Preparation method of a supported metallocene catalyst

Patent metadata

Field	Value
Publication number	US-9657119-B2
Application number	US-201415033866-A
Country	US
Kind code	B2
Filing date	Nov 28, 2014
Priority date	Nov 28, 2013
Publication date	May 23, 2017
Grant date	May 23, 2017

Abstract

The present invention relates to a preparation method of a highly active supported metallocene catalyst which can prepare a polyolefin of high bulk density. More specifically, the present invention provides a method of preparing the supported metallocene catalyst in which one or more metallocene catalysts are loaded on the silica carrier of which the inside is penetrated by more cocatalyst than the prior art and the outside is attached with a substantial amount of the cocatalyst. The catalyst according to the present invention can prepare a polyolefin polymer with improved bulk density and efficiency while maintaining its highly active catalytic characteristic.

First claim

The invention claimed is:

1. A method of preparing a supported metallocene catalyst, including the steps of:
preparing a silica carrier;
loading an alkylaluminoxane on the inside and the surface of the silica carrier by bringing the silica carrier into contact with the alkylaluminoxane, a cocatalyst component; and
sequentially loading one or more metallocene compounds on the silica carrier on which the alkylaluminoxane is loaded,
wherein the alkylaluminoxane is dividedly loaded at different temperatures by a separate-input method, and
wherein the amount of the alkylaluminoxane loaded on the silica carrier is 5 to 15 mmol/g based on 1 g of the silica carrier.

2. The method of preparing a supported metallocene catalyst according to claim 1 , wherein the alkylaluminoxane is loaded on the silica carrier by the separate-input method of primarily loading a part of the whole input of the alkylaluminoxane at the temperature of 50° C. or more and secondarily loading the rest of the whole input of the same at the temperature of 40° C. or less.

3. The method of preparing a supported metallocene catalyst according to claim 1 , wherein the silica carrier on which the alkylaluminoxane is loaded is obtained by the method of primarily loading 50 to 90 wt % of the whole input of the alkylaluminoxane on the silica carrier and carrying out the former reaction at 50 to 150° C., and secondarily loading the rest of the alkylaluminoxane on the silica carrier and carrying out the latter reaction at −10 to 40° C.

4. The method of preparing a supported metallocene catalyst according to claim 1 , wherein the supported metallocene catalyst is composed of: an outer layer including the area from each surface to a 1/3 position of the particle diameter toward the center and an inner layer including the rest of the area from the 1/3 position of the particle diameter to the center, in the cross-section of the supported catalyst particle, and includes the silica carrier on which the inside and surface thereof the alkylaluminoxane is loaded; and one or more metallocene compounds loaded on the silica carrier, and
the content ratio (wt %) of Al/Si elements of the inner layer is 65% or more compared to the content ratio (wt %) of Al/Si elements of the outer layer.

5. The method of preparing a supported metallocene catalyst according to claim 1 , wherein the content ratio (wt %) of Al/Si elements of the inner layer is 90 to 150% compared to the content ratio (wt %) of Al/Si elements of the outer layer.

6. The method of preparing a supported metallocene catalyst according to claim 1 , wherein the metallocene compound is one or more compounds selected from the group consisting of a metallocene compound including the combination of a non-bridge Cp and a Cp type, a metallocene compound including the combination of a Si bridge Cp and a Cp type, a metallocene compound including the combination of a C bridge Cp and a Cp type, a metallocene compound including the combination of a Si bridge Cp and an amine type, a metallocene compound including the combination of an ethylene bridge Cp and a Cp type, a metallocene compound including the combination of a phenylene bridge Cp and an amine type, and a metallocene compound including a C—C bridge, a Si—C bridge, or a Si—Si bridge.

