Hybrid catalyst composition, catalyst comprising same, and preparation method thereof
阅读说明：本技术 杂化催化剂组合物、包含其的催化剂及它们的制备方法 (Hybrid catalyst composition, catalyst comprising same, and preparation method thereof ) 是由 朴兰花 朴娍演 李泫承 郑旭 于 2020-03-27 设计创作，主要内容包括：本发明涉及包含不同种类的过渡金属化合物的杂化催化剂组合物、包含其的用于聚合烯烃的催化剂、及它们的制备方法。具体地,本发明涉及能够制备具有优异的加工性和机械性能的各种聚烯烃的、包含不同种类过渡金属化合物的杂化催化剂组合物、包含其的用于聚合烯烃的催化剂、以及通过调节杂化过渡金属化合物的比例而制备杂化催化剂组合物和包含其的催化剂的方法。(The present invention relates to a hybrid catalyst composition comprising different kinds of transition metal compounds, a catalyst for polymerizing olefins comprising the same, and a method for preparing the same. In particular, the present invention relates to a hybrid catalyst composition comprising different kinds of transition metal compounds capable of preparing various polyolefins having excellent processability and mechanical properties, a catalyst for polymerizing olefins comprising the same, and a method of preparing the hybrid catalyst composition and the catalyst comprising the same by adjusting a ratio of the hybrid transition metal compounds.)
1. A hybrid catalyst composition comprising at least two of transition metal compounds represented by the following chemical formulas 1 to 3,
[ chemical formula 1 ]
[ chemical formula 2 ]
[ chemical formula 3 ]
In the chemical formulas 1 to 3, M is each titanium, zirconium or hafnium,
x is each independently halogen, C1-20Alkyl radical, C2-20Alkenyl radical, C2-20Alkynyl, C6-20Aryl radical, C1-20Alkyl radical C6-20Aryl radical, C6-20Aryl radical C1-20Alkyl radical, C1-20Alkylamide group, C6-20Aryl amido radical or C1-20An alkylene group or a substituted alkylene group,
R1to R5And R6To R12Each independently hydrogen, substituted or unsubstituted C1-20Alkyl, substituted or unsubstituted C2-20Alkenyl, substituted or unsubstituted C6-20Aryl, substituted or unsubstituted C1-20Alkyl radical C6-20Aryl, substituted or unsubstituted C6-20Aryl radical C1-20Alkyl, substituted or unsubstituted C1-20Heteroalkyl, substituted or unsubstituted C3-20Heteroaryl, substituted or unsubstituted C1-20Alkylamido, substituted or unsubstituted C6-20Arylamido, substituted or unsubstituted C1-20Alkylene, or substituted or unsubstituted C1-20A silyl group (a) having a silyl group (a),
R1to R5And R6To R12Each independently forming a substituted or unsubstituted saturated or unsaturated C by linking to an adjacent group4-20And (4) a ring.
2. The hybrid catalyst composition of claim 1 wherein each M is zirconium or hafnium and each X is haloElement, or substituted or unsubstituted C1-20Alkyl radical, R1To R5And R6To R12Each is hydrogen, substituted or unsubstituted C1-20Alkyl, or substituted or unsubstituted C6-20And (4) an aryl group.
3. The hybrid catalyst composition according to claim 1, wherein the transition metal compound represented by chemical formula 1 is at least one selected from the transition metal compounds represented by chemical formulas 1-1 to 1-10 below, the transition metal compound represented by chemical formula 2 is at least one selected from the transition metal compounds represented by chemical formulas 2-1 to 2-10 below, the transition metal compound represented by chemical formula 3 is at least one selected from the transition metal compounds represented by chemical formulas 3-1 to 3-10 below,
[ chemical formula 1-10 ]
[ chemical formula 2-10 ]
[ chemical formula 3-10 ]
4. A method of preparing a hybrid catalyst composition, the method comprising the steps of:
(1) dissolving a compound represented by the following chemical formula 4 and a compound represented by the following chemical formula 5 in a solvent;
(2) adding a compound represented by the following chemical formula 6 to the solution obtained in step (1), and then stirring to obtain a hybrid catalyst composition comprising at least two of transition metal compounds represented by the following chemical formulas 1 to 3,
wherein a molar ratio of the compound represented by chemical formula 4 to the compound represented by chemical formula 5 is 10: 1 to 1: 10,
[ chemical formula 1 ]
[ chemical formula 2 ]
[ chemical formula 3 ]
[ chemical formula 4 ]
[ chemical formula 5 ]
[ chemical formula 6 ]
MX4，
In the chemical formulas 1 to 6, M, X, R1To R5And R6To R12As defined in claim 1.
5. The method for preparing a hybrid catalyst composition according to claim 4, wherein the compound represented by chemical formula 4 is at least one selected from the group consisting of the compounds represented by the following chemical formulae 4-1 to 4-10, the compound represented by chemical formula 5 is at least one selected from the group consisting of the compounds represented by the following chemical formulae 5-1 to 5-10,
[ chemical formula 4-10 ]
[ chemical formula 5-10 ]
6. The method for preparing the hybrid catalyst composition according to claim 4, wherein the compound represented by chemical formula 6 is ZrCl4。
7. The method for preparing the hybrid catalyst composition according to claim 4, wherein the solvent comprises at least one selected from the group consisting of hexane, pentane, toluene, benzene, dichloromethane, diethyl ether, tetrahydrofuran, acetone, and ethyl acetate.
8. The method for preparing the hybrid catalyst composition according to claim 4, further comprising the steps of: (2') drying the hybrid catalyst composition obtained in the step (2).
9. The method for preparing the hybrid catalyst composition according to claim 8, further comprising the steps of: (2') dissolving the dried hybrid catalyst composition obtained in the step (2') in a solvent, and then removing unreacted materials and/or impurities through a filter.
10. The method for preparing the hybrid catalyst composition according to claim 9, wherein the solvent comprises at least one selected from the group consisting of hexane, pentane, toluene, benzene, dichloromethane, diethyl ether, tetrahydrofuran, acetone, and ethyl acetate.
11. A catalyst for polymerizing olefins, comprising: the hybrid catalyst composition according to any one of claims 1 to 3; and a cocatalyst compound.
