Method for producing polar group-containing olefin polymer

Patent metadata

Field	Value
Publication number	US-10414837-B2
Application number	US-201515522439-A
Country	US
Kind code	B2
Filing date	Sep 15, 2015
Priority date	Oct 28, 2014
Publication date	Sep 17, 2019
Grant date	Sep 17, 2019

Abstract

The present invention relates to a method for producing a copolymer of ethylene and a polar group-containing olefin using as a catalyst a metal complex of group 10 elements having a structure represented by formula (C4) and (C5)

(in the formula, “Men” represents a menthyl group and “Me” represents a methyl group). The method of the present invention makes it possible to produce a polar group-containing olefin polymer available for various applications, as being a high molecular weight body, which has been difficult to produce, and to produce the polymer in a molecular weight range such that the polymer has good moldability.

First claim

The invention claimed is:

1. A method for producing a homopolymer of ethylene, or a copolymer of ethylene and a monomer comprising a polar group-containing olefin represented by formula (1),

in the formula, R 1 represents a substituent group selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 10 carbon atoms, an ester group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an amino group, a substituted amino group having 1 to 12 carbon atoms, a substituted amide group having 2 to 12 carbon atoms, a substituted pyridyl group having 5 to 10 carbon atoms, a substituted pyrrolidyl group having 4 to 10 carbon atoms, a substituted piperidyl group having 5 to 10 carbon atoms, a substituted hydrofuryl group having 4 to 10 carbon atoms, a substituted imidazolyl group having 4 to 10 carbon atoms, a mercapto group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, an epoxy group, and a halogen atom, and n is an integer from 0 to 6,
the method comprising polymerizing ethylene, or ethylene and the monomer comprising a polar group-containing olefin represented by formula (1), in the presence of a metal complex represented by formula (C2) as a polymerization catalyst,

in the formula, M represents a metal atom of group 10 element in the periodic system;
X represents a phosphorous (P) atom or an arsenic (As) atom;
R 5 represents a substituent group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted by a halogen atom, a hydrocarbon group having 2 to 30 carbon atoms substituted by an alkoxy group having 1 to 10 carbon atoms, a hydrocarbon group having 7 to 30 carbon atoms substituted by an aryloxy group having 6 to 20 carbon atoms, a hydrocarbon group having 3 to 30 carbon atoms substituted by an amide group having 2 to 10 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, and an acyloxy group having 2 to 10 carbon atoms;
R 6 and R 7 independently represent a hydrogen atom, an alkoxy group, an aryloxy group, a silyl group, an amino group or a hydrocarbon group having 1 to 120 carbon atoms which may be substituted by one or more groups selected from a halogen atom, an alkoxy group and an aryloxy group; and at least one of R 6 and R 7 represents an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 4 to 106 carbon atoms;
R 12 to R 15 each independently represents a hydrogen atom, a silyl group, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted by a silyl group or a halogen atom, at least one of R 12 to R 15 is a silyl group;
L represents an electron-donating ligand, and
q is 0, ½, 1 or 2.

2. The method for producing a polymer as claimed in claim 1 , wherein n in formula (1) is 0.

3. The method for producing a polymer as claimed in claim 1 , wherein n in formula (1) is 1.

4. The method for producing a polymer as claimed in claim 1 , wherein the copolymer is a copolymer of ethylene, a polar group-containing olefin represented by formula (1) and α-olefin represented by formula (2),
CH 2 ═CHR 2   (2)

in the formula, R 2 represents a hydrocarbon group having 1 to 20 carbon atoms; and the molar ratios of 1, m and p of the monomer units represented by formula (3), formula (4) and formula (5), each corresponding to ethylene, a monomer represented by formula (1) and a monomer represented by formula (2), respectively, satisfies the relationship expressed by the following equation:
{ l /( l+p )}×100≥60,

5. The method for producing a polymer as claimed in claim 1 , wherein formula (C2) is represented by formula (C3), in which R 12 in formula (C2) is a silyl group,

in the formula, three R 16 's independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms and may be the same or different from each other, M, X, R 5 , R 6 , R 7 , R 13 , R 14 , R 15 , L and q have the same meanings as described in formula (C2).

6. The method for producing a polymer as claimed in claim 5 , wherein all the R 16 's in formula (C3) are a methyl group.

7. The method for producing a polymer as claimed in claim 5 , wherein R 13 in formula (C3) is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.

8. The method for producing a polymer as claimed in claim 5 , wherein R 13 in formula (C3) is a hydrogen atom, an isopropyl group or a phenyl group.

9. The method for producing a polymer as claimed in claim 5 , wherein both of R 14 and R 15 in formula (C3) are a hydrogen atom.

10. A method for producing a hydroxyl group-containing copolymer, comprising producing a copolymer from ethylene and a polar group-containing olefin according to the method claimed in claim 1 , in which R 1 in formula (1) is an acyloxy group having 2 to 10 carbon atoms, and subjecting the copolymer to a saponification reaction or a hydrolysis reaction.

11. A catalyst for polymerization of olefin, containing a metal complex represented by formula (C2),

in the formula, M represents a metal atom of group 10 element in the periodic system;
X represents a phosphorous (P) atom or an arsenic (As) atom;
R 5 represents a substituent group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted by a halogen atom, a hydrocarbon group having 2 to 30 carbon atoms substituted by an alkoxy group having 1 to 10 carbon atoms, a hydrocarbon group having 7 to 30 carbon atoms substituted by an aryloxy group having 6 to 20 carbon atoms, a hydrocarbon group having 3 to 30 carbon atoms substituted by an amide group having 2 to 10 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, and an acyloxy group having 2 to 10 carbon atoms;
R 6 and R 7 independently represent a hydrogen atom, an alkoxy group, an aryloxy group, a silyl group, an amino group or a hydrocarbon group having 1 to 120 carbon atoms which may be substituted by one or more groups selected from a halogen atom, an alkoxy group and an aryloxy group; and at least one of R 6 and R 7 represents an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 4 to 106 carbon atoms;
R 12 to R 15 each independently represents a hydrogen atom, a silyl group, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted by a silyl group or a halogen atom, at least one of R 12 to R 15 is a silyl group;
L represents an electron-donating ligand, and
q is 0, ½, 1 or

Assignees

• Univ Tokyo
• Showa Denko Kk
• Japan Polyethylene Corp

Inventors

• Nozaki Kyoko
• Ito Shingo
• Ota Yusuke
• Okumura Yoshikuni
• Kuroda Junichi
• Koyano Masafumi
• Kobayashi Minoru
• Shimizu Hiroyuki

Classifications

• C08F4/80

  selected from iron group metals or platinum group metals · CPC title

• C08F210/16 Primary

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title

• C08F10/02 Primary

  Ethene · CPC title

• C08F218/12

  with unsaturated alcohols containing three or more carbon atoms · CPC title