Ethylene-based quaterpolymer having low glass transition temperature and preparation method thereof

Patent metadata

Field	Value
Publication number	US-9540466-B2
Application number	US-201514769014-A
Country	US
Kind code	B2
Filing date	Apr 8, 2015
Priority date	Apr 8, 2014
Publication date	Jan 10, 2017
Grant date	Jan 10, 2017

Abstract

The present invention relates to a highly elastic, ethylene-based quaterpolymer and a preparation method thereof. More particularly, the present invention relates to a highly elastic, ethylene-based quaterpolymer which comprises a specific molar ratio of an ethylene unit, a C 4-6 α-olefin unit, a C 8-12 α-olefin unit and at least one functional unit derived from a styrene-based monomer and to a method for preparing the ethylene-based quaterpolymer using a metallocene catalyst.

First claim

The invention claimed is:

1. An elastic, ethylene-based quaterpolymer comprising:
55-93.9 mol % of an ethylene unit;
3-40 mol % of a C 4-6 α-olefin unit;
3-40 mol % of a C 8-12 α-olefin unit; and
0.1-5 mol % of a functional unit derived from at least one styrene-based monomer,
the ethylene-based quaterpolymer having a weight-average molecular weight of 50,000-300,000 and a glass transition temperature between −40° C. and −80° C.

2. The elastic, ethylene-based quaterpolymer according to claim 1 , wherein the copolymer comprises:
65-85 mol % of an ethylene unit;
3-25 mol % of a C 4-6 α-olefin unit;
5-25 mol % of a C 8-12 α-olefin unit; and
0.3-2 mol % of a functional unit derived from at least one styrene-based monomer.

3. The elastic, ethylene-based quaterpolymer according to claim 1 , wherein the styrene-based monomer is styrene, divinylbenzene, p-methylstyrene, α-methylstyrene, butylstyrene, methoxystyrene, isopropylstyrene or butenylstyrene.

4. The elastic, ethylene-based quaterpolymer according to claim 1 , wherein the copolymer has a molecular weight distribution of 1-3.

5. The elastic, ethylene-based quaterpolymer according to claim 1 , wherein the copolymer has a Tan δ of 0.3 or greater.

6. A method for preparing an ethylene-based quaterpolymer, comprising polymerizing 55-93.9 mol % of an ethylene monomer, 3-40 mol % of a C 4-6 α-olefin monomer, 3-40 mol % of a C 8-12 α-olefin monomer and 0.1-5 mol % of at least one styrene-based monomer using a metallocene catalyst.

7. The method for preparing an ethylene-based quaterpolymer according to claim 6 , wherein the metallocene catalyst comprises a group 4 transition metal as a metal center; cyclopentadienyl or a derivative thereof, fluorenyl or a derivative thereof, or indenyl or a derivative thereof as a ligand; and has a bridged (ansa) structure or a non-bridged structure.

8. The method for preparing an ethylene-based quaterpolymer according to claim 7 , wherein the metallocene catalyst is ethylene bis(indenyl)zirconium dichloride.

9. The method for preparing an ethylene-based quaterpolymer according to claim 6 , wherein the catalytic activity in the polymerization is 5,000 kg (polymer)/μmol (catalyst)·hr or higher.

10. The method for preparing an ethylene-based quaterpolymer according to claim 6 , wherein the metallocene catalyst is used together with a metallocene cocatalyst selected from the group consisting of an alkylaluminoxane cocatalyst, an organic alkylaluminum cocatalyst, a boron compound cocatalyst and a mixture thereof.

11. The method for preparing an ethylene-based quaterpolymer according to claim 10 ,
wherein
the alkylaluminoxane cocatalyst is selected from the group consisting of methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane and isobutylaluminoxane;
the organic alkylaluminum cocatalyst is selected from the group consisting of trimethylaluminum, triethylaluminum, diisobutylaluminum, triisobutylaluminum and tri-n-octylaluminum; and
the boron compound cocatalyst is selected from the group consisting of tris(pentafluorophenyl)borane, trityl tetrakis(pentafluorophenyl)borate, dimethylanilinium tetrakis(pentafluorophenyl)borate and triphenylmethylinium tetrakis(pentafluorophenyl)borate.

12. The method for preparing an ethylene-based quaterpolymer according to claim 6 , wherein the polymerization is performed at 20-70° C.

13. The method for preparing an ethylene-based quaterpolymer according to claim 6 , wherein the polymerization is performed for from 20 minutes to 1 hour.

Assignees

• Korea Ind Tech Inst

Inventors

• Kim Dong Hyun
• Kim Jung Soo
• Jeon Dong Gyu
• Jang Ji Hoon

Classifications

• C08F212/36

  Divinylbenzene · CPC title

• C08F210/18 Primary

  with non-conjugated dienes, e.g. EPT rubbers · CPC title

• C08F4/6592

  containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring · CPC title

• C08F210/14

  Monomers containing five or more carbon atoms · CPC title

• C08F212/08

  Styrene · CPC title