US 11,697,698 B2
Method for producing copolymer of allyl monomer having polar group
Kyoko Nozaki, Tokyo (JP); Shingo Ito, Tokyo (JP); Junichi Kuroda, Oita (JP); Yoshikuni Okumura, Oita (JP); Shinya Hayashi, Oita (JP); Minoru Kobayashi, Yokkaichi (JP); and Yuichiro Yasukawa, Kawasaki (JP)
Assigned to THE UNIVERSITY OF TOKYO, Tokyo (JP); SHOWA DENKO K.K., Tokyo (JP); and JAPAN POLYETHYLENE CORPORATION, Tokyo (JP)
Appl. No. 17/46,036
Filed by The University of Tokyo, Tokyo (JP); SHOWA DENKO K. K., Tokyo (JP); and Japan Polyethylene Corporation, Tokyo (JP)
PCT Filed Mar. 7, 2019, PCT No. PCT/JP2019/009072
§ 371(c)(1), (2) Date Oct. 8, 2020,
PCT Pub. No. WO2019/207969, PCT Pub. Date Oct. 31, 2019.
Claims priority of application No. 2018-083743 (JP), filed on Apr. 25, 2018.
Prior Publication US 2021/0040251 A1, Feb. 11, 2021
Int. Cl. C08F 4/80 (2006.01); C08F 4/52 (2006.01); C08F 210/02 (2006.01); C08F 218/12 (2006.01); C08F 4/70 (2006.01); C08F 218/10 (2006.01); C08K 5/00 (2006.01); C08K 5/55 (2006.01)
CPC C08F 210/02 (2013.01) [C08F 4/52 (2013.01); C08F 4/7062 (2013.01); C08F 4/7098 (2013.01); C08F 4/80 (2013.01); C08F 218/10 (2013.01); C08K 5/0091 (2013.01); C08K 5/55 (2013.01)] 16 Claims
 
1. A method for producing a copolymer of ethylene and an allyl monomer having a polar group represented by formula (1)
CH2═CH—CH2—R1  (1),
wherein R1 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)

OG Complex Work Unit Chemistry
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 (—SiH2—), 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(—R8)(—R9)═O, and —C(—R10)═O, wherein R8, R9 and R10 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(—R8)(—R9)═O-M, or Y—C(—R10)═O-M, R5 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, R6 and R7 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 R5 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, Zn− 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.