Production method of polar group-containing olefin polymers

Patent metadata

Field	Value
Publication number	US-9499644-B2
Application number	US-201414762598-A
Country	US
Kind code	B2
Filing date	Jan 22, 2014
Priority date	Jan 23, 2013
Publication date	Nov 22, 2016
Grant date	Nov 22, 2016

Abstract

The present invention relates to a method for producing a homopolymer of olefin represented by formula (1): CH 2 ═CHR 1 (R 1 is a hydrogen atom or hydrocarbon group having 1 to 20 carbon atoms) or a copolymer of two or more thereof or a method for producing a copolymer of olefin represented by formula (1) with olefin containing a polar group represented by formula (2): CH 2 ═CHR 2 R 3 (R 2 is a hydrogen atom or methyl group, R 3 is —COOR 12 , —CN, —OCOR 12 , —OR 12 , —CH 2 —OCOR 12 , —CH 2 OH, —CH 2 —N(R 13 ) 2 or —CH 2 -Hal (R 12 , R 13 and Hal have the same meanings as stated in the description), using as a catalyst a metal complex of group 10 elements in the periodic system typified by the structure represented by formula 1 (“Men” represents a menthyl group and “Me” represents a methyl group). The present invention enables the production of high molecular weight polymers of the polar group-containing monomers such as polar group-containing allyl compounds.

First claim

The invention claimed is:

1. A method for producing a homopolymer or copolymer of monomers comprising olefin represented by formula (1)
CH 2 ═CHR 1   (1)

in the formula, R 1 represents a hydrogen atom or hydrocarbon group having 1 to 20 carbon atoms, using as a polymerization catalyst a metal complex represented by formula (C1)

in the formula, M represents a metal atom of group 10 element in the periodic system; X represents a phosphorous atom (P) or an arsenic atom (As); R 5 represents a hydrogen atom or hydrocarbon group having 1 to 30 carbon atoms which is optionally substituted by one or more groups selected from a halogen atom, alkoxy group, aryloxy group and acyloxy group; Y, R 6 and R 7 independently represent a hydrogen atom, alkoxy group, aryloxy group, silyl group, amino group or hydrocarbon group having 1 to 30 carbon atoms which is optionally substituted by one or more groups selected from a halogen atom, alkoxy group and aryloxy group; and at least one of R 6 and R 7 represents a cycloalkyl group represented by formula (5)

in the formula, R represents an alkylene group having 1 to 14 carbon atoms which optionally have a substituent; R 9 , R 10 and R 11 independently represent a hydrogen atom, alkoxy group, aryloxy group, silyl group, amino group or hydrocarbon group having 1 to 30 carbon atoms which is optionally substituted by one or more groups selected from a halogen atom, alkoxy group and aryloxy group; at least one of R 9 and R 10 is not a hydrogen atom; R 9 , R 10 , R 11 and the above-mentioned alkylene group R optionally bond to each other to form a ring structure; in the formula, the bond of the carbon atom to X in formula (C1) is also shown;
Q represents a bivalent group indicated in the brackets of Z[—S(═O) 2 —O-]M, Z[—C(═O)—O-]M, Z[—P(═O)(—OH)—O-]M or Z[—S-]M, wherein Z and M at the beginning and at the end of the formulae are described to show the coupling direction of the groups; Z represents a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms which is optionally substituted by one or more groups selected from a halogen atom, alkoxy group and aryloxy group; Y and Z optionally bond to each other to form a ring structure; R 6 or R 7 optionally bond to Y to form a ring structure; 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 the copolymer is the copolymer of olefin represented by formula (1)
CH 2 ═CHR 1   (1)

and a polar group-containing olefin represented by formula (2)
CH 2 ═CR 2 R 3   (2)

in the formula, R 2 represents a hydrogen atom or a methyl group; R 3 represents —COOR 12 , —CN, —OCOR 12 , —OR 12 , —CH 2 —OCOR 12 , —CH 2 OH, —CH 2 —N(R 13 ) 2 or —CH 2 -Hal, wherein R 12 represents a hydrogen atom or hydrocarbon group having 1 to 5 carbon atoms; R 13 represents a hydrogen atom, hydrocarbon group having 1 to 5 carbon atoms, aromatic substituent having 6 to 18 carbon atoms or alkoxy carbonyl group; and Hal represents a halogen atom.

