Polyolefin-Polystyrene Multi-Block Copolymer, Organozinc Compound for Preparing Same, and Method for Preparing Polyolefin-Polystyrene Multi-Block Copolymer

Patent metadata

Field	Value
Publication number	US-2020031978-A1
Application number	US-201816497655-A
Country	US
Kind code	A1
Filing date	Feb 14, 2018
Priority date	Mar 31, 2017
Publication date	Jan 30, 2020
Grant date	—

Abstract

The present invention relates to a polyolefin-polystyrene multi-block copolymer having a structure comprising a polyolefin block and polystyrene blocks bonded to both ends of the polyolefin block, to an organozinc compound for preparing the same, and a method for preparing the polyolefin-polystyrene multi-block copolymer.

First claim

1 . A polyolefin-polystyrene multi-block copolymer comprising a repeating unit represented by Formula 1 below:

wherein, in Formula 1, Ar is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; n is 0 or has an average value of 10 to 1,000; m has an average value of 0 to 1,000; A is a substituted or unsubstituted meta- or para-phenylene group; R is hydrogen, a methyl group, an ethyl group, a butyl group or a hexyl group; a has an average value of 10 to 10,000; * is each independently the end of the repeating unit or a site connected with a Z moiety by covalent bonding; and Z is a binding site derived from an anionic polymerization initiator and connected with a silicon atom-containing alkyl group having 1 to 20 carbon atoms, a silicon atom-free alkyl group having 1 to 20 carbon atoms, a silicon atom-containing arylalkyl group having 7 to 20 carbon atoms, a silicon atom-free arylalkyl group having 7 to 20 carbon atoms, or the * by covalent bonding.

2 . The polyolefin-polystyrene multi-block copolymer of claim 1 , wherein, in Formula 1, Z is a binding site derived from an anionic polymerization initiator and connected with a silicon atom-containing alkyl group having 1 to 20 carbon atoms, a silicon atom-containing arylalkyl group having 7 to 20 carbon atoms or the * by covalent bonding.

3 . The polyolefin-polystyrene multi-block copolymer of claim 1 , wherein, in Formula 1, Ar is an unsubstituted phenyl group; A is an unsubstituted meta- or para-phenylene group; and Z is a binding site connected with (CH 3 ) 3 SiCH 2 — or the * by covalent bonding.

4 . An organozinc compound represented by Formula 2 below:
CH 2 ═CH-A-CH 2 CH 2 —{[CH(R)—CH 2 ] a } p —Zn—{[CH(R)—CH 2 ] a } q —CH 2 CH 2 -A-CH═CH 2   [Formula 2]
wherein, in Formula 2, A is a substituted or unsubstituted meta- or para-phenylene group; a has an average value of 10 to 10,000; R is hydrogen, a methyl group, an ethyl group, a butyl group or a hexyl group; and each of p and q is independently 0 or 1.

5 . The organozinc compound of claim 4 , which is represented by Formula 2-1 or Formula 2-2 below:
CH 2 ═CH-A-CH 2 CH 2 —Zn—CH 2 CH 2 -A-CH═CH 2 ,  [Formula 2-1]
CH 2 ═CH-A-CH 2 CH 2 —[CH(R)—CH 2 ] a —Zn—[CH 2 —CH(R)] a —CH 2 CH 2 -A-CH═CH 2   [Formula 2-2]
wherein, in Formulas 2-1 and 2-2, A is a meta- or para-phenylene group, a has an average value of 10 to 10,000; and R is hydrogen, a methyl group an ethyl group, a butyl group or a hexyl group.

6 . (canceled)

7 . A method of preparing the polyolefin-polystyrene multi-block copolymer of claim 1 , comprising:
a first step of preparing a compound represented by Formula 2-2 below by coordination polymerization of an olefin monomer with a transition metal catalyst in the presence of an organozinc compound represented by Formula 2-1 below; and a second step of sequentially inputting a silicon atom-containing alkyl lithium compound, a triamine compound and a styrene-based monomer and performing anionic polymerization;
CH 2 ═CH-A-CH 2 CH 2 —Zn—CH 2 CH 2 -A-CH═CH 2   [Formula 2-1]

CH 2 ═CH-A-CH 2 CH 2 —[CH(R)—CH 2 ] a —Zn—[CH 2 —CH(R)] a —CH 2 CH 2 -A-CH═CH 2   [Formula 2-2]

wherein, in Formulas 2-1 and 2-2, A is a meta- or para-phenylene group; a has an average value of 10 to 10,000; and R is hydrogen, a methyl group, an ethyl group, a butyl group or a hexyl group.

