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-11292863-B2
Application number	US-201816497655-A
Country	US
Kind code	B2
Filing date	Feb 14, 2018
Priority date	Mar 31, 2017
Publication date	Apr 5, 2022
Grant date	Apr 5, 2022

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

The invention claiemd is:

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. 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.

7. The method of claim 6 , wherein the silicon atom-containing alkyl lithium compound is represented by Formula 3 below, and the triamine compound is represented by Formula 4 below:

8. The method of claim 6 , 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.

9. The method of claim 6 , 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.

10. The method of claim 6 , 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.

11. The method of claim 6 , 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.

12. The method of claim 6 , 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.

13. 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 is hydrogen, methyl, ethyl, butyl, hexyl or octyl, Y′ is methyl, butyl, or hexyl, 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.

14. The polystyrene-polyolefin-polystyrene tri-block copolymer according to claim 13 , wherein, in Formula 7, Ar is phenyl; m has an average value of 20 to 200; Y is hydrogen; Y′ is methyl, butyl or hexyl; R 2 and R 3 are hydrogen; and z is 0 or 2.

15. A method of preparing the 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, 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.

16. The method of claim 15 , 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.

17. The method of claim 15 , 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.

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

• C08F297/086 Primary

  the block polymer contains at least three blocks · CPC title

• C08F297/02 Primary

  using a catalyst of the anionic type · CPC title

• C08F295/00

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

• C08F12/08 Primary

  Styrene · CPC title