Method of preparing polyolefin, and polyolefin prepared thereby

Patent metadata

Field	Value
Publication number	US-9975969-B2
Application number	US-201415021238-A
Country	US
Kind code	B2
Filing date	Nov 21, 2014
Priority date	Nov 21, 2013
Publication date	May 22, 2018
Grant date	May 22, 2018

Abstract

A method of preparing a polyolefin, wherein the method is used to more effectively prepare a polyolefin which has a high molecular weight and multimodal molecular weight distribution, thereby being preferably used for blow-molding or the like, and a polyolefin prepared thereby, are provided.

First claim

The invention claimed is:

1. A method of preparing a polyolefin, the method comprising the step of
polymerizing olefin monomers in the presence of a metallocene catalyst, and a molecular weight modifier including a mixture of a cyclopentadienyl metal compound of Chemical Formula 1 and an organic aluminum compound of Chemical Formula 2 or a reaction product thereof,
wherein the polymerization step is performed in a cascade reactor including a first reactor and a second reactor, and wherein the metallocene catalyst is fed into the first reactor and the molecular weight modifier is fed into the second reactor:
(R 1 -Cp 1 )(R 2 -Cp 2 )M 1 X 2   [Chemical Formula 1]

wherein Cp 1 and Cp 2 are each independently a ligand including a cyclopentadienyl group, an indenyl group, or a fluorenyl group; R 1 and R 2 are substituents of Cp 1 and Cp 2 , and are each independently an alkyl having 2 to 20 carbon atoms, an alkenyl having 2 to 20 carbon atoms, an alkylaryl having 7 to 20 carbon atoms, an arylalkyl having 7 to 20 carbon atoms, an aryl having 6 to 20 carbon atoms, a heteroalkyl having 1 to 20 carbon atoms, a heteroalkenyl having 2 to 20 carbon atoms, a heteroalkylaryl having 6 to 20 carbon atoms, a heteroarylalkyl having 6 to 20 carbon atoms, or a heteroaryl having 5 to 20 carbon atoms; M 1 is a Group 4 transition metal element; and X is a halogen,
R 3 R 4 R 5 Al  [Chemical Formula 2]

wherein R 3 , R 4 , and R 5 are each independently an alkyl having 4 to 20 carbon atoms or a halogen, and at least one of R 3 , R 4 , and R 5 is an alkyl having 4 to 20 carbon atoms.

2. A method of preparing a polyolefin, the method comprising the step of
solution-polymerizing olefin monomers in the presence of a metallocene catalyst, and a molecular weight modifier including a mixture of a cyclopentadienyl metal compound of Chemical Formula 3 and an organic aluminum compound of Chemical Formula 4 or a reaction product thereof,
wherein the polymerization step is performed in a cascade reactor including a first reactor and a second reactor, and wherein the metallocene catalyst is fed into the first reactor and the molecular weight modifier is fed into the second reactor:
(R 6 -Cp 3 )(R 7 -Cp 4 )M 2 X′ 2   [Chemical Formula 3]

wherein Cp 3 and Cp 4 are each independently a ligand including a cyclopentadienyl group, an indenyl group, or a fluorenyl group; R 6 and R 7 are substituents of Cp 3 and Cp 4 and are each independently hydrogen or a methyl; M 2 is a Group 4 transition metal element; and X′ is a halogen,
R 8 R 9 R 10 Al  [Chemical Formula 4]

wherein R 8 , R 9 , and R 10 are each independently an alkyl having 4 to 20 carbon atoms or a halogen, and at least one of R 8 , R 9 , and R 10 is an alkyl having 4 to 20 carbon atoms.

3. The method of claim 1 , wherein R 1 and R 2 are each independently selected from the group consisting of an ethyl, a butyl, and a t-butoxy hexyl.

4. The method of claim 1 , wherein R 3 , R 4 and R 5 are each independently an isobutyl.

5. The method of claim 1 , wherein M 1 is selected from the group consisting of titanium, zirconium, and hafnium.

6. The method of claim 1 , wherein X is selected from the group consisting of F, Cl, Br, and I.

7. The method of claim 1 , wherein the olefin monomer includes one or more selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eitocene, norbornene, norbornadiene, ethylidene norbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinyl benzene, and 3-chloromethylstyrene.

8. The method of claim 1 , wherein the molecular weight modifier is represented by the following Chemical Formula 5, Chemical Formula 6, or Chemical Formula 7:

9. The method of claim 2 , wherein the molecular weight modifier is represented by the following Chemical Formula 8:

10. The method of claim 1 , wherein the molecular weight modifier is used in an amount of about 10 −7 to 10 −1 parts by weight, based on a total of 100 parts by weight of the olefin monomer.

