Method for preparing hybrid supported metallocene catalyst

Patent metadata

Field	Value
Publication number	US-2016237188-A1
Application number	US-201415029196-A
Country	US
Kind code	A1
Filing date	Oct 15, 2014
Priority date	Oct 18, 2013
Publication date	Aug 18, 2016
Grant date	—

Abstract

The present invention relates to a method for preparing a hybrid supported metallocene catalyst. More specifically, the present invention relates to a method for preparing a hybrid supported metallocene catalyst by using two or more different types of metallocene compounds. One type of the metallocene compounds shows a high polymerization activity even when it is supported, and thus the catalyst has an excellent activity and can be utilized in the polymerization of olefinic polymers having ultra-high molecular weight. Based on the hybrid supported metallocene catalyst obtained according to the preparation method of the present invention, an olefinic polymer having high molecular weight and the desired physical property can be prepared.

First claim

What is claimed is:

1 . A method for preparing a hybrid supported metallocene catalyst which comprises the steps of
supporting a first cocatalyst compound on a support; supporting one or more first metallocene compounds represented by the following Chemical Formula 1 and one or more second metallocene compounds selected among the compounds represented by the following Chemical Formula 3 to 5 on the support on which the first cocatalyst compound has been supported; and supporting a second cocatalyst compound on the support on which the first cocatalyst compound, the first metallocene compound and the second metallocene compound have been supported:

in Chemical Formula 1,
A is hydrogen, halogen, C 1 -C 20 alkyl group, C 2 -C 20 alkenyl group, C 6 -C 20 aryl group, C 7 -C 20 alkylaryl group, C 7 -C 20 arylalkyl group, C 1 -C 20 alkoxy group, C 2 -C 20 alkoxyalkyl group, C 3 -C 20 heterocycloalkyl group, or C 5 -C 20 heteroaryl group;
D is —O—, —S—, —N(R)—, or —Si(R)(R′)—, wherein R and R′ are same as or different from each other and each are independently hydrogen, halogen, C 1 -C 20 alkyl group, C 2 -C 20 alkenyl group, or C 6 -C 20 aryl group;
L is C 1 -C 10 linear or branched alkylene group;
B is carbon, silicon, or germanium;
Q is hydrogen, halogen, C 1 -C 20 alkyl group, C 2 -C 20 alkenyl group, C 6 -C 20 aryl group, C 7 -C 20 alkylaryl group, or C 7 -C 20 arylalkyl group;
M is a Group 4 transition metal;
X 1 and X 2 are same as or different from each other, and each are independently halogen, C 1 -C 20 alkyl group, C 2 -C 20 alkenyl group, C 6 -C 20 aryl group, nitro group, amido group, C 1 -C 20 alkylsilyl group, C 1 -C 20 alkoxy group, or C 1 -C 20 sulfonate group;
C 1 and C 2 are same as or different from each other, and each is independently represented by any one of the following Chemical Formula 2a, Chemical Formula 2b or Chemical Formula 2c, provided that both C 1 and C 2 are not represented by Chemical Formula 2c:

in Chemical Formulae 2a, 2b and 2c, R 1 to R 17 and R 1 ′ to R 9 ′ are same as or different from each other, and each independently hydrogen, halogen, C 1 -C 20 alkyl group, C 2 -C 20 alkenyl group, C 1 -C 20 alkylsilyl group, C 1 -C 20 silylalkyl group, C 1 -C 20 alkoxysilyl group, C 1 -C 20 alkoxy group, C 6 -C 20 aryl group, C 7 -C 20 alkylaryl group, or C 7 -C 20 arylalkyl group, wherein two or more adjacent groups among R 10 to R 17 may be connected together to form substituted or unsubstituted aliphatic or aromatic ring;
(Cp 1 R a ) n (Cp 2 R b )M 1 Z 1 3-n   [Chemical Formula 3]

