Method of preparing supported metallocene catalyst

Patent metadata

Field	Value
Publication number	US-2018094084-A1
Application number	US-201615566098-A
Country	US
Kind code	A1
Filing date	Jun 13, 2016
Priority date	Jun 15, 2015
Publication date	Apr 5, 2018
Grant date	—

Abstract

A method of preparing a supported metallocene catalyst capable of more effectively preparing a polyolefin which may be preferably used for blow molding, etc., because its molecular weight distribution is such that polymer elasticity is increased to improve swell, is provided.

First claim

1 . A method of preparing a supported metallocene catalyst, comprising: preparing a molecular weight modifier composition by mixing a cyclopentadienyl metal compound of the following Chemical Formula 1 and an organic aluminum compound of the following Chemical Formula 2 and stirring a resulting mixture at room temperature for 50 hours to 108 hours; and supporting one or more metallocene compounds represented by any one of the following Chemical Formulae 3 to 6 and the molecular weight modifier composition on a support:
(R 1 -Cp 1 )(R 2 -Cp 2 )M 4 X 2   Chemical Formula 1
in Chemical Formula 1, Cp 1 and Cp 2 are each independently a ligand comprising 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 hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, a heteroalkenyl group having 2 to 20 carbon atoms, a heteroalkylaryl group having 6 to 20 carbon atoms, a heteroarylalkyl group having 6 to 20 carbon atoms, or a heteroaryl group having 5 to 20 carbon atoms; M 4 is a Group 4 transition metal element; and X is a halogen,
R 3 R 4 R 5 Al  Chemical Formula 2

in Chemical Formula 2, R 3 , R 4 , and R 5 are each independently an alkyl group having 4 to 20 carbon atoms or a halogen, and at least one of R 3 , R 4 , and R 5 is an alkyl group having 4 to 20 carbon atoms,
(Cp 5 R a ) n (Cp 6 R b )M 1 Z 1 3-n   Chemical Formula 3

in Chemical Formula 3, M 1 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 may be 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 5 R d )M 2 Z 2 3-m   Chemical Formula 4

in Chemical Formula 4, M 2 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 crosslink 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 3 Z 3 2   Chemical Formula 5

in Chemical Formula 5, M 3 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, silicon, phosphorus, or nitrogen atom-containing radicals, which crosslink a Cp 5 R e ring to J, or a combination thereof; J is any one selected from the group consisting of NR f , O, PR f and S; and R f is a C1 to C20 alkyl, aryl, substituted alkyl, or substituted aryl,

in Chemical Formula 6,
A is hydrogen, a 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′)—, in which R and R′ are the same as or different from each other, and are each independently hydrogen, a 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 straight or branched alkylene group;
B is carbon, silicon, or germanium;
Q is hydrogen, a 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 a Group 4 transition metal;
X 1 and X 2 are the same as or different from each other, and are each independently a 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 the same as or different from each other, and are each independently represented by any one of the following Chemical Formula 7a, Chemical Formula 7b, and Chemical Formula 7c, excluding that both C 1 and C 2 are Chemical Formula 7c,

in Chemical Formulae 7a, 7b, and 7c,
R 1 to R 17 and R 1 ′ to R 9 ′ are the same as or different from each other, and are each independently hydrogen, a 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 R 1 to R 17 are connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring.

2 . The method of preparing the supported metallocene catalyst of claim 1 , wherein the supporting is performed by mixing the support, the metallocene catalyst, and the molecular weight modifier composition, and stirring a resulting mixture at a temperature of 30° C. to 100° C. for 1 hour to 12 hours.

3 . The method of preparing the supported metallocene catalyst of claim 1 , wherein the molecular weight modifier composition is supported in an amount of about 1 mol % to 85 mol %, based on the total weight of the metallocene compound.

4 . The method of prepa

Assignees

• Lg Chemical Ltd

Inventors

• You Young Suk
• Cho Kyung Jin
• Kwon Hyuck Ju
• Choi Yi Young
• Lee Ki Soo
• Song Eun Kyoung
• Kim Woo Ri

Classifications

• C08F2410/01

  Additive used together with the catalyst, excluding compounds containing Al or B · CPC title

• C08F2410/03

  Multinuclear procatalyst, i.e. containing two or more metals, being different or not · CPC title

• C08F4/65927

  two cyclopentadienyl rings being mutually bridged · CPC title

• C08F4/65916

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

• C08F2420/04

  Cp or analog not bridged to a non-Cp X ancillary anionic donor · CPC title