7. The method of preparing a supported metallocene catalyst according to claim 1 , wherein the metallocene compound is one or more compounds selected from the group consisting of the compounds represented the following Chemical Formulae 1 to 6:
(Cp 1 R a ) n (Cp 2 R b )M 1 Z 1 3-n   [Chemical Formula 1]

wherein, in Chemical Formula 1,
M 1 is a group 4 transition metal;
Cp 1 and Cp 2 are the same as or different from each other, and are independently any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and a fluorenyl radical, and they may be substituted with a C1-C20 hydrocarbon;
R a and R b are the same as or different from each other, and are independently hydrogen, a C1-C20 alkyl, a C1-C10 alkoxy, a C2-C20 alkoxyalkyl, a C6-C20 aryl, a C6-C10 aryloxy, a C2-C20 alkenyl, a C7-C40 alkylaryl, a C7-C40 arylalkyl, a C8-C40 arylalkenyl, or a C2-C10 alkynyl;
Z 1 is a halogen, a C1-C20 alkyl, a C2-C10 alkenyl, a C7-C40 alkylaryl, a C7-C40 arylalkyl, a C6-C20 aryl, a substituted or non-substituted C1-C20 alkylidene, a substituted or non-substituted amino group, a C2-C20 alkylalkoxy, or a C7-C40 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 2]

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

wherein, in Chemical Formula 3,
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 a fluorenyl radical, and it may be substituted with a C1-C20 hydrocarbon;
R e is hydrogen, a C1-C20 alkyl, a C1-C10 alkoxy, a C2-C20 alkoxyalkyl, a C6-C20 aryl, a C6-C10 aryloxy, a C2-C20 alkenyl, a C7-C40 alkylaryl, a C7-C40 arylalkyl, a C8-C40 arylalkenyl, or a C2-C10 alkynyl;
Z 3 is a halogen, a C1-C20 alkyl, a C2-C10 alkenyl, a C7-C40 alkylaryl, a C7-C40 arylalkyl, a C6-C20 aryl, a substituted or non-substituted C1-C20 alkylidene, a substituted or non-substituted amino group, a C2-C20 alkylalkoxy, or a C7-C40 arylalkoxy;
B 2 is one or more radicals including a carbon, germanium, silicon, phosphorus, or nitrogen atom, or a combination thereof, which crosslink the Cp 5 R e ring with J; and
J is any one selected from the group consisting of NR f , O, PR f , and S, where R f is a C1-C20 alkyl, aryl, substituted alkyl, or substituted aryl,

wherein, in Chemical Formula 4,
R10 to R13 and R10′ to R13′ are the same as or different from each other, and are independently hydrogen, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C6-C20 aryl group, a C7-C20 alkylaryl group, a C7-C20 arylalkyl group, or a C1-C20 amine group, and 2 or more adjacent groups among R10 to R13 and R10′ to R13′ may be connected to each other and form one or more aliphatic rings, aromatic rings, or hetero rings;
Z1 and Z2 are the same as or different from each other, and are independently hydrogen, a C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C1-C20 alkoxy group, a C6-C20 aryl group, a C6-C10 aryloxy group, a C2-C20 alkenyl group, a C7-C40 alkylaryl group, or a C7-C40 arylalkyl group;
Q is a C1-C20 alkylene group, a C3-C20 cycloalkylene group, a C6-C20 arylene group, a C7-C40 alkylarylene group, or a C7-C40 arylalkylene group;
M2 is a group 4 t

Assignees

• Lg Chemical Ltd

Inventors

• Lee Seung Mi
• Choi Yi Young
• Lee Ki Soo
• Song Eun Kyoung
• Kwon Heon Yong
• Cho Min Seok
• Hong Dae Sik
• Kwon Hyun Jee
• Sung Yu Taek
• Jeong Dong Hoon

Classifications

• C08F4/65908

  in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+ · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C08F4/65916

  supported on a carrier, e.g. silica, MgCl2, polymer · CPC title

• C08F2420/05

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

• C08F110/02 Primary

  Ethene · CPC title