12. The catalyst for polymerizing olefins according to claim 11, wherein the co-catalyst compound is one or more compounds selected from the group consisting of a compound represented by the following chemical formula 7, a compound represented by chemical formula 8, and a compound represented by chemical formula 9,
[ chemical formula 7 ]
[ chemical formula 8 ]
[ chemical formula 9 ]
[L-H]+[Z(A)4]-Or [ L]+[Z(A)4]-，
In the chemical formula 7, n is an integer of 2 or more, RaIs a halogen atom, C1-20Hydrocarbyl, or C substituted by halogen1-20A hydrocarbon group,
in the chemical formula 8, D is aluminum or boron, Rb、RcAnd RdEach independently is a halogen atom, C1-20Hydrocarbyl, halogen-substituted C1-20Hydrocarbyl or C1-20An alkoxy group,
in the chemical formula 9, L is a neutral or cationic Lewis base, [ L-H ]]+And [ L]+Is a Bronsted acid, Z is a group 13 element, A are each independently substituted or unsubstituted C6-20Aryl, or substituted or unsubstituted C1-20An alkyl group.
13. The catalyst for polymerizing olefins according to claim 12, wherein the compound represented by chemical formula 7 is at least one selected from the group consisting of methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane.
14. The catalyst for polymerizing olefins according to claim 12, wherein the compound represented by chemical formula 8 is at least one selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylaluminum chloride, triisopropylaluminum, tri-sec-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethylaluminum methoxide, dimethylaluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, and tributylboron.
15. The catalyst for polymerizing olefins according to claim 12, wherein the compound represented by chemical formula 9 is selected from triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (p-tolyl) boron, trimethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetra (pentafluorophenyl) boron, N-diethylanilinium tetraphenylboron, N-diethylanilinium tetra (pentafluorophenyl) boron, diethylammonium tetra (pentafluorophenyl) boron, triphenylphosphonium tetraphenylboron, trimethylphosphorylboron, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, trimethylammoniuminumtetraphenylaluminum, tripropylammonium tetraphenylaluminum, triethylammonium tetraphenylboron, At least one compound selected from the group consisting of trimethylammonium tetrakis (p-tolyl) aluminum, tripropylammonium tetrakis (p-tolyl) aluminum, triethylammonium tetrakis (o, p-dimethylphenyl) aluminum, tributylammonium tetrakis (p-trifluoromethylphenyl) aluminum, trimethylammonium tetrakis (p-trifluoromethylphenyl) aluminum, tributylammonium tetrakis (pentafluorophenyl) aluminum, N-diethylaniliniumtetraphenylaluminum, N-diethylaniliniumtetrakis (pentafluorophenyl) aluminum, diethylammonium tetrakis (pentafluorophenyl) aluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, tripropylammonium tetrakis (p-tolyl) boron, triethylammonium tetrakis (o, p-dimethylphenyl) boron, tributylammonium tetrakis (p-trifluoromethylphenyl) boron, triphenylcarbonium tetrakis (p-trifluoromethylphenyl) boron, and triphenylcarbonium tetrakis (pentafluorophenyl) boron.
16. The catalyst for polymerizing olefins of claim 11 further comprising a support supporting the hybrid catalyst composition, the co-catalyst compound, or the hybrid catalyst composition and the co-catalyst compound.
17. The catalyst for polymerizing olefins of claim 16 wherein the support comprises at least one member selected from the group consisting of silica, alumina, and magnesia.
18. The catalyst for polymerizing olefins of claim 16, wherein the hybrid transition metal compound is supported on the carrier in a total amount of 0.001 to 1mmole and the cocatalyst compound is supported on the carrier in an amount of 2 to 15mmole, based on 1g of the carrier.
19. A method of preparing a catalyst for polymerizing olefins, the method comprising the steps of:
(1) dissolving a compound represented by the following chemical formula 4 and a compound represented by the following chemical formula 5 in a solvent;
(2) adding a compound represented by the following chemical formula 6 to the solution obtained in step (1), and then stirring to obtain a hybrid catalyst composition comprising at least two of transition metal compounds represented by the following chemical formulas 1 to 3;
(3) loading the hybrid catalyst composition, the cocatalyst compound or both obtained in step (2) on a support,
wherein a molar ratio of the compound represented by chemical formula 4 to the compound represented by chemical formula 5 is 10: 1 to 1: 10,
[ chemical formula 1 ]
[ chemical formula 2 ]
[ chemical formula 3 ]
[ chemical formula 4 ]
[ chemical formula 5 ]
[ chemical formula 6 ]
MX4，
In the chemical formulas 1 to 6, M, X, R1To R5And R6To R12As defined in claim 1.
Technical Field
The present invention relates to a hybrid catalyst composition comprising different kinds of transition metal compounds, a catalyst for polymerizing olefins comprising the same, and a method for preparing the same. In particular, the present invention relates to a hybrid catalyst composition comprising two or more transition metal compounds capable of preparing various polyolefins having excellent processability and mechanical properties, a catalyst for polymerizing olefins comprising the same, and a method for preparing the hybrid catalyst composition and the catalyst.
Background
Polyolefin polymers are widely used in actual life as materials for shopping bags, vinyl houses, fishing nets, cigarette wrapping paper, instant noodle bags, yogurt bottles, battery cases, automobile bumpers, interior materials, shoe soles, washing machines, and the like.
In the prior art, polyolefin polymers such as polyethylene, polypropylene and ethylene-alpha olefin copolymers and their copolymers are prepared under heterogeneous catalysts, such as Ziegler-Natta (Ziegler-Natta) catalysts consisting of a titanium compound and an alkylaluminum compound.
Recently, a method of preparing polyolefins by using a metallocene catalyst, which is a homogeneous catalyst having an extremely high catalytic activity, has been studied. The metallocene catalyst is a compound in which a transition metal or a transition metal halide is coordinated and bonded to a ligand such as cyclopentadienyl (cyclopentadienyl), indenyl (indenyl), cycloheptadienyl (cyclopentadienyl), and the like, and has a basic form of a sandwich structure. In this case, the ligand will have various molecular structures depending on the form of the ligand and the type of the central metal.
As a heterogeneous catalyst, a ziegler-natta catalyst is not uniform in the property of an active center because a metal component as the active center is dispersed on the surface of an inert solid, whereas a metallocene catalyst is a compound having a fixed structure and thus is considered as a single-site catalyst (single-site catalyst) in which all active centers have the same polymerization characteristics.
Generally, since the metallocene catalyst itself has no activity as a polymerization catalyst, it is used together with a cocatalyst such as methylaluminoxane. The metallocene catalyst is activated to a cation by the action of the cocatalyst, and the cocatalyst is an anion which does not coordinate with the metallocene catalyst, and stabilizes the unsaturated cationic active species, thereby forming a catalyst system which is active in various olefin polymerizations.