3. The method for producing a polymer as claimed in claim 1 , wherein the number of carbon atoms of the alkylene group R in formula (5) is 2 to 6.

4. The method for producing a polymer as claimed in claim 1 , wherein the number of carbon atoms of the alkylene group R in formula (5) is 4.

5. The method for producing a polymer as claimed in claim 1 , wherein at least one of R 9 and R 10 in formula (5) is an alkyl group having 1 to 6 carbon atoms or cycloalkyl group having 3 to 8 carbon atoms.

6. The method for producing a polymer as claimed in claim 1 , wherein at least one of R 9 and R 10 in formula (5) is an isopropyl group.

7. The method for producing a polymer as claimed in claim 1 , wherein at least one of R 6 and R 7 in formula (C1) is 2-isopropyl-5-methylcyclohexyl group (menthyl group) represented by the following formula

in the formula, the bond between the carbon atom and X is also shown and X has the same meaning as described in formula (C1).

8. The method for producing a polymer as claimed in claim 1 , wherein both of R 6 and R 7 in formula (C1) are 2-isopropyl-5-methylcyclohexyl group (menthyl group).

9. The method for producing a polymer as claimed in claim 1 , wherein the catalyst represented by formula (C1) is represented by formula (C2)

in the formula, Y 1 represents a halogen atom or bivalent hydrocarbon group having 1 to 70 carbon atoms which is optionally substituted by one or more groups selected from alkoxy group and aryloxy group; Q, M, X, R 5 , R 6 , R 7 , L and q have the same meaning as described in formula (C1).

10. The method for producing a polymer as claimed in claim 9 , wherein Q in formula (C2) is —SO 2 —O—, provided that S bonds to Y 1 and O bonds to M.

11. The method for producing a polymer as claimed in claim 9 , wherein the catalyst represented by formula (C2) is represented by formula (C3)

in the formula, four R 8 s independently represent a hydrogen atom, alkyl group having 1 to 8 carbon atoms, alkoxy group having 1 to 8 carbon atoms, aryloxy group having 6 to 18 carbon atoms or a halogen atom; and M, X, R 5 , R 6 , R 7 , L and q have the same meanings as described in formula (C1).

12. The method for producing a polymer as claimed in claim 11 , wherein all of R 8 s in formula (C3) are a hydrogen atom.

13. The method for producing a polymer as claimed in claim 1 , wherein M is Pd.

14. The method for producing a polymer as claimed in claim 1 , wherein X is P.

15. The method for producing a polymer as claimed in claim 1 , wherein the olefin represented by formula (1) is ethylene.

16. The method for producing a polymer as claimed in claim 1 , wherein the polar group-containing olefin represented by formula (2) is an allyl compound in which R 3 represents —CH 2 —OCOR 12 , —CH 2 OH, —CH 2 N—(R 13 ) 2 or —CH 2 -Hal, wherein R 12 , R 13 and Hal have the same meanings as described in formula (2).

17. The method for producing a polymer as claimed in claim 1 , wherein the polar group-containing olefin represented by formula (2) is allyl acetate.

18. The method for producing a polymer as claimed in claim 10 , wherein the catalyst represented by formula (C2) is represented by formula (C3)

in the formula, four R 8 s independently represent a hydrogen atom, alkyl group having 1 to 8 carbon atoms, alkoxy group having 1 to 8 carbon atoms, aryloxy group having 6 to 18 carbon atoms or a halogen atom; and M, X, R 5 , R 6 , R 7 , L and q have the same meanings as described in formula (C1).

19. The method for producing a polymer as claimed in claim 18 , wherein all of R 8 s in formula (C3) are a hydrogen atom.

Assignees

• Univ Tokyo
• Showa Denko Kk

Inventors

• Ito Shingo
• Nozaki Kyoko
• Ota Yusuke
• Okumura Yoshikuni
• Kuroda Junichi

Classifications

• C08F4/60031

  PO · CPC title

• C08F220/02

  Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof · CPC title

• C07F15/006

  Palladium compounds · CPC title

• C07F15/0066

  without a metal-carbon linkage · CPC title

• C08F4/80

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