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