The metallocene catalyst is easy to copolymerize, and the three-dimensional structure of the polymer can be adjusted according to the symmetry of the catalyst, so that the prepared macromolecule has the advantages of narrow molecular weight distribution and uniform comonomer distribution.
On the other hand, since the polymer produced under the metallocene catalyst has a narrow molecular weight distribution, it has a problem of poor processability although it has excellent mechanical strength. In order to solve these problems, various methods have been proposed such as changing the molecular structure of the polymer or broadening the molecular weight distribution. For example, in U.S. Pat. No. 5,272,236, processability of a polymer is improved by using a catalyst capable of introducing a Long Chain Branch (LCB) as a side chain into the main chain of the polymer, but there is a problem in that the activity of a supported catalyst is low.
In order to solve the problems of such a single metallocene catalyst and to more conveniently develop a catalyst having excellent activity and improved processability, a method of hybrid-supporting metallocene catalysts having different characteristics (different kinds of metallocene catalysts) has been proposed. For example, in U.S. Pat. No. 4,935,474, U.S. Pat. No. 6,828,394, U.S. Pat. No. 6,894,128, korean patent No. 1437509, U.S. Pat. No. 6,841,631, a method of preparing a polyolefin having a bimodal molecular weight distribution by using catalysts having different reactivities to comonomers is disclosed. Polyolefins having a bimodal molecular weight distribution prepared by the above-described method, although having improved processability, have lower homogeneity due to having a different molecular weight distribution. Therefore, it is difficult to obtain a product having uniform physical properties after processing, and there is a problem that mechanical strength is lowered.
In addition, in order to solve the problem of the heterogeneous metallocene hybrid supported catalyst, a method of using a dinuclear metallocene catalyst having two active centers has been proposed. For example, korean patent application laid-open No. 2004-.
Disclosure of Invention
Technical problem
An object of the present invention is to provide a hybrid catalyst composition comprising different kinds of transition metal compounds capable of preparing various polyolefins having excellent processability and mechanical properties, and a catalyst for polymerizing olefins comprising the same.
It is another object of the present invention to provide a method for preparing a hybrid catalyst composition and a catalyst for polymerizing olefins comprising the same by adjusting the ratio of transition metal compounds.
Technical scheme
In order to achieve the above objects, in one embodiment, the present invention provides a hybrid catalyst composition comprising at least two of transition metal compounds represented by the following chemical formulas 1 to 3.
[ chemical formula 1 ]
[ chemical formula 2 ]
[ chemical formula 3 ]
In the chemical formulas 1 to 3, M is each titanium (Ti), zirconium (Zr), or hafnium (Hf),
each X is independently halogen、C1-20Alkyl radical, C2-20Alkenyl radical, C2-20Alkynyl, C6-20Aryl radical, C1-20Alkyl radical C6-20Aryl radical, C6-20Aryl radical C1-20Alkyl radical, C1-20Alkylamide group, C6-20Aryl amido radical or C1-20An alkylene group or a substituted alkylene group,
R1to R5And R6To R12Each independently hydrogen, substituted or unsubstituted C1-20Alkyl, substituted or unsubstituted C2-20Alkenyl, substituted or unsubstituted C6-20Aryl, substituted or unsubstituted C1-20Alkyl radical C6-20Aryl, substituted or unsubstituted C6-20Aryl radical C1-20Alkyl, substituted or unsubstituted C1-20Heteroalkyl, substituted or unsubstituted C3-20Heteroaryl, substituted or unsubstituted C1-20Alkylamido, substituted or unsubstituted C6-20Arylamido, substituted or unsubstituted C1-20Alkylene, or substituted or unsubstituted C1-20A silyl group (a) having a silyl group (a),
R1to R5And R6To R12May each independently form a substituted or unsubstituted saturated or unsaturated C by linking to an adjacent group4-20And (4) a ring.
Specifically, in the chemical formulas 1 to 3, M is zirconium or hafnium, and X are each halogen, or substituted or unsubstituted C1-20Alkyl radical, R1To R5And R6To R12Each is hydrogen, substituted or unsubstituted C1-20Alkyl, or substituted or unsubstituted C6-20And (4) an aryl group.
Preferably, the transition metal compound represented by chemical formula 1 is at least one selected from the transition metal compounds represented by chemical formulas 1-1 to 1-10 below, the transition metal compound represented by chemical formula 2 is at least one selected from the transition metal compounds represented by chemical formulas 2-1 to 2-10 below, and the transition metal compound represented by chemical formula 3 is at least one selected from the transition metal compounds represented by chemical formulas 3-1 to 3-10 below.
[ chemical formula 1-10 ]
[ chemical formula 2-10 ]
[ chemical formula 3-10 ]
In one particular embodiment, the present invention provides a method of preparing a hybrid catalyst composition, the method comprising the steps of: (1) dissolving a compound represented by the following chemical formula 4 and a compound represented by the following chemical formula 5 in a solvent; (2) adding a compound represented by the following chemical formula 6 to the solution obtained in step (1), and then stirring to obtain a hybrid catalyst composition comprising at least two of the transition metal compounds represented by the chemical formulas 1 to 3, wherein the molar ratio of the compound represented by chemical formula 4 to the compound represented by chemical formula 5 is 10: 1 to 1: 10.
[ chemical formula 4 ]
[ chemical formula 5 ]
[ chemical formula 6 ]
MX4
In the chemical formulas 4 to 6, M, X, R1To R5And R6To R12As defined in the hybrid catalyst composition section above.
Preferably, the compound represented by the chemical formula 4 is at least one selected from the group consisting of the compounds represented by the following chemical formulae 4-1 to 4-10, and the compound represented by the chemical formula 5 is at least one selected from the group consisting of the compounds represented by the following chemical formulae 5-1 to 5-10.
[ chemical formula 4-10 ]
[ chemical formula 5-10 ]
Preferably, the compound represented by the chemical formula 6 is ZrCl4。
The solvent may include at least one selected from hexane, pentane, toluene, benzene, dichloromethane, diethyl ether, tetrahydrofuran, acetone, and ethyl acetate.
In a particular embodiment, the method of preparing the hybrid catalyst composition can further comprise the steps of: (2') drying the hybrid catalyst composition in the step (2).
