Homogeneous catalyst system for producing ethylene homopolymer or ethylene copolymers with alpha-olefins
View Patent ↗Disclosed is a homogeneous catalyst system for producing an ethylene homopolymer or an ethylene copolymer with α-olefin. Specifically, this invention pertains to a transition metal catalyst which has stability under high temperature solution polymerization at 120˜250° C., in which a cyclopentadiene derivative and an electron donating substituent, both of which are bonded to a Group IV transition metal acting as a central metal, are crosslinked through a silyl derivative substituted with a cyclohexyl, to a catalyst system including such a transition metal catalyst and an aluminoxane cocatalyst or a boron compound cocatalyst, and to a method of producing an ethylene homopolymer or an ethylene copolymer with α-olefin, having high molecular weight, using the catalyst system under conditions of high-temperature solution polymerization. The catalyst according to this invention has excellent thermal stability and compatibility with a paraffin hydrocarbon solvent and thus is effective in the production of an ethylene homopolymer or an ethylene copolymer with α-olefin having various properties in commercial polymerization processes.
1. A homogenous catalyst system, comprising:
a homogenous catalyst which has stability under high temperature solution polymerization at 120-250° C. for producing an ethylene polymer represented by Formula 1 below, in which:
a cyclopentadiene derivative and an electron donating substituent, both of which are bonded to a Group IV transition metal,
are crosslinked through a silyl derivative substituted with a cyclic hydrocarbon, and tris(pentafluoro)borane cocatalyst, an aluminoxane cocatalyst and tris(pentafluoro)borane cocatalyst, or an organic alkyl aluminum and tris(pentafluoro)borane cocatalyst:
wherein M is a Group IV transition metal in the periodic table;
Cp is cyclopentadienyl or a derivative thereof, which is η 5 -bonded to a central metal;
D is an electron donating substituent including any one element selected from the group consisting of nitrogen, phosphorus, oxygen, and sulfur, with a C1-C20 alkyl group;
X is a halogen atom, a C1-C20 alkyl group with the exception of Cp derivatives, a C7-C30 arylalkyl group, a C1-C20 alkyl-containing alkoxy group, a C3-C20 alkyl-substituted siloxy group, or a C1-C20 hydrocarbon-containing amido group;
m is 3; and
n is 1 or 2 depending on an oxidation value of the transition metal,
wherein aluminoxane or organic alkyl aluminum is mixed such that a molar ratio of central transition metal:boron atom:aluminum atom is 1:0.5-5:25-500.
2. The catalyst according to claim 1 , wherein the aluminoxane cocatalyst is methylaluminoxane.
3. The catalyst system according to claim 1 , wherein the aluminoxane is selected from the group of compounds represented by Formulas 2 and 3 below, and the organic alkyl aluminum is trimethylaluminum, triethylaluminum or triisobutylaluminum:
(—Al(R 8 )—O—) p Formula 2
(R 8 ) 2 Al—(—O(R 8 )—) q —(R 8 ) 2 Formula 3
wherein R 8 is a C1-C20 alkyl group, and p and q are each an integer of 5 or more.
4. The catalyst system according to claim 1 , wherein the catalyst has stability under high temperature solution polymerization at 140-210° C.
5. A method of producing an ethylene homopolymer or an ethylene copolymer with α-olefin using the catalyst system of claim 1 , in which pressure in a reaction system is 10-150 atm, and polymerization is conducted at 120-250° C.
6. A method of producing an ethylene copolymer with α-olefin using the catalyst system of claim 1 , in which α-olefin polymerized with ethylene monomer is at least one selected from the group consisting of 1-butene, 1-hexene, 1-octene, and 1-decene, and the copolymer has 60 wt % or more ethylene.