Catalyst for synthesizing polyolefins

Patent metadata

Field	Value
Publication number	US-9303101-B2
Application number	US-201314400188-A
Country	US
Kind code	B2
Filing date	Apr 30, 2013
Priority date	May 11, 2012
Publication date	Apr 5, 2016
Grant date	Apr 5, 2016

Abstract

The present invention relates to a method for producing a high-molecular-weight copolymer of polar group-containing allyl monomers comprising monomer units represented by formulae (3) and (4) (in the formulae, R 1 represents a hydrogen atom (H) or hydrocarbon group having 1 to 6 carbon atoms; R 2 represents —OH, —OCOR 3 (R 3 represents hydrocarbon group having 1 to 5 carbon atoms), —N(R 4 ) 2 (R 4 represents a hydrogen atom or hydrocarbon group having 1 to 5 carbon atoms); and n and m are a value representing the molar ratio of each of the monomer units), which has few branches and unsaturated group at the molecular end, by copolymerizing olefin and an allyl compound using a metal complex of group 10 elements in the periodic system represented by formula (I) as a catalyst.
The present invention enables providing a high-molecular-weight copolymer of polar group-containing allyl monomers, which copolymer has a novel structure, is available for various applications and has been considered to be difficult to synthesize by other polymerization methods such as radical polymerization; and a method for producing the same.

First claim

The invention claimed is:

1. A method for producing copolymers, comprising a process of reacting non-polar olefins with polar olefins under polymerization conditions in the presence of a catalyst composition containing an organometallic compound,
wherein polar olefins are represented by formula (VII)
CH 2 ═CR 13 R 14   (VII)

wherein R 13 represents a hydrogen atom or a methyl group; R 14 represents —COOR 15 , —CN, —OCOR 15 , —OR 15 , —CH 2 —OCOR 15 , —CH 2 OH, —CH 2 —N(R 16 ) 2 or —CH 2 —Hal, wherein R 15 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 18 carbon atoms; R 16 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 18 carbon atoms or an alkoxycarbonyl group; and Hal represents a halogen atom, and
wherein the organometallic compound contains bisphosphine monoxide (BPMO) represented by formula (I) and a metal center M comprising elements belonging to Group 10 in the periodic system that forms a complex with BPMO

R 1a , R 1b , R 2a and R 2b may be the same or different with each other, and independently represent a substituted or unsubstituted alkyl group having 1 to 14 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 14 carbon atoms, a substituted or unsubstituted biphenyl group or a substituted or unsubstituted aryl group; a pair of R 1a and R 1b and a pair of R 2a and R 2b may be bonded to form a ring structure; and A 1 represents an arylene group, a monocyclic heteroarylene group, a bivalent heterocyclic group, an alkylene group having 1 to 2 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, an alkenylene group having 2 to 8 carbon atoms, or a cycloalkenylene group having 3 to 10 carbon atoms.

2. The method for producing copolymers as claimed in claim 1 , wherein both of R 1a and R 1b are isopropyl group or t-butyl group.

3. The method for producing copolymers as claimed in claim 1 , wherein both of R 2a and R 2b are t-butyl group.

4. The method for producing copolymers as claimed in claim claim 1 , wherein R 14 is CH 2 —OCOR 15 , CH 2 OH, —CH 2 —N(R 16 ) 2 or —CH 2 —Hal.

5. The method for producing copolymers as claimed in claim 1 , wherein the organometallic compound is represented by formula (II)

