IP Library Patent Application 14360544
Patent Application
App. No. 14/360,544

CATALYST FOR OLEFIN POLYMERIZATION AND COPOLYMERIZATION, AND OLEFIN POLYMERIZATION OR COPOLYMERIZATION METHOD USING SAME

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Patent No.
US None
App. No.
14/360,544
Abstract

The provided is an olefin (co)polymerization catalyst with an excellent catalyst activity, wherein the catalyst component is prepared by using a metallocene compound and titanocene compound or a half-titanocene compound so as to provide polyolefins having a high molecular weight and a low melt index, and also a method for olefin (co)polymerization using said catalyst.

Claims (34)

1 . A catalyst for olefin (co)polymerization prepared by the method comprising:

(1) supporting aluminoxane, a metallocene compound and a titanocene compound or half-titanocene compound onto a support, wherein the molar ratio of the titanocene compound or half-titanocene compound to the metallocene compound is 0.03:1-10:1, wherein the metallocene compound is selected from the compounds having the chemical formulas (1) to (3), and wherein the titanocene compound or half-titanocene compound is selected from the compounds having the chemical formula (4):

(CpR n )(CpR′ m )ML q   (1)

wherein Cp is a cyclopentadienyl, indenyl or fluorenyl;

each of R and R′ independently is hydrogen, alkyl, alkylether, allylether, phosphine or amine;

L is an alkyl, allyl, arylalkyl, amide, alkoxy or halogen;

M is a transition metal of Group 4 or 5 in the periodic table; and

each of n, m and q is an integer within the following range: 0≦n<5, 0≦m<5, and 1≦q≦4;

Q(CPR n )(CpR′ m )ML q   (2)

wherein, each of Cp, R, R′, M and L has the same meaning as defined in the chemical formula (1);

Q is a crosslinkage between the carbon rings, which is selected from dialkyl, alkylaryl, diaryl silicon or C1-C20 hydrocarbon group; and

each of n, m and q is an integer within the following range: 0≦n<4, 0≦m<4, and 1≦q≦4;

wherein, x is 0, 1, 2, 3 or 4; y is 0 or 1;

R is hydrogen, or a substituent having 1-20 non-hydrogen atom(s) selected from the group consisting of C1-C20 hydrocarbon group, silyl, germyl, cyano, halogen and a combination thereof;

Y′ is —O—, —S—, —NR*—, or —PR*—, wherein R* is hydrogen, C1-C12 hydrocarbon group, C1-C8 hydrocarbyloxy, silyl, C1-C8 halogenated alkyl, C6-C20 halogenated aryl or a combination thereof;

Z is SiR* 2 , CR* 2 , SiR* 2 SiR* 2 , CR* 2 CR* 2 , CR*═CR*, CR* 2 SiR* 2 or GeR* 2 , wherein R* is as previously defined;

each L independently is a substituent having 1-20 non-hydrogen atom(s) selected from the group consisting of halide, C1-C20 hydrocarbon group, C1-C18 hydrocarbyloxy, C1-C19 hydrocarbylamino, C1-C18 hydrocarbylamide, C1-C18 hydrocarbylphosphide, C1-C18 hydrocarbylsulfide and a combination thereof, or two Ls together represent C1-C30 neutral conjugated dien or divalent group; and

M is a transition metal of Group 4 or 5 of the periodic table;

(CpR n )(CpR′ m )TiL q   (4)

wherein, Cp is cyclopentadienyl, indenyl, tetrahydroindenyl or fluorenyl;

each of R and R′ independently is hydrogen, C1-C20 hydrocarbon group, alkylether, alkylsilyl, allylether, alkoxyalkyl, phosphine or amine;

L is alkyl, allyl, arylalkyl, amide, alkoxy or halogen; and

each of n, m and q is an integer within the following range: 0≦n<5, 0≦m<5 and 1≦q≦4;

(2) washing the supported catalyst obtained from the above step (1) with an organic solvent; and

(3) drying the catalyst washed from the above step (2) and thus collecting the catalyst in the form of powder.

2 . The catalyst according to claim 1 , wherein the supporting of the step (1) is conducted by adding a solution obtained by dissolving the metallocene compound together with the titanocene compound or half-titanocene compound in aluminoxane solution to a support slurry, and stirring the mixture.

3 . The catalyst according to claim 1 , wherein the supporting of the step (1) is conducted by adding aluminoxane to a support slurry and stirring the mixture so as to obtain an aluminoxane supported support slurry, and adding thereto the metallocene compound and the titanocene compound or half-titanocene compound and stirring the mixture.

4 . The catalyst according to claim 1 , wherein the support is silica having the average particle size of 10-250 μm; micropores of which average diameter is 50-500 Å and volume is 0.1-10 ml/g; and the surface area of 5-1000 m 2 /g.

5 . The catalyst according to claim 1 , wherein the aluminoxane is selected from linear aluminoxane oligomers and cyclic aluminoxane oligomers.

6 . A method for polymerizing olefins or copolymerizing olefin with comonomer(s) by using a catalyst according to claim 1 .

7 . A method for polymerizing olefins or copolymerizing olefin with comonomer(s) by using a catalyst according to claim 2 .

8 . A method for polymerizing olefins or copolymerizing olefin with comonomer(s) by using a catalyst according to claim 3 .

9 . A method for polymerizing olefins or copolymerizing olefin with comonomer(s) by using a catalyst according to claim 4 .

10 . A method for polymerizing olefins or copolymerizing olefin with comonomer(s) by using a catalyst according to claim 5 .

Assignments (3)
CORRECTIVE ASSIGNMENT TO CORRECT THE RECEIVING PARTY ADDRESS PREVIOUSLY RECORDED AT REEL: 036548 FRAME: 0271. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT. Recorded Nov 9, 2015
From: SAMSUNG ATOFINA CO., LTD.; SAMSUNG TOTAL PETROCHEMICALS CO., LTD.
To: HANWHA TOTAL PETROCHEMICAL CO., LTD.
Reel/Frame 037071/0433 →
CHANGE OF NAME Recorded Sep 3, 2015
From: SAMSUNG ATOFINA CO., LTD.; SAMSUNG TOTAL PETROCHEMICALS CO., LTD.
To: HANWHA TOTAL PETROCHEMICAL CO., LTD.
Reel/Frame 036548/0271 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 23, 2014
From: YANG, CHUN BYUNG; PARK, JOON RYEO
To: SAMSUNG TOTAL PETROCHEMICALS CO., LTD.
Reel/Frame 033013/0196 →