Cross-copolymer and method for producing same

Patent metadata

Field	Value
Publication number	US-2017145135-A1
Application number	US-201515310403-A
Country	US
Kind code	A1
Filing date	May 14, 2015
Priority date	May 15, 2014
Publication date	May 25, 2017
Grant date	—

Abstract

The purpose of the present invention is to provide: a cross-copolymer in which a residual catalyst component remains in a reduced amount and which has improved transparency, applicability to medical materials and yellowish discoloration resistance; and a method for producing the cross-copolymer. According to the present invention, a cross-copolymer is provided, wherein the cross-copolymer is produced through a coordination polymerization step of carrying out copolymerization of an olefin monomer, an aromatic vinyl compound monomer and an aromatic polyene using a single-site coordination polymerization catalyst to synthesize an olefin-(aromatic vinyl compound)-(aromatic polyene) copolymer and a subsequent anionic polymerization step of carrying out polymerization in the co-presence of the olefin-(aromatic vinyl compound)-(aromatic polyene) copolymer and an aromatic vinyl compound monomer using an anionic polymerization initiator, the cross-copolymer being characterized in that the total mass of aluminum and lithium, which are residual catalyst components, contained in the cross-copolymer is 200 ppm or less.

First claim

1 . A cross-copolymer which is produced through a coordination polymerization step of carrying out copolymerization of an olefin monomer, an aromatic vinyl compound monomer and an aromatic polyene using a single-site coordination polymerization catalyst to synthesize an olefin-(aromatic vinyl compound)-(aromatic polyene) copolymer and a subsequent anionic polymerization step of carrying out polymerization in a co-presence of the olefin-(aromatic vinyl compound)-(aromatic polyene) copolymer and an aromatic vinyl compound monomer using an anionic polymerization initiator,
wherein a total mass of aluminum and lithium, which are residual catalyst components, contained in the cross-copolymer is 200 ppm or less.

2 . The cross-copolymer according to claim 1 , wherein all the following conditions (1) to (4) are met:
(1) in the coordination polymerization step, the single site coordination polymerization catalyst is used to carry out the copolymerization of an ethylene monomer, an aromatic vinyl compound monomer, and an aromatic polyene, and then, an ethylene-(aromatic vinyl compound)-(aromatic polyene) copolymer is synthesized such that content of the aromatic vinyl compound unit is from 15 mol % to 30 mol %, content of the aromatic polyene unit is from 0.01 mol % to 0.2 mol %, and the rest are content of the ethylene unit; (2) a weight-average molecular weight of the ethylene-(aromatic vinyl compound)-(aromatic polyene) copolymer obtained in the coordination polymerization step is from 30,000 to 200,000, and a molecular weight distribution (Mw/Mn) thereof is from 1.8 to 4 inclusive; (3) a total amount (ΔH) of heat of crystal fusion as observed in a temperature range of 0 to 150° C. when the cross-copolymer is determined is 25 J/g or less; and (4) content of the ethylene-(aromatic vinyl compound)-(aromatic polyene) copolymer contained in the cross-copolymer is from 70 mass % to 95 mass % inclusive.

3 . A medical tube comprising the cross-copolymer according to claim 1 .

4 . A medical multilayer sheet comprising the cross-copolymer according to claim 1 .

5 . The cross-copolymer according to claim 1 , wherein all the following conditions (a) to (e) are met:
(a) in the coordination polymerization step, the single site coordination polymerization catalyst is used to carry out the copolymerization of an ethylene monomer, an aromatic vinyl compound monomer, and an aromatic polyene, and then, an ethylene-(aromatic vinyl compound)-(aromatic polyene) copolymer is synthesized such that content of the aromatic vinyl compound unit is from 10 mol % to 35 mol %, content of the aromatic polyene unit is from 0.01 mol % to 0.2 mol %, and the rest are content of the ethylene unit; (b) a weight-average molecular weight of the ethylene-(aromatic vinyl compound)-(aromatic polyene) copolymer obtained in the coordination polymerization step is from 30,000 to 150,000, and a molecular weight distribution (Mw/Mn) thereof is from 1.8 to 3 inclusive; (c) an amount (ΔH) of heat of crystal fusion as observed in a temperature range of 0 to 150° C. when the ethylene-(aromatic vinyl compound)-(aromatic polyene) copolymer is determined is 30 J/g or less; (d) a ratio of TUS (i.e., a total amount of polymerizable unsaturated groups included in the copolymer; the total number of terminal double bonds+double bonds contained in the divinylbenzene unit) to DOU (i.e., content of the divinylbenzene unit of the copolymer) of the ethylene-(aromatic vinyl compound)-(aromatic polyene) copolymer is within a range: 1.3≦TUS/DOU≦10; and (e) content of the ethylene-(aromatic vinyl compound)-(aromatic polyene) copolymer contained in the cross-copolymer is from 40 mass % to 90 mass % inclusive.

6 . A solar cell sealant comprising the cross-copolymer according to claim 1 .

7 . A method for producing a cross-copolymer, comprising the steps of:
obtaining a polymer solution containing a cross-copolymer; preparing liquid containing the polymer solution, water, and an organic acid and subjecting the liquid to emulsification/dispersion, and thereafter; separating and removing the water from the polymer solution; and collecting the cross-copolymer from the polymer solution, wherein the cross-copolymer is produced through a coordination polymerization step in which a single site coordination polymerization catalyst is used to carry out copolymerization of an olefin monomer, an aromatic vinyl compound monomer, and an aromatic polyene to synthesize an olefin-(aromatic vinyl compound)-(aromatic polyene) copolymer, and a subsequent anionic polymerization step in which an anionic polymerization initiator is used to carry out polymerization in a co-presence of the ethylene-(aromatic vinyl compound)-(aromatic polyene) copolymer and an aromatic vinyl compound monomer, and wherein the organic acid has a pKa of from 1 to 7 and solubility of the organic acid is 5 g or more per 100 g of water at 20° C.

Assignees

• Denka Company Ltd

Inventors

• Arai Toru
• Tsukamoto Ayumu
• Sasaki Eri

Classifications

• C08J5/18

  Manufacture of films or sheets · CPC title

• C09J151/06

  grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond · CPC title

• C08F255/02 Primary

  on to polymers of olefins having two or three carbon atoms · CPC title

• Y02E10/50

  Photovoltaic [PV] energy · CPC title

• B32B27/30

  comprising vinyl {(co)polymers; comprising acrylic (co)polymers} · CPC title