Method for preparing polyolefin and polyolefin prepared thereby

Patent metadata

Field	Value
Publication number	US-9988469-B2
Application number	US-201515303437-A
Country	US
Kind code	B2
Filing date	Jun 3, 2015
Priority date	Jun 3, 2014
Publication date	Jun 5, 2018
Grant date	Jun 5, 2018

Abstract

The present invention relates to a method for preparing polyolefin that can easily and effectively prepare polyolefin having high molecular weight and various molecular weight distributions, which was difficult to prepare using the existing metallocene catalyst, and polyolefin prepared thereby. The method for preparing polyolefin comprises the step of polymerizing olefin monomers, in the presence of a metallocene supported catalyst wherein a metallocene compound having a specific chemical structure is supported in a carrier, and hydrogen gas.

First claim

What is claimed is:

1. A method for preparing polyolefin comprising the step of polymerizing olefin monomers, in the presence of a supported metallocence catalyst wherein one or more kind of a first metallocene compound represented by the following Chemical Formula 1 and a cocatalyst are supported in a carrier, and hydrogen gas:

in the Chemical Formula 1,
A is hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, a C7 to C20 arylalkyl group, a C1 to C20 alkoxy group, a C2 to C20 alkoxyalkyl group, a C3 to C20 heterocycloalkyl group, or a C5 to C20 heteroaryl group;
D is —O—, —S—, —N(R)— or —Si(R)(R′)—, and R and R′ are identical to or different from each other, and are each independently hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, or a C6 to C20 aryl group;
L is a C1 to C10 linear or branched alkylene group;
B is carbon, silicon or germanium;
Q is hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group;
M is Group 4 transition metal;
X 1 and X 2 are identical to or different to each other, and are each independently halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a nitro group, an amido group, a C1 to C20 alkylsilyl group, a C1 to C20 alkoxy group, or a C1 to C20 sulfonate group;
C 1 and C 2 are identical to or different from each other, and are each independently represented by one of the following Chemical Formula 2a, Chemical Formula 2b or Chemical Formula 2c, provided that both C 1 and C 2 are not Chemical Formula 2c;

in the Chemical Formula 2a, 2b and 2c,
R1 to R17 and R1′ to R9′ are identical to or different from each other, and are each independently hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C1 to C20 alkylsilyl group, a C1 to C20 silylalkyl group, a C1 to C20 alkoxysilyl group, a C1 to C20 alkoxy group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group, and two or more neighboring groups of R10 to R17 may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring.

2. The method according to claim 1 , wherein the supported metallocene catalyst further comprises one or more kind of a second metallocene compound selected from the compounds represented by the following Chemical Formulae 3 to 5:
(Cp 1 R a ) n (Cp 2 R b )M 1 Z 1 3-n   [Chemical Formula 3]

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

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

in the Chemical Formula 5,
M 3 is a Group 4 transition metal;
Cp 5 is one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radicals, which may be substituted with hydrocarbon having a carbon number of 1 to 20;
R e is hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 to C20 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C8 to C40 arylalkenyl, or C2 to C10 alkynyl;
Z 3 is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene, substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 arylalkoxy;
B 2 is one or more of carbon, germanium, silicon, phosphorus or nitrogen-containing radical or a combination thereof, which crosslinks a Cp 5 R e ring with J; and
J is one selected from the group consisting of NR f , O, PR f and S, wherein R f is C 1-20 alkyl, aryl, substituted alkyl, or substituted aryl.

3. The method according to claim 1 , wherein the metallocene compound represented by the Chemical Formula 1 is selected from the group consisting of the following Structural Formulae:

4. The method according to claim 2 , wherein the second metallocene compound represented by the Chemical Formula 3 is selected from the group consisting of the following Structural Formulae:

5. The method according to claim 2 , wherein the second metallocene compound represented by the Chemical Formula 4 is selected from the group consisting of the following Structural Formulae:

6. The method according to claim 2 , wherein the second metallocene compound represented by the Chemical Formula 5 is selected from the group consisting of the following Structural Formulae:

Assignees

• Lg Chemical Ltd

Inventors

• Song Eun Kyoung
• Kwon Heon Yong
• Kwon Hyuck Ju
• Lee Yong Ho
• Choi Yi Young
• Hong Dae Sik
• Lee Ki Soo
• Cho Kyung Jin

Classifications

• C08F210/16

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

• C08F4/65927

  two cyclopentadienyl rings being mutually bridged · CPC title

• C08F2500/01

  High molecular weight, e.g. >800,000 Da. · CPC title

• C08F4/65904

  in combination with another component of C08F4/64 · CPC title

• C08F110/02 Primary

  Ethene · CPC title