Conjugated diene polymer and method for producing same

Patent metadata

Field	Value
Publication number	US-9745394-B2
Application number	US-201514970183-A
Country	US
Kind code	B2
Filing date	Dec 15, 2015
Priority date	Sep 12, 2011
Publication date	Aug 29, 2017
Grant date	Aug 29, 2017

Abstract

Conjugated diene polymer comprising at least a conjugated diene monomer unit, the conjugated diene polymer has a number-average molecular weight (Mn) in terms of polystyrene of 1,000 to 1,000,000, a ratio (Mw/Mn) of a weight-average molecular weight (Mw) to the number-average molecular weight (Mn) of lower than 2.0 and the polymer bears a halogen atom at a terminal of the polymer chain. Method for producing the conjugated diene polymer comprises subjecting a monomer containing at least a conjugated diene to living radical polymerization using a polymerization initiator comprising a halogenocyclopentadienyl triorganophosphine η 2 -olefin ruthenium complex represented by formula (6) (and an organic halide.

First claim

The invention claimed is:

1. A method for producing a conjugated diene polymer, which comprises subjecting a monomer containing at least a conjugated diene to living radical polymerization using a polymerization initiator comprising a halogenocyclopentadienyl triorganophosphine η 2 -olefin ruthenium complex represented by formula (6) and an organic halide

wherein in formula (6) R 11 , R 12 , R 13 and R 14 each represent a hydrogen atom, a cyano group, a carbonyl group represented by formula (7), an ester group represented by formula (8), an amide group represented by formula (9), a nitro group, or a halogen atom with the proviso that at least one of R 11 , R 12 , R 13 and R 14 is not a hydrogen atom; R 15 represents a chlorine atom, a bromine atom or an iodine atom; R 16 , R 17 and R 18 each represent an optionally substituted organic group having 1 to 10 carbon atoms; R 16 , R 17 and R 18 are the same as or different from each other; and L represents an optionally substituted cyclopentadienyl ring,

wherein in formula (7) Y 4 represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 10 carbon atoms,

wherein in formula (8) Y 5 represents a hydrogen atom or an optionally substituted organic group having 1 to 10 carbon atoms, and

wherein in formula (9) Y 6 and Y 7 each represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 10 carbon atoms,
wherein the conjugated diene polymer comprises at least a conjugated diene monomer unit, wherein the conjugated diene polymer has a number-average molecular weight (Mn) in terms of polystyrene of 1,000 to 1,000,000, a ratio (Mw/Mn) of a weight-average molecular weight (Mw) to the number-average molecular weight (Mn) of lower than 2.0 and the conjugated diene polymer bears a halogen atom at a terminal of the polymer chain, and
wherein 10% or higher of all conjugated diene polymer chains have a halogen atom at its terminal.

2. The method of claim 1 , wherein the conjugated diene polymer has at least one group selected from the group consisting of a group represented by formula (1), a group represented by formula (2), and a group represented by formula (3), as a terminal group of the polymer chain,

wherein in formula (1) X represents a chlorine atom, a bromine atom or an iodine atom; and R 1 , R 2 , R 3 and R 4 each represent a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom,

wherein in formula (2) X represents a chlorine atom, a bromine atom or an iodine atom; and R 5 , R 6 , R 7 and R 8 each represent a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom,

wherein in formula (3) X represents a chlorine atom, a bromine atom or an iodine atom; R 9 represents an aryl group, a cyano group, an ester group represented by formula (4), an amide group represented by formula (5), or a halogen atom; and R 10 represents a hydrogen atom or a methyl group,

wherein in formula (4) Y 1 represents a hydrogen atom or an optionally substituted organic group having 1 to 10 carbon atoms, and

wherein in formula (5) Y 2 and Y 3 each represent a hydrogen atom or an optionally substituted organic group having 1 to 10 carbon atoms; and Y 2 and Y 3 may be the same as or different from each other.

3. The method of claim 1 , wherein a ligand represented by formula (10) in the complex of formula (6) is an electron-withdrawing olefin copolymerizable with the conjugated diene monomer,

wherein in formula (10) R 11 , R 12 , R 13 and R 14 are the same as R 11 , R 12 , R 13 and R 14 , respectively, of formula (6).

4. The method of claim 2 , wherein a ligand represented by formula (10) in the complex of formula (6) is an electron-withdrawing olefin copolymerizable with the conjugated diene monomer,

wherein in formula (10) R 11 , R 12 , R 13 and R 14 are the same as R 11 , R R12 , R 13 and R 14 , respectively, of formula (6).

5. The method of claim 1 , wherein the polymerization is carried out by causing a halogenocyclopentadienyl bis(triorganophosphine) ruthenium represented by formula (11) to react with an electron-withdrawing olefin in a polymerization solvent to form a halogenocyclopentadienyl triorganophosphine η 2 -olefin ruthenium complex represented by formula (6) in the reaction system, and then adding a monomer, containing at least a conjugated diene monomer, and an organic halide to the complex,

wherein in formula (11) L is the same as L of formula (6); R 19 is the same as R 15 of formula (6); R 20 to R 25 each represent an optionally substituted organic group having 1 to 10 carbon atoms and may be the same as or different from each other; and either R 20 to R 22 or R 23 to R 25 corresponds to R 16 to R 18 of formula (6).

6. The method of claim 2 , wherein the polymerization is carried out by causing a halogenocyclopentadienyl bis(triorganophosphine) ruthenium represented by formula (11) to react with an electron-withdrawing olefin in a polymerization solvent to form a halogenocyclopentadienyl triorganophosphine η 2 -olefin ruthenium complex represented by formula (6) in the reaction system, and then adding a monomer, containing at least a conjugated diene monomer, and an organic halide to the complex,

wherein in formula (11) L is the same as L of formula (6); R 19 is the same as R 15 of formula (6); R 20 to R 25 each represent an optionally substituted organic group having 1 to 10 carbon atoms and may be the same as or different from each other; and either R 20 to R 22 or R 23 to R 25 corresponds to R 16 to R 18 of formula (6).

7. The method of claim 3 , wherein the polymerization is carried out by causing a halogenocyclopentadienyl bis(triorganophosphine) ruthenium represented by formula (11) to react with an electron-withdrawing olefin in a polymerization solvent to form a halogenocyclopentadienyl triorganophosphine η 2 -olefin ruthenium complex represented by formula (6) in the reaction system, and then adding a monomer, containing at least a conjugated diene monomer, and an organic halide to the complex,

wherein in formula (11) L is the same as L of formula (6); R 19 is the same as R 15 of formula (6); R 20

Assignees

• Zeon Corp
• Univ Kyoto

Inventors

• Bando Fumiaki
• Okuno Shingo
• Hayano Shigetaka
• Sawamoto Mitsuo
• Ouchi Makoto

Classifications

• C08F4/72

  selected from metals not provided for in group C08F4/44 (C08F4/54 - C08F4/70 take precedence) · CPC title

• C08F236/12

  with nitriles · CPC title

• C08F136/08 Primary

  Isoprene · CPC title

• C07F15/0046

  Ruthenium compounds · CPC title

• C08F236/04

  conjugated · CPC title