In a particular embodiment, the method of preparing the hybrid catalyst composition can further comprise the steps of: (2') dissolving the dried hybrid catalyst composition obtained in the step (2') in a solvent, and then removing unreacted materials and/or impurities through a filter.
To achieve another object, in one embodiment, the present invention provides a catalyst for polymerizing olefins, comprising: a hybrid catalyst composition comprising at least two of the transition metal compounds represented by the chemical formulas 1 to 3; and a cocatalyst compound.
Wherein the cocatalyst compound may be one or more compounds selected from the group consisting of a compound represented by the following chemical formula 7, a compound represented by chemical formula 8, and a compound represented by chemical formula 9.
[ chemical formula 7 ]
[ chemical formula 8 ]
[ chemical formula 9 ]
[L-H]+[Z(A)4]-Or [ L]+[Z(A)4]-
In the chemical formula 7, n is an integer of 2 or more, RaIs a halogen atom, C1-20Hydrocarbyl, or C substituted by halogen1-20A hydrocarbon group,
in the chemical formula 8, D is aluminum (Al) or boron (B), Rb、RcAnd RdEach independently is a halogen atom, C1-20Hydrocarbyl, halogen-substituted C1-20Hydrocarbyl or C1-20An alkoxy group,
in the chemical formula 9, L is a neutral or cationic Lewis base, [ L-H ]]+And [ L]+Is a Bronsted acid, Z is a group 13 element, A are each independently substituted or unsubstituted C6-20Aryl, or substituted or unsubstituted C1-20An alkyl group.
Specifically, the compound represented by the chemical formula 7 is at least one selected from the group consisting of methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane.
Further, the compound represented by chemical formula 8 is at least one selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylaluminum chloride, triisopropylaluminum, tri-sec-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethylaluminum methoxide (dimethylaluminum methoxide), dimethylaluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, and tributylboron.
Further, the compound represented by said chemical formula 9 is selected from triethylammoniumtetraphenylboron, tributylammoniumtetraphenylboron, trimethylammoniumtetraphenylboron, tripropylammoniumtetraphenylboron, trimethylammoniumtetrakis (p-tolyl) boron, trimethylammoniumtetrakis (o, p-dimethylphenyl) boron, tributylammoniumtetrakis (p-trifluoromethylphenyl) boron, trimethylammoniumtetrakis (pentafluorophenyl) boron, N-diethylphenylammonium tetraphenylboron, N-diethylphenylammonium tetrakis (pentafluorophenyl) boron, diethylammonium tetrakis (pentafluorophenyl) boron, triphenylphosphonytetraphenylboron, trimethylphosphonatetetraphenylboron, triethylammoniumtetraphenylaluminum, tributylammoniumtetraphenylaluminum, trimethylammoniumtetraphenylaluminum, tripropylammoniumtetraphenylaluminum, trimethylammoniumtetrakis (p-tolyl) aluminum, tripropylammoniumtetraphenylaluminum (p-tolyl), tripropylammoniumtetrakis (p-tolyl) aluminum, At least one member selected from the group consisting of triethylammoniumtetra (o, p-dimethylphenyl) aluminum, tributylammoniumtetra (p-trifluoromethylphenyl) aluminum, trimethylammoniumtetra (p-trifluoromethylphenyl) aluminum, tributylammoniumtetra (pentafluorophenyl) aluminum, N-diethylphenylammonium tetraphenylaluminum, N-diethylphenylammonium tetrakis (pentafluorophenyl) aluminum, diethylammonium tetrakis (pentafluorophenyl) aluminum, triphenylphosphoniumtetraphenylaluminum, trimethylphosphonateuminum, tripropylammoniumtetra (p-tolyl) boron, triethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (p-trifluoromethylphenyl) boron, triphenylcarboniumtetrakis (p-trifluoromethylphenyl) boron, and triphenylcarboniumtetrakis (pentafluorophenyl) boron.
Preferably, the catalyst for polymerizing olefins further comprises a support supporting the hybrid catalyst composition. In particular, the support may simultaneously support the hybrid catalyst composition and the co-catalyst compound.
Specifically, the support may comprise at least one selected from silica, alumina and magnesia.
Wherein the total amount of the hybrid transition metal compound supported on the carrier is 0.001 to 1mmole, and the amount of the cocatalyst compound supported on the carrier is 2 to 15mmole, based on 1g of the carrier.
In one embodiment, the present invention provides a method for preparing a catalyst for polymerizing olefins, the method comprising the steps of: (1) dissolving the compound represented by chemical formula 4 and the compound represented by chemical formula 5 in a solvent; (2) adding the compound represented by chemical formula 6 to the solution obtained in step (1), followed by stirring to obtain a hybrid catalyst composition comprising at least two of the transition metal compounds represented by chemical formulae 1 to 3; (3) supporting the hybrid catalyst composition, the co-catalyst compound, or both obtained in the step (2) on a carrier, wherein a molar ratio of the compound represented by the chemical formula 4 to the compound represented by the chemical formula 5 is 10: 1 to 1: 10.
Advantageous effects
According to one embodiment of the present invention, a hybrid catalyst composition comprising different kinds of transition metal compounds, and a catalyst for polymerizing olefins comprising the same can prepare polyolefins having excellent processability and mechanical properties according to the content of the transition metal compounds.
In addition, in the hybrid catalyst composition comprising different kinds of transition metal compounds and the preparation method of the catalyst for polymerizing olefins comprising the same, a catalyst for polymerizing polyolefins having excellent processability and mechanical properties can be easily provided by precisely adjusting the ratio of the hybrid transition metal compound.
Detailed Description
Hereinafter, the present invention will be described in detail.
Hybrid catalyst composition comprising different kinds of transition metal compounds
In one embodiment, the present invention provides a hybrid catalyst composition comprising at least two of transition metal compounds represented by the following chemical formulas 1 to 3.
[ chemical formula 1 ]
[ chemical formula 2 ]
[ chemical formula 3 ]
In the chemical formulas 1 to 3, M is titanium (Ti), zirconium (Zr), or hafnium (Hf). Specifically, M may be zirconium or hafnium.
X is each independently halogen, C1-20Alkyl, aryl, heteroaryl, and heteroaryl,C2-20Alkenyl radical, C2-20Alkynyl, C6-20Aryl radical, C1-20Alkyl radical C6-20Aryl radical, C6-20Aryl radical C1-20Alkyl radical, C1-20Alkylamide group, C6-20Aryl amido radical or C1-20An alkylene group. Specifically, each X may be halogen, or substituted or unsubstituted C1-20An alkyl group. More specifically, each X may be chlorine.