8 . The method of claim 7 , wherein the silicon atom-containing alkyl lithium compound is represented by Formula 3 below, and the triamine compound is represented by Formula 4 below:

9 . (canceled)

10 . The method of claim 7 , wherein the olefin monomer is ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene or a mixture thereof, and the styrene-based monomer is styrene.

11 . The method of claim 7 , wherein the coordination polymerization in the first step is performed by solution polymerization using a solvent including one or more selected from isobutane, hexane, cyclohexane or methylcyclohexane.

12 . The method of claim 7 , wherein a molar ratio ([Li]/[Zn]) of the silicon atom-containing alkyl lithium compound input in the second step and the organozinc compound represented by Formula 2-1 input in the first step is 0.5 to 2.

13 . The method of claim 7 , wherein a molar ratio of the triamine compound and the silicon atom-containing alkyl lithium compound input in the second step is 1:0.5 to 1:1.

14 . The method of claim 7 , wherein a molar ratio ([styrene]/[Zn]) of the styrene-based monomer input in the second step and a zinc atom in the reaction solution is 250 to 1,000.

15 . A polystyrene-polyolefin-polystyrene tri-block copolymer represented by Formula 7 below:

wherein, in Formula 7, Ar is an aryl group having 6 to 20 carbon atoms; m has an average value of 20 to 10,000; Y and Y′ are each independently hydrogen, methyl, ethyl, butyl, hexyl or octyl, and Y and Y′ are not the same as each other; p and 1−p are mole fractions of respective repeating subunit constituting repeating unit n, wherein p is 0 to 1; n has an average value of 40 to 10,000; R2 and R3 are each independently hydrogen or a hydrocarbyl having 1 to 20 carbon atoms; and z is an integer of 0 to 10.

16 . The polystyrene-polyolefin-polystyrene tri-block copolymer according to claim 15 , wherein, in Formula 7, Ar is phenyl; m has an average value of 20 to 200; Y is hydrogen; Y′ is methyl, ethyl, butyl or hexyl; R 2 and R 3 are hydrogen; and z is 0 or 2.

17 . (canceled)

18 . A method of preparing the polystyrene-polyolefin-polystyrene tri-block copolymer of claim 15 , comprising:
forming a polyolefin block by chain transfer polymerization of an olefin monomer using a polynuclear zinc compound as a chain transfer agent; and forming a polystyrene block by inputting a silicon atom-containing alkyl lithium compound, a triamine compound and a styrene-based monomer to the polyolefin block and performing anionic polymerization.

19 . The method of claim 18 , wherein the polynuclear zinc compound is represented by Formula 8 below:

wherein, in Formula 8, R 1 is hydrocarbyl having 1 to 20 carbon atoms; R 2 and R 3 are each independently hydrogen or hydrocarbyl having 1 to 20 carbon atoms; z is an integer of 0 to 10; and a has an average value of 1 to 10.

20 . The method of claim 18 , wherein the polynuclear zinc compound is represented by any one of Formula 8-1 and Formula 8-2 below:
CH 3 CH 2 —[Zn—(CH 2 ) 6 ] a —Zn—CH 2 CH 3   [Formula 8-1]
CH 3 —[Zn—(CH 2 ) 6 ] a —Zn—CH 3   [Formula 8-2]
wherein, in Formulas 8-1 and 8-2, a has an average value of 1 to 10.

21 . The method of claim 18 , wherein the silicon atom-containing alkyl lithium compound is represented by Formula 3 below, and the triamine compound is represented by Formula 4 below:

22 . (canceled)

23 . The method of claim 18 , wherein the molar ratio ([styrene]/[Zn]) of the input styrene-based monomer to a zinc atoms in the step of forming the polystyrene block is 250

Assignees

• Lg Chemical Ltd

Inventors

• Lee Bun Yeoul
• Park Seung Soo
• Kim Chung Sol
• Lee Hyun Mo
• Kim Sung Dong

Classifications

• C08F2410/01

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

• C08F295/00

  Macromolecular compounds obtained by polymerisation using successively different catalyst types without deactivating the intermediate polymer · CPC title

• C07F3/06

  Zinc compounds · CPC title

• C08F297/02 Primary

  using a catalyst of the anionic type · CPC title

• C08F297/086 Primary

  the block polymer contains at least three blocks · CPC title