Modified conjugated diene-based polymer and method for producing the same, and modified conjugated diene-based polymer composition

Patent metadata

Field	Value
Publication number	US-10766972-B2
Application number	US-201615551548-A
Country	US
Kind code	B2
Filing date	Feb 19, 2016
Priority date	Feb 19, 2015
Publication date	Sep 8, 2020
Grant date	Sep 8, 2020

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.

First claim

The invention claimed is:

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.

2. 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.

3. 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.

4. 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.

5. 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.

6. 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.

7. The modified conjugated diene-based polymer according to claim 1 , represented by following general formula (A) or (B):

wherein
R 21 to R 24 each independently denote an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms;
R 25 and R 26 each independently denote an alkylene group having 1 to 20 carbon atoms;
R 27 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 R 21 , R 23 , or (Polym) they are independent of each other;

wherein
R 28 to R 33 each independently denote an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms;
R 34 to R 36 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 R 28 , R 30 , R 32 , or (Polym) they are independent of each other;

wherein
R 10 and R 11 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;
R 10 and R 11 may be attached together to form a cyclic structure together with an adjacent nitrogen atom, and in this case, R 10 and R 11 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
R 15 and R 16 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;
R 15 and R 16 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;
R 14 denotes an alkylene group having 1 to 20 carbon atoms or a conjugated diene-based polymer having 1 to 20 carbon atoms;

wherein
R 15 and R 16 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
R 15 and R 16 may be attached together to form a cyclic structure together with an adjacent nitrogen atom, and in this case, R 15 and R 16 denote an alkylene group having 5 to 12 carbon atoms, and may have a branched structure in a part thereof;

wherein
R 17 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
R 18 denotes an alkyl group having 1 to 12 carbon atoms, and may have a branched structure in a part thereof.

8. 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.

9. 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 R 1 to R 4 each independently denote an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms; R 5 denotes an alkylene group having 1 to 10 carbon atoms; R 6 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 R 1 to R 4 , they are independent of each other;

wherein R 1 to R 6 each indepe

Assignees

• Asahi Chemical Ind

Inventors

• Yamada Chigusa
• Yamaura Yukio
• Hisamura Kenta
• Yoshida Junichi

Classifications

• C08F236/06 Primary

  Butadiene · CPC title

• C08L47/00

  Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers (C08L45/00 takes precedence; of conjugated diene rubbers C08L9/00 - C08L21/00) · CPC title

• C08L9/06

  Copolymers with styrene · CPC title

• C08K5/5477

  containing nitrogen in a heterocyclic ring · CPC title

• C08K5/5445

  containing at least one Si-N bond · CPC title