R1To R5And R6To R12Each independently hydrogen, substituted or unsubstituted C1-20Alkyl, substituted or unsubstituted C2-20Alkenyl, substituted or unsubstituted C6-20Aryl, substituted or unsubstituted C1-20Alkyl radical C6-20Aryl, substituted or unsubstituted C6-20Aryl radical C1-20Alkyl, substituted or unsubstituted C1-20Heteroalkyl, substituted or unsubstituted C3-20Heteroaryl, substituted or unsubstituted C1-20Alkylamido, substituted or unsubstituted C6-20Arylamido, substituted or unsubstituted C1-20Alkylene, or substituted or unsubstituted C1-20A silyl group. Wherein R is1To R5And R6To R12May each independently form a substituted or unsubstituted saturated or unsaturated C by linking to an adjacent group4-20And (4) a ring. Specifically, R1To R5And R6To R12Each of which may be hydrogen, substituted or unsubstituted C1-20Alkyl, or substituted or unsubstituted C6-20And (4) an aryl group.
Specifically, in the chemical formulas 1 to 3, M may be zirconium or hafnium, and each X may be halogen, or substituted or unsubstituted C1-20Alkyl radical, R1To R5And R6To R12Each of which may be hydrogen, substituted or unsubstituted C1-20Alkyl, or substituted or unsubstituted C6-20And (4) an aryl group.
In a preferred embodiment of the present invention, the transition metal compound represented by chemical formula 1 may be at least one selected from the transition metal compounds represented by the following chemical formulae 1-1 to 1-10, the transition metal compound represented by chemical formula 2 may be at least one selected from the transition metal compounds represented by the following chemical formulae 2-1 to 2-10, and the transition metal compound represented by chemical formula 3 may be at least one selected from the transition metal compounds represented by the following chemical formulae 3-1 to 3-10.
[ chemical formula 1-10 ]
[ chemical formula 2-10 ]
[ chemical formula 3-10 ]
Method for preparing hybrid catalyst composition
In one particular embodiment, the present invention provides a method of preparing a hybrid catalyst composition, the method comprising the steps of: (1) dissolving a compound represented by the following chemical formula 4 and a compound represented by the following chemical formula 5 in a solvent; (2) the compound represented by the following chemical formula 6 is added to the solution obtained in the step (1), and then stirring is performed to obtain a hybrid catalyst composition including at least two of the transition metal compounds represented by the following chemical formulas 1 to 3, wherein the molar ratio of the compound represented by the chemical formula 4 to the compound represented by the chemical formula 5 is 10: 1 to 1: 10.
[ chemical formula 4 ]
[ chemical formula 5 ]
[ chemical formula 6 ]
MX4
In the chemical formulas 4 to 6, M, X, R1To R5And R6To R12As defined in the hybrid catalyst composition section above.
Specifically, in the step (1), the compound represented by chemical formula 4 and the compound represented by chemical formula 5 are dissolved in a solvent.
Preferably, the compound represented by the chemical formula 4 is at least one selected from the group consisting of the compounds represented by the following chemical formulae 4-1 to 4-10, and the compound represented by the chemical formula 5 is at least one selected from the group consisting of the compounds represented by the following chemical formulae 5-1 to 5-10.
[ chemical formula 4-10 ]
[ chemical formula 5-10 ]
Further, the solvent may contain at least one selected from the group consisting of aliphatic hydrocarbon solvents such as hexane and pentane, aromatic hydrocarbon solvents such as toluene and benzene, hydrocarbon solvents substituted with chlorine atoms such as methylene chloride, ether solvents such as diethyl ether and tetrahydrofuran, acetone, and ethyl acetate. Preferably, the solvent may be a mixed solvent of toluene and tetrahydrofuran, but is not particularly limited thereto.
In dissolving the compound represented by chemical formula 4 and the compound represented by chemical formula 5 in a solvent, the order of addition of the respective compounds is not particularly limited. That is, the compound represented by chemical formula 4 may be first added to a solvent and dissolved, and then the compound represented by chemical formula 5 may be added to the solvent and dissolved, or the compounds may be dissolved in the reverse order. Further, both compounds may be added to a solvent and dissolved at the same time.
In dissolving the compound represented by chemical formula 4 and the compound represented by chemical formula 5 in a solvent, the temperature and the dissolution time are not particularly limited. For example, the compound represented by chemical formula 4 and the compound represented by chemical formula 5 may be added to a solvent at a temperature of-78 ℃ to 30 ℃, preferably-40 ℃ to 10 ℃, more preferably about-30 ℃ separately or simultaneously, and stirred for 1 hour to 24 hours, preferably 5 hours to 20 hours, more preferably about 15 hours, to be dissolved.
In the step (1), the molar ratio of the compound represented by chemical formula 4 to the compound represented by chemical formula 5 dissolved in the solvent is 10: 1 to 1: 10. Preferably, the molar ratio of the two compounds is from 5:1 to 1: 5. More preferably, the molar ratio of the two compounds is from 3: 1 to 1: 3.
In the step (2), the compound represented by the chemical formula 6 is added to the solution obtained in the step (1), and then stirring is performed to obtain a hybrid catalyst composition including at least two of the transition metal compounds represented by the chemical formulas 1 to 3,
preferably, the compound represented by the chemical formula 6 is ZrCl4。
When the compound represented by chemical formula 6 is added, the temperature range is preferably-78 ℃ to 30 ℃. More preferably, the temperature may be-40 ℃ to 10 ℃ when the compound represented by chemical formula 6 is added. Most preferably, the temperature may be about-30 ℃ when the compound represented by chemical formula 6 is added.
After the addition of the compound represented by chemical formula 6, the temperature is slowly raised to-30 ℃ to 100 ℃, more preferably 0 ℃ to 50 ℃, most preferably about 25 ℃, and stirring is performed for 1 hour to 24 hours, preferably 5 hours to 20 hours, more preferably about 15 hours to perform the reaction.
In another specific embodiment, the method of preparing the hybrid catalyst composition of the present invention may further comprise the steps of: (2') drying the hybrid catalyst composition obtained in the step (2). Among them, the drying conditions of the composition are not particularly limited and may be carried out at a temperature of 25 ℃ to 80 ℃, more preferably 25 ℃ to 50 ℃, most preferably about 25 ℃.
