturated bond or a branched structure in a part thereof;
wherein R12 and R13 are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms; R12 and R13 may be attached together to form a cyclic structure together with an adjacent nitrogen atom, and in this case, R12 and R13 denote an alkyl group having 5 to 12 carbon atoms, and may have an unsaturated bond or a branched structure in a part thereof; and V denotes an alkylene group having 1 to 20 carbon atoms or a conjugated diene-based polymer having 4 to 20 carbon atoms;
wherein R15 and R16 are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aryl group having 6 to 20 carbon atoms; R15 and R16 may be attached together to form a cyclic structure together with an adjacent nitrogen atom, and in this case, R15 and R16 denote an alkylene group having 5 to 12 carbon atoms, and may have a branched structure in a part thereof;
wherein R17 denotes a hydrocarbon group having 2 to 10 carbon atoms, and may have an unsaturated bond or a branched structure in a part thereof; and R18 denotes an alkyl group having 1 to 12 carbon atoms, and may have a branched structure in a part thereof.

### Claim 12 (depends on 8)

The method for producing the modified conjugated diene-based polymer according to claim 8, wherein, in the polymerization step, polymerization is performed in a continuous type, a polymerization temperature is 45° C. or more and 80° C. or less, and a solid content is 16% by mass or less.

### Claim 13 (depends on 8)

The method for producing the modified conjugated diene-based polymer according to claim 8, wherein, in the polymerization step, polymerization is performed in a continuous type, and a concentration of the organolithium compound is 0.010 mol/L or less based on a volume of a hydrocarbon solvent.

### Claim 14 (depends on 8)

A modified conjugated diene-based polymer obtained through the method for producing the modified conjugated diene-based polymer according to claim 8.

### Claim 15 (depends on 8)

The method for producing the modified conjugated diene-based polymer according to claim 8, wherein the modifier comprises a modifier represented by general formula (1):
wherein
R1 to R4 each independently denote an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms;
R5 denotes an alkylene group having 1 to 10 carbon atoms;
R6 denotes an alkylene group having 1 to 20 carbon atoms;
m denotes an integer of 1 or 2;
n denotes an integer of 2 or 3;
(m+n) denotes an integer of 4 or more; and
in a case that a plurality of moieties is present as any of R1 to R4, they are independent of each other.

### Claim 16 (depends on 8)

The method for producing the modified conjugated diene-based polymer according to claim 8, wherein the organolithium compound comprises an organolithium compound represented by general formula (14):
wherein
R10 and R11 are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms;
R10 and R11 may be attached together to form a cyclic structure together with an adjacent nitrogen atom, and in this case, R10 and R11 denote an alkylene group having 5 to 12 carbon atoms, and may have an unsaturated bond or a branched structure in a part thereof.

### Claim 17 (depends on 1)

A modified conjugated diene-based polymer composition comprising:
a rubber component and
0.5 parts by mass or more and 300 parts by mass or less of a silica-based inorganic filler based on 100 parts by mass of the rubber component,
wherein the rubber component comprises 20 parts by mass or more of the modified conjugated diene-based polymer according to claim 1 based on 100 parts by mass of the rubber component.

### Claim 18

A method for producing a modified conjugated diene-based polymer comprising a nitrogen atom, the method comprising steps of:
polymerizing at least a conjugated diene compound in a presence of an organolithium compound having at least one nitrogen atom in a molecule to obtain a conjugated diene-based polymer; and
modifying the conjugated diene-based polymer with a modifier having four or more alkoxy groups bonding to a silyl group and a tertiary amino group in one molecule,
wherein, in the modification step, a content of the conjugated diene compound is 100 ppm by mass or more and 50000 ppm by mass or less based on a total amount of a monomer and a polymer,
wherein the modified conjugated diene-based polymer comprising a nitrogen atom has a content of the nitrogen atom of 25 ppm by mass or more based on a total amount of the modified conjugated diene-based polymer,
a Mooney stress-relaxation rate measured at 110° C. of 0.45 or less,
a modification percentage of 75% by mass or more, and
a ratio of a first weight-average molecular weight to a first number-average molecular weight of 1.50 or more and 3.50 or less.

### Claim 19 (depends on 18)

The method according to claim 18, wherein the modified conjugated diene-based polymer comprising a nitrogen atom has a content of the nitrogen atom of 40 ppm by mass or more based on a total amount of the modified conjugated diene-based polymer,
a Mooney stress-relaxation rate measured at 110° C. of 0.45 or less,
a modification percentage of 84.8% by mass or more, and
a ratio of a first weight-average molecular weight to a first number-average molecular weight of 1.50 or more and 3.50 or less.