Method for producing copolymer of allyl monomer having polar group

Patent metadata

Field	Value
Publication number	US-11697698-B2
Application number	US-201917046036-A
Country	US
Kind code	B2
Filing date	Mar 7, 2019
Priority date	Apr 25, 2018
Publication date	Jul 11, 2023
Grant date	Jul 11, 2023

Abstract

The present invention pertains to a method for producing a copolymer of ethylene and an allyl monomer having a polar group represented by general formula (1), or a copolymer of ethylene, an allyl monomer having a polar group represented by general formula (1), and other monomers, wherein the copolymer is produced in the presence of a boron compound having a boron-hydrogen bond or a boron-carbon bond (for example, a compound represented by general formula (2)) by using a metal complex represented by general formula (C1) as a polymerization catalyst (the symbols in the formulas are as described in the description). According to the present invention, a copolymer of ethylene and an allyl monomer can be efficiently produced with high catalytic activity, wherein the copolymer has a polar group and can be used in 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, 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, the method comprising polymerizing ethylene and the allyl monomer having a polar group represented by formula (1), or ethylene, the allyl monomer having a polar group represented by formula (1), and another monomer, in the presence of a metal complex, wherein the metal complex is 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 substituent 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 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 number of charges of the metal complex represented by formula (C1) and is 0 or 1, Z n− represents a counteranion, and is absent when n is 0, as a catalyst, and by allowing a boron compound having one or more boron-hydrogen bonds (B—H) or boron-carbon bonds (B—C) to coexist during polymerization.

2. The method for producing a copolymer according to claim 1 , wherein the boron compound having one or more boron-hydrogen bonds (B—H) or boron-carbon bonds (B—C) is a borane compound, a boroxine compound, a boronic acid compound, a boronic ester compound, a borinic acid compound, or a borinic ester compound.

3. The method for producing a copolymer according to claim 1 , wherein the boron compound having one or more boron-hydrogen bonds (B—H) or boron-carbon bonds (B—C) is a boroxine 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, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and an acyloxy group having 2 to 10 carbon atoms, and at least one of R 2 , R 3 and R 4 is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 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 3 , wherein R 2 , R 3 and R 4 in formula (2) are each independently a hydrogen atom, 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.

5. The method for producing a copolymer according to claim 1 , wherein the metal complex is 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.

6. The method for producing a copolymer according to claim 5 , wherein the metal complex is 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).

7. The method for producing a copolymer according to claim 5 , 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.

8. The method for producing a copolymer according to claim 5 , wherein R 6 and R 7 in formula (C2) are both an alkyl group having 3 to 20 carbon atoms.

9. The method for producing a copolymer according to claim 1 , wherein the metal complex is 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).

10. The method for producing a copolymer according to claim 9 , wherein Y in formula (C3) is a substituted or unsubsti

Assignees

• Univ Tokyo
• Showa Denko Kk
• Japan Polyethylene Corp

Inventors

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

Classifications

• C08F4/52

  selected from boron, aluminium, gallium, indium, thallium or rare earths (C08F4/14 takes precedence) · CPC title

• C08F210/02 Primary

  Ethene · CPC title

• C08F218/10

  of monocarboxylic acids containing three or more carbon atoms · CPC title

• C08K5/0091

  Complexes with metal-heteroatom-bonds · CPC title

• C08F4/7098

  Nickel or compounds thereof · CPC title