In another specific embodiment, the method of preparing the hybrid catalyst composition of the present invention may further comprise the steps of: (2') dissolving the dried hybrid catalyst composition obtained in the step (2') in a solvent, and then removing unreacted materials and/or impurities through a filter. Wherein the solvent may be substantially the same as the solvent used in the step (1). Preferably, dichloromethane may be used. The filter for removing unreacted materials and/or impurities is not particularly limited, but a diatomaceous earth (Celite) filter is preferably used.
Catalyst for polymerization of olefins
In one embodiment, the present invention provides a catalyst for polymerizing olefins, comprising: a hybrid catalyst composition comprising at least two of transition metal compounds represented by the following chemical formulas 1 to 3; and a cocatalyst compound.
[ chemical formula 1 ]
[ chemical formula 2 ]
[ chemical formula 3 ]
In the chemical formulas 1 to 3, M, X, R1To R5And R6To R12As defined in the hybrid catalyst composition section above.
In a preferred embodiment of the present invention, the transition metal compound represented by chemical formula 1 may be at least one selected from the transition metal compounds represented by the following chemical formulae 1-1 to 1-10, the transition metal compound represented by chemical formula 2 may be at least one selected from the transition metal compounds represented by the following chemical formulae 2-1 to 2-10, and the transition metal compound represented by chemical formula 3 may be at least one selected from the transition metal compounds represented by the following chemical formulae 3-1 to 3-10.
[ chemical formula 1-10 ]
[ chemical formula 2-10 ]
[ chemical formula 3-10 ]
In addition, the cocatalyst compound may include one or more selected from the group consisting of a compound represented by the following chemical formula 7, a compound represented by the following chemical formula 8, and a compound represented by the following chemical formula 9.
[ chemical formula 7 ]
In the chemical formula 7, n may be an integer of 2 or more, and RaCan be a halogen atom, C1-20Hydrocarbons, or C substituted by halogen1-20A hydrocarbon. Specifically, RaAnd may be methyl, ethyl, n-butyl or isobutyl.
[ chemical formula 8 ]
In the chemical formula 8, D is aluminum or boron, Rb、RcAnd RdEach independently is a halogen atom, C1-20Hydrocarbyl, halogen-substituted C1-20Hydrocarbyl or C1-20An alkoxy group. Specifically, when D is aluminum, Rb、RcAnd RdEach independently may be methyl or isobutyl, when D is boron, Rb、RcAnd RdEach may be pentafluorophenyl.
[ chemical formula 9 ]
[L-H]+[Z(A)4]-Or [ L]+[Z(A)4]-
In the chemical formula 9, L is a neutral or cationic Lewis base, [ L-H ]]+And [ L]+Is a Bronsted acid (acid), Z is a group 13 element, A is each independently substituted or unsubstituted C6-20Aryl, or substituted or unsubstituted C1-20An alkyl group. Specifically, [ L-H ]]+Can be a dimethylanilinium cation, [ Z (A) ]4]-Can be [ B (C)6F5)4]-，[L]+Can be [ (C)6H5)3C]+。
Specifically, the compound represented by the chemical formula 7 may be, for example, methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, etc., and is preferably methylaluminoxane, but is not limited thereto.
The compound represented by the chemical formula 8 may be, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylaluminum chloride, triisopropylaluminum, tri-sec-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethylaluminum methoxide (dimethylaluminum methoxide), dimethylaluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron, etc., and is preferably trimethylaluminum, triethylaluminum, and triisobutylaluminum, but not limited thereto.
The compound represented by the chemical formula 9 may be, for example, triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetrakis (p-tolyl) boron, trimethylammonium tetrakis (o, p-dimethylphenyl) boron, tributylammonium tetrakis (p-trifluoromethylphenyl) boron, trimethylammonium tetrakis (p-trifluoromethylphenyl) boron, tributylammonium tetrakis (pentafluorophenyl) boron, N-diethylanilinium tetraphenylboron, N-diethylanilinium tetrakis (pentafluorophenyl) boron, diethylammonium tetrakis (pentafluorophenyl) boron, triphenylphosphoranylphenyl boron (triphenylphosphoranylphenyl boron), trimethylphosphorylboron (trimethylphosphorylboron), triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, trimethylammonium tetraphenylaluminum, tripropylammonium tetraphenylaluminum, trimethylammonium tetrakis (p-tolyl) aluminum, Tripropylammonium tetrakis (p-tolyl) aluminum, triethylammonium tetrakis (o, p-dimethylphenyl) aluminum, tributylammonium tetrakis (p-trifluoromethylphenyl) aluminum, trimethylammonium tetrakis (p-trifluoromethylphenyl) aluminum, tributylammonium tetrakis (pentafluorophenyl) aluminum, N-diethylanilinium tetraphenylaluminum, N-diethylanilinium tetrakis (pentafluorophenyl) aluminum, diethylammonium tetrakis (pentafluorophenyl) aluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, tripropylammonium tetrakis (p-tolyl) boron, triethylammonium tetrakis (o, p-dimethylphenyl) boron, tributylammonium tetrakis (p-trifluoromethylphenyl) boron, triphenylcarbenium tetrakis (p-trifluoromethylphenyl) boron, and triphenylcarbenium tetrakis (pentafluorophenyl) boron, and the like.
In a preferred embodiment of the present invention, the catalyst for polymerizing olefins may further comprise a support, which supports the hybrid catalyst composition. In particular, the support may simultaneously support the hybrid catalyst composition and the co-catalyst compound.
In this case, the surface of the support may contain a substance containing a hydroxyl group, and a substance which has been dried to remove moisture from the surface and has a highly reactive hydroxyl group and a siloxane group can be preferably used. For example, the support may comprise at least one selected from silica, alumina and magnesia. Specifically, silica-alumina, silica-magnesia, and the like dried at high temperature may be used as the carrier, and they may usually contain, for example, Na2O、K2CO3、BaSO4And Mg (NO)3)2Oxide, carbonate, sulfate and nitrate components. In addition, they may contain carbon, zeolites, magnesium chloride, and the like. However, the support is not limited thereto, and is not particularly limited as long as it can support the transition metal compound and the co-catalyst compound.
The average particle diameter of the carrier may be 10 μm to 250 μm, preferably 10 μm to 150 μm, and more preferably 20 μm to 100 μm.
The micropore volume of the support may be from 0.1cc/g to 10cc/g, preferably from 0.5cc/g to 5cc/g, more preferably from 1.0cc/g to 3.0 cc/g.