wherein
M represents an element belonging to Group 10 in the periodic system;
R 1a , R 1b , R 2a and R 2b may be the same or different with each other, and independently represent a substituted or unsubstituted alkyl group having 1 to 14 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 14 carbon atoms, a substituted or unsubstituted biphenyl group or a substituted or unsubstituted aryl group; a pair of R 1a and R 1b and a pair of R 2a and R 2b may be bonded to form a ring structure;
A 1 represents an arylene group, a monocyclic heteroarylene group, a bivalent heterocyclic group, an alkylene group having 1 to 2 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, an alkenylene group having 2 to 8 carbon atoms, or a cycloalkenylene group having 3 to 10 carbon atoms;
R 3 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or a bivalent group represented by A 2 (A 2 represents an arylene group, a monocyclic heteroarylene group, a monocyclic cycloalkylene group, a monocyclic cycloalkenylene group, a monocyclic heterocycloalkylene group, a monocyclic heterocycloalkenylene group, a heterocyclic group or a C2-C4 alkylene group;
R 4 represents a neutral electron-donating ligand; R 3 and R 4 may be crosslinked; when R 3 and R 4 are crosslinked, L represents a single bond or a bivalent group selected from an alkylene group, a haloalkylene group, an alkenylene group or an alkynylene group; and when R 3 and R 4 are not crosslinked (that is, when L does not exist), R 4 needs not to exist; and
X − represents a counterion of the cationic organometallic compound.

6. The method for producing copolymers as claimed in claim 5 , wherein ligand R 4 is:
(i) selected from pyridine, a substituted pyridine, a nitrile compound, ammonia, an alkylamine, a substituted alkylamine, an arylamine or a substituted arylamine; or
(ii) represented by formula (1)

(wherein W represents C or S; Z is selected from O, S, NH or NR a (R a represents an alkyl group or an aryl group) and Y needs not to exist; when Y exists, Y is selected from O, S, NH or NR b (R b represents an alkyl group or an aryl group); R 5 represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, —OR c (R c represents an alkyl group or an aryl group) or —NR d 2 (R d represents an alkyl group or an aryl group).

7. The method for producing copolymers as claimed in claim 1 , wherein the organometallic compound is represented by formula (IIa)

wherein
M represents an element belonging to Group 10 in the periodic system;
R 1a , R 1b , R 2a and R 2b may be the same or different with each other, and independently represent a substituted or unsubstituted alkyl group having 1 to 14 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 14 carbon atoms, a substituted or unsubstituted biphenyl group or a substituted or unsubstituted aryl group; a pair of R 1a and R 1b and a pair of R 2a and R 2b may be bonded to form a ring structure;
R 6 represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group or an aryl group;
A 1 represents an arylene group, a monocyclic heteroarylene group, a bivalent heterocyclic group, an alkylene group having 1 to 2 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, an alkenylene group having 2 to 8 carbon atoms, or a cycloalkenylene group having 3 to 10 carbon atoms; and
X − represents a counterion of the cationic organometallic compound.

8. The method for producing copolymers as claimed in claim 7 , wherein A 1 is a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group or substituted or an unsubstituted methylene group.

9. The method for producing copolymers as claimed in claim 7 , wherein R 1a , R 1b , R 2a and R 2b independently represent a branched alkyl group having 3 to 6 carbon atoms.

10. The method for producing copolymers as claimed in claim 7 , wherein X— is selected from SbF 6 − , BPh 4 − , BArF 4 − (ArF 4 is [3,5-(CF 3 ) 2 C 6 H 3 ] 4 ), BF 4 − or PF 6 − .

11. The method for producing copolymers as claimed in claim 7 , wherein M is palladium.

12. The method for producing copolymers as claimed in claim 1 , wherein the organometallic compound is represented by formula (III)

wherein
M represents an element belonging to Group 10 in the periodic system;
R 1a , R 1b , R 2a and R 2b may be the same or different with each other, and independently represent a substituted or unsubstituted alkyl group having 1 to 14 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 14 carbon atoms, a substituted or unsubstituted biphenyl group or a substituted or unsubstituted aryl group; a pair of R 1a and R 1b and a pair of R 2a a

Assignees

• Univ Tokyo
• Showa Denko Kk

Inventors

• Nozaki Kyoko
• CARROW Brad
• Okumura Yoshikuni
• Kuroda Junichi

Classifications

• C08F210/00

  Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond · CPC title

• C07F19/00

  Metal compounds according to more than one of main groups C07F1/00 - C07F17/00 · CPC title

• C07F9/5325

  Aromatic phosphine oxides or thioxides (P-C aromatic linkage) · CPC title

• C07F15/006 Primary

  Palladium compounds · CPC title

• C07F9/5312 Primary

  substituted by a phosphorus atom (C07F9/5329 takes precedence) · CPC title