Organic zinc compound comprising polyolefin-polystyrene block copolymer, and method for preparing the same

Patent metadata

Field	Value
Publication number	US-10577448-B2
Application number	US-201615549343-A
Country	US
Kind code	B2
Filing date	Jan 21, 2016
Priority date	Feb 10, 2015
Publication date	Mar 3, 2020
Grant date	Mar 3, 2020

Abstract

The present invention relates to an organic zinc compound comprising a styrene-based polymer or a polyolefin-polystyrene block copolymer at both ends. Also, the present invention relates to a method for preparing the organic zinc compound, the method preparing an intermediate by coordination-polymerizing an olefin monomer using a transition metal catalyst, and then performing anionic polymerization by inserting an alkyllithium compound, an amine ligand, and a styrene-based monomer into the intermediate. Accordingly, the present invention can provide a method for preparing a commercially useful styrene-based polymer or polyolefin-polystyrene block copolymer directly from an olefin monomer and a styrene monomer in a one-pot manner.

First claim

The invention claimed is:

1. A method for preparing an organic zinc compound represented by Formula 1 below, the method comprising:
a first step of preparing a compound represented by Formula 3 through coordination polymerization of an olefin monomer using a transition metal catalyst in the presence of organic zinc represented by Formula 2; and
a second step of sequentially adding an alkyl lithium compound represented by Formula 4, an amine ligand represented by Formula 5 and a styrene-based monomer to the compound represented by Formula 3 to perform anionic polymerization;
wherein a ratio of an amount of the amine ligand to an amount of the organic zinc is from 0.2 to 1.0;
wherein a ratio of an amount of the styrene-based monomer to an amount of the organic zinc is from 500 to 900;
wherein the transition metal catalyst is a homogeneous catalyst; and
wherein the organic zinc represented by Formula 2 is converted into the organic zinc compound of Formula 1:

where R 1 and R 2 are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms; Ar is an aryl group having 6 to 20 carbon atoms; A is a hydrocarbon group having 1 to 20 carbon atoms; an average value of a 1 and a 2 is approximately 0 to 10,000; and an average value of b 1 and b 2 is approximately 10 to 1,000; and
(A) 2 Zn  [Formula 2]

where A is a hydrocarbon group having 1 to 20 carbon atoms; and

where R 1 and R 2 are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms; A is a hydrocarbon group having 1 to 20 carbon atoms; and an average value of a 1 and a 2 ranges from approximately 0 to 10,000;
B—Li  [Formula 4]

where B is an alkyl group having 1 to 20 carbon atoms;

where R 51 and R 52 are each independently a hydrocarbon group having 1 to 20 carbon atoms, and z is an integer of approximately 2 or 3.

2. The method of claim 1 , wherein the olefin monomer (CH 2 ═CH—R) is ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene or a mixture thereof, and the styrene-based monomer (ArCH═CH 2 ) is styrene.

3. The method of claim 1 , wherein the olefin monomer (CH 2 ═CH—R) is a mixture of any one of propylene, 1-butene, 1-hexene and 1-octene; and ethylene, and the styrene-based monomer (ArCH═CH 2 ) is styrene.

4. The method of claim 1 , wherein A of Formula 2 is one of a methyl group, an ethyl group, a hexyl group, a phenyl group and a benzyl group.

5. The method of claim 1 , wherein the transition metal catalyst is a transition metal compound represented by Formula 6A or 6B below:

In Formula 6A, R 61 is hydrogen or methyl, and R 62 is hydrogen or phenyl;

6. The method of claim 1 , wherein the polymerization in the first step is performed by solution polymerization using a solvent containing one or more of isobutane, hexane, cyclohexane and methylcyclohexane.

7. The method of claim 1 , wherein the alkyl lithium compound is n-BuLi.

8. The method of claim 1 , wherein the amine ligand is a compound represented by Formula 5 is a compound in which R 51 is methyl, R 52 is hydrogen, and z is approximately 2.

9. The method of claim 1 , wherein a molar ratio of the alkyl lithium compound and the amine ligand is approximately 1:0.5 to 1:1.5.

10. A composition prepared by the method of claim 1 , comprising the organic zinc compound represented by the Formula 1:

where R 1 and R 2 are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms; Ar is an aryl group having 6 to 20 carbon atoms; A is a hydrocarbon group having 1 to 20 carbon atoms; an average value of a 1 and a 2 is approximately 0 to 10,000; and an average value of b 1 and b 2 is approximately 10 to 1,000,
wherein a ratio of [(a number of polystyrene polymer chains)−(an amount of alkyl lithium)]/(an amount of zinc) is about 2.

11. The organic zinc compound of claim 10 , wherein R 1 and R 2 of Formula 1 are each independently any one of hydrogen, a methyl group, an ethyl group, a butyl group, a hexyl group and an octyl group; Ar is a phenyl group; A is any one of a methyl group, an ethyl group, a hexyl group, a phenyl group and a benzyl group.

12. The organic zinc compound of claim 10 , wherein the organic zinc compound is represented by Formula 1A below:

where R 3 , R 4 , R 5 and R 6 are each independently any one of hydrogen, a methyl group, an ethyl group, a butyl group, a hexyl group and an octyl group, R 3 and R 4 are not the same, R 5 and R 6 are not the same; Ar is a phenyl group; A is a methyl group, an ethyl group, a hexyl group, a phenyl group or a benzyl group; p and 1-p are mole fractions of respective repeating blocks constituting a repeating unit a 1 , p ranges from approximately more than 0 less than 1; q and 1-q are mole fractions of respective repeating blocks constituting a repeating unit a 2 , q ranges from approximately more than 0 less than 1; an average value of a 1 and a 2 is approximately more than 0 to 10,000; and an average value of b 1 and b 2 is approximately 10 to 1,000.

13. The organic zinc compound of claim 12 , wherein any one of R 3 and R 4 of Formula 1A is hydrogen, and the other one is a methyl group, an ethyl group, a butyl group or a hexyl group; any one of R 5 and R 6 is hydrogen, and the other one is a methyl group, an ethyl group, a butyl group or a hexyl group.

Assignees

• Lg Chemical Ltd

Inventors

• Lee Bun Yeoul
• Jeon Jong Yeob
• Park Geun Ho

Classifications

• C07F3/06

  Zinc compounds · CPC title

• C07F19/00

  Metal compounds according to more than one of main groups C07F1/00 - C07F17/00 · CPC title

• C08F295/00

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

• C07F17/00 Primary

  Metallocenes · CPC title

• C08F112/08

  Styrene · CPC title