The specific surface area of the carrier can be from 1 square meter per gram to 1,000 square meters per gram, preferably from 100 square meters per gram to 800 square meters per gram, more preferably from 200 square meters per gram to 600 square meters per gram.
In a preferred embodiment, when the support is silica, the drying temperature of the silica may be from room temperature to 900 ℃. The drying temperature may preferably be from room temperature to 800 deg.c, more preferably from room temperature to 700 deg.c. When the drying temperature is lower than the normal temperature, the surface moisture reacts with the cocatalyst due to the excessive moisture, and when it exceeds 900 ℃, the structure of the support may collapse.
The concentration of hydroxyl groups in the dried silica may be from 0.1 to 5mmole/g, preferably from 0.7 to 4mmole/g, more preferably from 1.0 to 2 mmole/g. When the concentration of the hydroxyl group is less than 0.1mmole/g, the supported amount of the cocatalyst may be reduced, and when the concentration of the hydroxyl group exceeds 5mmole/g, there may occur a problem of deactivation of the catalyst component.
The total amount of the hybrid transition metal compound supported on the carrier may be 0.001mmol to 1mmol e based on 1g of the carrier. When the ratio of the hybrid transition metal compound to the support satisfies the above range, appropriate supported catalyst activity is exhibited, thereby contributing to maintenance of catalyst activity and economy.
The amount of the cocatalyst compound supported on the carrier may be 2mmole to 15mmole, based on 1g of the carrier. When the ratio of the cocatalyst compound to the support satisfies the above range, maintenance of catalyst activity and economy may be facilitated.
One, two or more kinds of carriers may be used. For example, the hybrid catalyst composition and the co-catalyst compound may be supported on one kind of support, or the hybrid catalyst composition and the co-catalyst compound may be supported on two or more kinds of supports, respectively. In addition, only one of the hybrid catalyst composition and the co-catalyst compound may also be supported on the support.
Process for preparing catalyst for polymerizing olefins
In one embodiment, the present invention provides a method for preparing a catalyst for polymerizing olefins, the method comprising the steps of: (1) dissolving a compound represented by the following chemical formula 4 and a compound represented by the following chemical formula 5 in a solvent; (2) adding a compound represented by the following chemical formula 6 to the solution obtained in step (1), and then stirring to obtain a hybrid catalyst composition comprising at least two of transition metal compounds represented by the following chemical formulas 1 to 3; (3) supporting the hybrid catalyst composition, the co-catalyst compound, or both obtained in the step (2) on a carrier, wherein a molar ratio of the compound represented by chemical formula 4 to the compound represented by chemical formula 5 is 10: 1 to 1: 10.
[ chemical formula 1 ]
[ chemical formula 2 ]
[ chemical formula 3 ]
[ chemical formula 4 ]
[ chemical formula 5 ]
[ chemical formula 6 ]
MX4
In the chemical formulas 1 to 6, M, X, R1To R5And R6To R12As defined in the hybrid catalyst composition section above.
The specific contents of the above step (1) and step (2) are substantially the same as those of the step (1) and step (2) in the preparation method of the hybrid catalyst composition.
In another embodiment, the method for preparing a catalyst for polymerizing olefins according to the present invention may further include the steps of: (2') drying the composition obtained in said step (2). At this time, the detailed contents of step (2') are substantially the same as those of step (2') in the preparation method of the hybrid catalyst composition.
In another embodiment, the method for preparing a catalyst for polymerizing olefins according to the present invention may further include the steps of: (2') dissolving the dried composition obtained in the step (2') in a solvent, and then removing unreacted materials and/or impurities through a filter. At this time, the specific contents of step (2 ") are substantially the same as those of step (2") in the preparation method of the hybrid catalyst composition.
In said step (3), the hybrid catalyst composition, the cocatalyst compound or both are supported on a support.
The method of loading the hybrid catalyst composition and/or the co-catalyst compound can be by physical adsorption or chemical adsorption.
For example, the physical adsorption method may be a method in which a solution in which the hybrid catalyst composition is dissolved is brought into contact with a support and then dried; a method of drying after contacting a solution in which the hybrid catalyst composition and the co-catalyst compound are dissolved with the support; or a method in which a solution in which the hybrid catalyst composition is dissolved is brought into contact with a support and then dried to prepare a support on which the hybrid catalyst composition is supported, or a solution in which the cocatalyst compound is dissolved is brought into contact with a support and then dried to prepare a support on which the cocatalyst compound is supported, and then these are mixed.
The chemisorption method may be a method in which the promoter compound is supported on the surface of the carrier, and then the hybrid catalyst composition is supported on the promoter compound; or a method of covalently bonding a functional group on the surface of the support (for example, in the case of silica, a hydroxyl group (-OH) on the surface of silica) to the hybrid transition metal compound.
Among them, the solvent used when supporting the hybrid catalyst composition and/or the co-catalyst compound is not particularly limited. For example, the solvent may include at least one selected from the group consisting of aliphatic hydrocarbon solvents such as hexane and pentane, aromatic hydrocarbon solvents such as toluene and benzene, hydrocarbon solvents substituted with chlorine atoms such as methylene chloride, ether solvents such as diethyl ether and tetrahydrofuran, acetone, and ethyl acetate.
In a preferred embodiment, in said step (3), the hybrid catalyst composition and/or the cocatalyst compound may be supported on the carrier at a temperature of 0 ℃ to 100 ℃, preferably room temperature to 90 ℃.
Further, in step (3), the hybrid catalyst composition and/or the co-catalyst compound may be supported on the support by subjecting the mixture of the hybrid catalyst composition and/or the co-catalyst compound and the support to sufficient stirring for 1 minute to 24 hours, preferably 5 minutes to 15 hours.
Polymerization of olefins
An olefin polymer may be prepared by polymerizing an olefin monomer under the conditions of a catalyst for polymerizing an olefin according to an embodiment of the present invention.
The olefin polymer may be, among others, a homopolymer (homopolymer) based on olefin monomers or a copolymer (copolymer) based on olefin monomers and comonomers.
The olefin monomer may be selected from C2-20Alpha-olefins (alpha-olefin), C1-20Diolefins (diolefrin), C3-20Cycloolefin (cyclic efin) and C3-20At least one of cyclodiolefins (cyclodiolefins).
For example, the olefin monomer may be ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, or the like, and the olefin polymer may be a homopolymer containing only one kind selected from the above exemplary olefin monomers, or a copolymer containing a plurality of kinds selected from the above exemplary olefin monomers.