11. The method of claim 1 , wherein the metallocene catalyst includes one or more metallocene compounds represented by any one of the following Chemical Formulae 9 to 12:
(Cp 5 R a ) n (Cp 6 R b )M 3 Z 1 3-n   [Chemical Formula 9]

wherein M 3 is a Group 4 transition metal;
Cp 5 and Cp 6 are the same as or different from each other, and are each independently any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals, and these are substituted with a hydrocarbon having 1 to 20 carbon atoms;
R a and R b are the same as or different from each other, and are each independently hydrogen, a C1 to C20 alkyl, a C1 to C10 alkoxy, a C2 to C20 alkoxyalkyl, a C6 to C20 aryl, a C6 to C10 aryloxy, a C2 to C20 alkenyl, a C7 to C40 alkylaryl, a C7 to C40 arylalkyl, a C8 to C40 arylalkenyl, or a C2 to C10 alkynyl;
Z 1 is a halogen atom, a C1 to C20 alkyl, a C2 to C10 alkenyl, a C7 to C40 alkylaryl, a C7 to C40 arylalkyl, a C6 to C20 aryl, a substituted or unsubstituted C1 to C20 alkylidene, a substituted or unsubstituted amino group, a C2 to C20 alkylalkoxy, or a C7 to C40 arylalkoxy; and
n is 1 or 0;
(Cp 7 R c ) m B 1 (Cp 8 R d )M 4 Z 2 3-m   [Chemical Formula 10]

wherein M 4 is a Group 4 transition metal;
Cp 7 and Cp 8 are the same as or different from each other, and are each independently any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals, and these are substituted with a hydrocarbon having 1 to 20 carbon atoms;
R c and R d are the same as or different from each other, and are each independently hydrogen, a C1 to C20 alkyl, a C1 to C10 alkoxy, a C2 to C20 alkoxyalkyl, a C6 to C20 aryl, a C6 to C10 aryloxy, a C2 to C20 alkenyl, a C7 to C40 alkylaryl, a C7 to C40 arylalkyl, a C8 to C40 arylalkenyl, or a C2 to C10 alkynyl;
Z 2 is a halogen atom, a C1 to C20 alkyl, a C2 to C10 alkenyl, a C7 to C40 alkylaryl, a C7 to C40 arylalkyl, a C6 to C20 aryl, a substituted or unsubstituted C1 to C20 alkylidene, a substituted or unsubstituted amino group, a C2 to C20 alkylalkoxy, or a C7 to C40 arylalkoxy;
B 1 is any one or more of carbon, germanium, silicon, phosphorus, or nitrogen atom-containing radicals, which crosslink a Cp 3 R c ring and a Cp 4 R d ring or crosslinks one Cp 4 R d ring to M 2 , or a combination thereof; and
m is 1 or 0;
(Cp 9 R e )B 2 (J)M 5 Z 3 2   [Chemical Formula 11]

wherein M 5 is a Group 4 transition metal;
Cp 9 is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals, and these are substituted with a hydrocarbon having 1 to 20 carbon atoms;
R e is hydrogen, a C1 to C20 alkyl, a C1 to C10 alkoxy, a C2 to C20 alkoxyalkyl, a C6 to C20 aryl, a C6 to C10 aryloxy, a C2 to C20 alkenyl, a C7 to C40 alkylaryl, a C7 to C40 arylalkyl, a C8 to C40 arylalkenyl, or a C2 to C10 alkynyl;
Z 3 is a halogen atom, a C1 to C20 alkyl, a C2 to C10 alkenyl, a C7 to C40 alkylaryl, a C7 to C40 arylalkyl, a C6 to C20 aryl, a substituted or unsubstituted C1 to C20 alkylidene, a substituted or unsubstituted amino group, a C2 to C20 alkylalkoxy, or a C7 to C40 arylalkoxy;
B 2 is any one or more of carbon, germanium, s

Assignees

• Lg Chemical Ltd

Inventors

• Cho Kyung Jin
• Lee Yong Ho
• Lee Ki Soo
• Cho Min Seok
• Kim Se Young
• Lee Sung Min
• Park Jin Young

Classifications

• C08F210/16

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title

• C08F4/65925

  two cyclopentadienyl rings being mutually non-bridged · CPC title

• C08F210/14

  Monomers containing five or more carbon atoms · CPC title

• C08F2420/06

  Cp analog where at least one of the carbon atoms of the non-coordinating part of the condensed ring is replaced by a heteroatom · CPC title

• C08F10/00 Primary

  Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond · CPC title