Method for producing copolymer of polar group-containing allyl monomer

Patent metadata

Field	Value
Publication number	US-11248074-B2
Application number	US-201916963574-A
Country	US
Kind code	B2
Filing date	Jan 29, 2019
Priority date	Feb 20, 2018
Publication date	Feb 15, 2022
Grant date	Feb 15, 2022

Abstract

The present invention relates to a method for producing a copolymer of ethylene and an allyl monomer that is represented by formula (1) and has a polar group, or a copolymer of ethylene, the allyl monomer that is represented by formula (1) and has a polar group, and another monomer. This production method is characterized by using a metal complex, which is represented by general formula (C1), as a polymerization catalyst and by having a silane compound, which is represented by general formula (2) and has a silicon-hydrogen bond, coexist with the metal complex. (In the formulae, the symbols are as defined in the description.) According to the present invention, a copolymer of an allyl monomer that has a polar group is able to be produced with high catalytic activity, said copolymer being capable of having various applications.

First claim

The invention claimed is:

1. A method for producing a copolymer of ethylene and an allyl monomer having a polar group represented by formula (1)
CH 2 ═CH—CH 2 —R 1   (1)

wherein R 1 represents a substituent selected from the group consisting of a hydroxy 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 (oxycarbonyl group; R—O—(C═O)—, R is an organic group), an acyloxy group having 2 to 10 carbon atoms, an amino group, a substituted amino group having 1 to 12 carbon atoms, a substituted amido 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, or a copolymer of ethylene, the allyl monomer having a polar group represented by formula (1) and another monomer, wherein the method comprises polymerizing ethylene and the allyl monomer having a polar group represented by formula (1) in the presence of a metal complex represented by formula (C1)

wherein M represents an element of Group 10 of the Periodic Table, X represents a phosphorus atom (P) or an arsenic atom (As), and Y represents a divalent group selected from a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 30 carbon atoms, a substituted or unsubstituted imino group (—NH—), an oxy group (—O—), and a substituted or unsubstituted silylene group (—SiH 2 —), Q represents an anionic ligand selected from —S(═O) 2 —O—, —C(═O)—O—, —P(═O)(—OH)—O—, —O—, and —S—, or a neutral ligand selected from —P(—R 8 )(—R 9 )═O, and —C(—R 10 )═O, wherein R 8 , R 9 and R 10 each independently represent a hydrogen atom, an alkoxy group, an aryloxy group, an amino group, or a hydrocarbon group having 1 to 30 carbon atoms which may be substituted with one or more groups selected from a halogen atom, an alkoxy group, an aryloxy group, and an amino group, wherein the bonding mode is Y—S(═O) 2 —O-M, Y—C(═O)—O-M, Y—P(═O)(—OH)—O-M, Y—O-M, Y—S-M, Y—P(—R 8 )(—R 9 )═O-M, or Y—C(—R 10 )═O-M, R 5 represents 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 with a halogen atom, a hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, a hydrocarbon group having 7 to 30 carbon atoms substituted with an aryloxy group having 6 to 20 carbon atoms, a hydrocarbon group having 3 to 30 carbon atoms substituted with an amido 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 each independently represent 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 with one or more groups selected from a halogen atom, an alkoxy group, and an aryloxy group, and may be bonded to each other to form a ring structure, L represents an electron-donating ligand and R 5 and L may form a ring, q is 0, ½, 1 or 2, n represents the charge of an organometallic compound and is 0 or 1, Z n− represents a counteranion of a cationic organometallic compound and when n is 0, it is not present, as a catalyst and by allowing a silane compound having one or more silicon-hydrogen bonds (Si—H) to coexist during polymerization.

2. The method for producing a copolymer according to claim 1 , wherein the silane compound having one or more silicon-hydrogen bonds (Si—H) is a silane compound represented by formula (2)

wherein R 2 , R 3 and R 4 each independently represent a substituent selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxy group, an amino group, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a substituted amino group having 1 to 20 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and R 2 , R 3 and R 4 may be bonded to each other to form a ring structure.

3. The method for producing a copolymer according to claim 2 , wherein R 2 , R 3 and R 4 in formula (2) are each independently a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

4. The method for producing a copolymer according to claim 1 , wherein n is 0 and Q is Q 1 in formula (C1), that is, the catalyst used is a metal complex represented by formula (C2)

wherein X, Y, M, L, q, R 5 , R 6 and R 7 represent the same meanings as described in formula (C1) and Q 1 represents an anionic ligand selected from —S(═O) 2 —O—, —C(═O)—O—, —P(═O)(—OH)—O—, —O—, and —S—.

5. The method for producing a copolymer according to claim 4 , wherein Q 1 in formula (C2) is —S(═O) 2 —O—, that is, the catalyst used is a metal complex represented by formula (C4)

wherein X, Y, M, L, q, R 5 , R 6 and R 7 represent the same meanings as described in formula (C1).

6. The method for producing a copolymer according to claim 4 , wherein Y in formula (C2) is a substituted or unsubstituted phenylene group, a substituted or unsubstituted methylene group, or a substituted or unsubstituted imino group.

7. The method for producing a copolymer according to claim 4 , wherein R 6 and R 7 in formula (C2) are both an alkyl group having 3 to 20 carbon atoms.

8. The method for producing a copolymer according to claim 1 , wherein n is 1 and Q is Q 2 in formula (C1), that is, the catalyst used is a metal complex represented by formula (C3)

wherein X, Y, M, L, q, R 5 , R 6 , R 7 , and Z have the same meanings as described in formula (C1), and Q 2 represents a neutral ligand selected from —P(—R 8 )(—R 9 )═O, and —C(—R 10 )═O, wherein R 8 , R 9 and R 10 represent the same meanings as described in formula (C1).

9. The method for producing a copolymer according to claim 8 , wherein Y in formula (C3) is a substituted or unsubstituted phenylene group, a substituted or unsubstituted methylene group, or a substituted or unsubstituted imino group.

10. The method for producing a copolymer according to claim 8 , wherein R 6 and R 7 in formula (C3) are both an alkyl group having 3 to 20 carbon atoms.

11. The method for producing a copolymer according to claim 8 , wherein Z in formula (C1) and formula (C3) is one selected from SbF 6 , BPh 4 , BArF 4 (ArF 4 ═[3,5-(CF 3 ) 2 C 6 H 3 ] 4 ),

Assignees

• Univ Tokyo
• Showa Denko Kk
• Japan Polyethylene Corp

Inventors

• Ito Shingo
• Nozaki Kyoko
• Kuroda Junichi
• Okumura Yoshikuni
• Hayashi Shinya
• Kobayashi Minoru
• Yasukawa Yuichiro

Classifications

• C08F218/12 Primary

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

• C08F210/02 Primary

  Ethene · CPC title

• C08F4/80

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

• C08F2410/01

  Additive used together with the catalyst, excluding compounds containing Al or B · CPC title