In exemplary embodiments, the olefin polymer may be a blend of ethylene and C3-20A copolymer obtained by copolymerizing alpha-olefin, and preferably a copolymer obtained by copolymerizing ethylene and 1-hexene, but is not limited thereto.
In this case, the content of ethylene is preferably 55 to 99.9% by weight, more preferably 90 to 99.9% by weight. The content of the alpha-olefin comonomer is preferably 0.1 to 45% by weight, more preferably 0.1 to 10% by weight.
The olefin polymer according to an embodiment of the present invention may be polymerized by polymerization such as, but not limited to, free radical (free radial), cationic (cationic), coordination (coordination), condensation (condensation), addition (addition), and the like.
In a preferred embodiment, the olefin polymers may be prepared by gas phase polymerization, solution polymerization, slurry polymerization, or the likeA compound (I) is provided. When the olefin polymer is produced by a solution polymerization method or a slurry polymerization method, usable as the solvent are, for example, C such as pentane, hexane, heptane, nonane, decane and isomers thereof5-12An aliphatic hydrocarbon solvent; aromatic hydrocarbon solvents such as toluene and benzene; hydrocarbon solvents substituted with a chlorine atom such as methylene chloride and chlorobenzene; and mixtures thereof, and the like, but are not limited thereto.
[ examples ] A method for producing a compound
Hereinafter, the present invention will be described more specifically by examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.
Example 1
157mg (1.29mmol, 3 equivalents) of the indenyllithium (Indenylithium; IndLi) of the chemical formula 5-1 and 31mg (0.43mmol, 1 equivalent) of the cyclopentadienyl lithium (cyclopentadienylithium; CpLi) of the chemical formula 4-1 are dissolved in 20mL of a mixed solvent of toluene/tetrahydrofuran (volume ratio 2: 1). To this solution was added 200mg (0.86mmol, 2 equiv.) of zirconium chloride (ZrCl) at-30 deg.C4) Then, the temperature was slowly raised to normal temperature and stirring was performed for 15 hours. The reaction product was dried, then added to a dichloromethane solvent and dissolved, and then lithium chloride (LiCl) was removed with a Celite filter, thereby obtaining 294mg (yield: 91%) of the hybrid transition metal compound.
By passing1H NMR confirmation of the hybrid transition Metal Compound, i.e., Ind2ZrCl2/CpIndZrCl2(1.25: 1).
1H-NMR(CDCl3,300MHz)7.69-7.66(m,1.6H),7.63-7.59(m,4H),7.32-7.26(m,5.6H),6.92(t,0.8H),6.53(d,1.4H),6.49-6.46(m,2.8H),6.16(s,5.7H).
Example 2
A254 mg (yield: 81%) hybrid transition metal compound was prepared in the same manner as in example 1, except that the amounts of indenyllithium, cyclopentadienyl lithium and zirconium chloride used were 140mg (1.14mmol, 2 equivalents), 41mg (0.57mmol, 1 equivalent) and 200mg (0.86mmol, 1.5 equivalents), respectively.
By passing1H NMR confirmation of the hybrid transition Metal Compound, i.e., Ind2ZrCl2/CpIndZrCl2(1: 1).
1H-NMR(CDCl3,300MHz)7.69-7.66(m,2H),7.63-7.59(m,4H),7.32-7.26(m,6H),6.92(t,1H),6.53(d,1H),6.49-6.46(m,2H),6.16(s,6H).
Example 3
A278 mg (yield: 95%) hybrid transition metal compound was prepared in the same manner as in example 1, except that the amounts of indenyllithium, cyclopentadienyl lithium and zirconium chloride used were 105mg (0.86mmol, 1 eq), 62mg (0.86mmol, 1 eq) and 200mg (0.86mmol, 1.0 eq), respectively.
By passing1H NMR confirmed the hybrid transition Metal Compound, i.e., Cp2ZrCl2/Ind2ZrCl2/CpIndZrCl2(1:1: 2).
1H-NMR(CDCl3,300MHz)7.69-7.66(m,4H),7.63-7.59(m,4H),7.32-7.26(m,8H),6.92(t,2H),6.53(d,4H),6.49-6.46(m,16H),6.16(s,12H).
Example 4
A207 mg (yield: 72%) hybrid transition metal compound was prepared in the same manner as in example 1, except that 70mg (0.57mmol, 1 equiv.), 82mg (1.14mmol, 2 equiv.) and 200mg (0.86mmol, 1.5 equiv.) of indenyllithium, cyclopentadienyl lithium and zirconium chloride were used.
By passing1H NMR confirmed the hybrid transition Metal Compound, i.e., Cp2ZrCl2/Ind2ZrCl2/CpIndZrCl2(1.5:1: 2).
1H-NMR(CDCl3,300MHz)7.69-7.66(m,4H),7.63-7.59(m,4H),7.32-7.26(m,8H),6.92(t,2H),6.53(d,4H),6.49-6.46(m,21H),6.16(s,12H).
Example 5
A254 mg (yield: 93%) hybrid transition metal compound was prepared in the same manner as in example 1, except that indenyllithium, cyclopentadienyl lithium and zirconium chloride were used in amounts of 52mg (0.43mmol, 1 equivalent), 93mg (1.29mmol, 3 equivalents) and 200mg (0.86mmol, 2 equivalents), respectively.
By passing1H NMR confirmed the hybrid transition Metal Compound, i.e., Cp2ZrCl2/Ind2ZrCl2/CpIndZrCl2(5:1: 2.5).
1H-NMR(CDCl3,300MHz)7.69-7.66(m,5H),7.63-7.59(m,4H),7.32-7.26(m,8H),6.92(t,2H),6.53(d,4H),6.49-6.46(m,49H),6.16(s,12H).
The composition ratios of the reactants and products of the above examples are shown in table 1 below.
[ TABLE 1 ]
Industrial applicability
According to one embodiment of the present invention, a hybrid catalyst composition comprising different kinds of transition metal compounds, and a catalyst for polymerizing olefins comprising the same can prepare various polyolefins having excellent processability and mechanical properties according to the content of the transition metal compounds.
In addition, in the hybrid catalyst composition and the method for preparing a catalyst for polymerizing olefins comprising the same, a catalyst for polymerizing polyolefins having excellent processability and mechanical properties can be easily provided by precisely adjusting the ratio of the hybrid transition metal compound.
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