in Chemical Formula 3,
M 1 is a Group 4 transition metal;
Cp 1 and Cp 2 are same as or different from each other, and each independently any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radical, each of which may be substituted by hydrocarbon having 1 to 20 carbon atoms;
R a and R b are same as or different from each other, and each independently hydrogen, C 1 -C 20 alkyl, C 1 -C 10 alkoxy, C 2 -C 20 alkoxyalkyl, C 6 -C 20 aryl, C 6 -C 10 aryloxy, C 2 -C 20 alkenyl, C 7 -C 40 alkylaryl, C 7 -C 40 arylalkyl, C 8 -C 40 arylalkenyl, or C 2 -C 10 alkinyl;
Z 1 is halogen atom, C 1 -C 20 alkyl, C 2 -C 10 alkenyl, C 7 -C 40 alkylaryl, C 7 -C 40 arylalkyl, C 6 -C 20 aryl, substituted or unsubstituted C 1 -C 20 alkylidene, substituted or unsubstituted amino group, C 2 -C 20 alkylalkoxy, or C 7 -C 40 arylalkoxy; and
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 Chemical Formula 4,
M 2 is a Group 4 transition metal;
Cp 3 and Cp 4 are same as or different from each other, and each independently any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radical, each of which may be substituted by hydrocarbon having 1 to 20 carbon atoms;
R c and R d are same as or different from each other, and each independently hydrogen, C 1 -C 20 alkyl, C 1 -C 10 alkoxy, C 2 -C 20 alkoxyalkyl, C 6 -C 20 aryl, C 6 -C 10 aryloxy, C 2 -C 20 alkenyl, C 7 -C 40 alkylaryl, C 7 -C 40 arylalkyl, C 8 -C 40 arylalkenyl, or C 2 -C 10 alkinyl;
Z 2 is halogen atom, C 1 -C 20 alkyl, C 2 -C 10 alkenyl, C 7 -C 40 alkylaryl, C 7 -C 40 arylalkyl, C 6 -C 20 aryl, substituted or unsubstituted C 1 -C 20 alkylidene, substituted or unsubstituted amino group, C 2 -C 20 alkylalkoxy, or C 7 -C 40 arylalkoxy;
B 1 is one or more selected among the radicals containing carbon, germanium, silicon, phosphorous or nitrogen atom, which crosslink Cp 3 R c ring to Cp 4 R d ring or crosslink one Cp 4 R d ring to M 2 , combinations thereof; and
m is 1 or 0;
(Cp 5 R e )B 2 (J)M 3 Z 3 2   [Chemical Formula 5]

in Chemical Formula 5,
M 3 is a Group 4 transition metal;
Cp 5 is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radical, each of which may be substituted by hydrocarbon having 1 to 20 carbon atoms;
R e is hydrogen, C 1 -C 20 alkyl, C 1 -C 10 alkoxy, C 2 -C 20 alkoxyalkyl, C 6 -C 20 aryl, C 6 -C 10 aryloxy, C 2 -C 20 alkenyl, C 7 -C 40 alkylaryl, C 7 -C 40 arylalkyl, C 8 -C 40 arylalkenyl, or C 2 -C 10 alkinyl;
Z 3 is halogen atom, C 1 -C 20 alkyl, C 2 -C 10 alkenyl, C 7 -C 40 alkylaryl, C 7 -C 40 arylalkyl, C 6 -C 20 aryl, substituted or unsubstituted C 1 -C 20 alkylidene, substituted or unsubstituted amino group, C 2 -C 20 alkylalkoxy, or C 7 -C 40 arylalkoxy;
B 2 is one or more selected among the radicals containing carbon, germanium, silicon, phosphorous or nitrogen atom, which crosslink Cp 5 R e ring to J, or combinations thereof, and
J is any one selected from the group consisting of NR f , O, PR f and S, wherein R f is C 1 -C 20 alkyl, aryl, substituted alkyl or substituted aryl.

2 . The method for preparing a hybrid supported metallocene catalyst according to claim 1 wherein R 1 to R 17 and R 1 ′ to R 9 ′ in Chemical Formulae 2a, 2b and 2c are each independently hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, phenyl group, halogen group, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tributylsilyl group, triisopropylsilyl group, trimethylsilylmethyl group, methoxy group, or ethoxy group.

3 . The method for preparing a hybrid supported metallocene catalyst according to claim 1 wherein L in Chemical Formula 1 is C 4 -C 8 linear or branched alkylene group.

4 . The method for preparing a hybrid supported metallocene catalyst according to claim 1 wherein A in Chemical Formula 1 is hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, methoxymethyl group, tert-butoxymethyl group, 1-ethoxyethyl group, 1-methyl-1-methoxyethyl group, tetrahydropyranyl group, or tetrahydrofuranyl group.

5 . The method for preparing a hybrid supported metallocene catalyst according to claim 1 wherein the first metallocene compound represented by Chemical Formula 1 is one of the compounds of the following structural formulae:

Assignees

• Lg Chemical Ltd

Inventors

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

Classifications

• C08F210/16 Primary

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

• C07F17/00 Primary

  Metallocenes · CPC title

• B01J31/12

  containing organo-metallic compounds or metal hydrides · CPC title

• C08F4/65925

  two cyclopentadienyl rings being mutually non-bridged · CPC title