JPH07206914A - Catalyst for olefin polymerization - Google Patents

Abstract

PURPOSE:To obtain a catalyst capable of readily synthesizing, for producing a polyolefin having narrow distribution of molecular weight and dispersion of composition and excellent in powdery properties in excellent polymerization yield per unit transition metal weight. CONSTITUTION:This catalyst for polymerization consists of a transition metal compound expressed by the formula ALML'n (A: Q or QZ; Q: polystyrene and a polystyrene having a substituent group; Z: a 1-20C hydrocarbon group or a group connecting Q selected from the group containing Si, Ge and Sn to L by a covalent bond; L: a cycloalkadienyl group selected from a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group and a fluorenyl group, each having A as a substituent group; L': a monovalent unidentate ligand selected from hydrogen atom, a hydrocarbon and a group coordinated by elements of the groups 5B.6B.7B of the Periodic table or a monovalent multidentate ligand selected from a tris group, a cycloalkadienyl group and a heterocyclic 5-membered ligand; M: transition metal elements of the groups 3A.4A.5A of the Periodic table).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an olefin polymer and a copolymer. Specifically, a method for producing an olefin polymer having an excellent polymer yield per unit catalyst weight and having an excellent powder property and a narrow molecular weight distribution, or an olefin copolymer having an excellent powder property and a narrow molecular weight distribution and a narrow composition distribution. Regarding

[0002]

2. Description of the Related Art In recent years, there has been proposed a method for producing a polyolefin having a narrow molecular weight distribution and a narrow compositional distribution by using a zirconium compound and an aluminoxane in combination as an olefin polymerization catalyst (for example, JP-A-58-193).
09, JP-A-61-130314). This catalyst system
It should be noted that the catalyst has a polymerization activity sufficient to omit the catalyst removal step after the polymerization. However, in this method, since most of the catalyst system is soluble in the solvent, the bulk density of the produced polymer is small, and it is difficult to obtain a polymer having excellent powder properties.

In order to solve this problem, attempts have been made so far to insolubilize the catalyst system in a solvent by supporting the catalyst system on a porous inorganic oxide such as silica, silica-alumina, or alumina, or an organic polymer carrier such as polystyrene. It has been done. As this attempt, for example, a method of supporting one or both of a zirconium compound and an aluminoxane in contact with a porous inorganic oxide in a solvent (JP-A-60-35006,
JP-A-61-31404, JP-A-61-276805, JP-A-61-108610, etc.), the zirconium compound and aluminoxane are contacted in advance, and then contacted with linear rhodity polyethylene or polynorbornene. Method (JP-A-63-92621, JP-A-2-84405), a method of carrying out pre-polymerization of an olefin using a zirconium compound and an aluminoxane in the presence of a carrier before the main polymerization, and carrying it in this process (Preliminary polymerization method, for example, JP-A No. 4-8704). However, in these methods, the polymerization activity is generally lower than in the homogeneous system, and in the case of loading by contact, the bond between the carrier and the catalyst is weak and the catalyst elutes during polymerization. There is a problem that an extra operation such as pre-polymerization is added before the polymerization.

In order to solve these problems, several methods of forming a covalent bond between the carrier and the zirconium compound and supporting the same have been attempted. For example, a method of forming and supporting a covalent bond between a zirconium compound ligand and a hydroxyl group on the silica surface (JP-A-63-312303), a covalent bond between a zirconium compound ligand and a polystyrene phenyl group. Method of making and supporting (JP-A-4-234405)
There is. However, even in these methods, the polymerization activity is generally lower than that in the homogeneous system. Further, the catalyst supported on polystyrene by a covalent bond has a drawback that a crosslinked cycloalkadienyl group is used as a ligand of a transition metal compound and synthesis of the crosslinked ligand is difficult. .

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the problems of the prior art. It has an excellent polymer yield per unit weight of transition metal, and has a narrow molecular weight distribution and a narrow compositional distribution to give powdery properties. An object of the present invention is to provide a catalyst which is easy to synthesize for producing an excellent polyolefin.

[0006]

DISCLOSURE OF THE INVENTION As a result of intensive studies aimed at achieving the above object, the present invention has revealed that a cycloalkadienyl group L having a substituent A represented by the following general formula (I).
The present invention has been completed by finding a catalyst for olefin polymerization, which is composed of a transition metal compound having a ligand as a ligand. ALML ′ _n (I) A: Q or QZ Q: polystyrene and polystyrene having a substituent on the benzene ring Z: C _{1 to} C ₂₀ hydrocarbon group, Si-containing group, Ge-containing group, Sn-containing group Group L that connects Q and L selected by a covalent bond L: A cycloalkadienyl group selected from a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, and a fluorenyl group having A as a substituent L ′: hydrogen Atom, hydrocarbon group, periodic table 5B ・ 6B ・ 7
Monovalent monodentate ligand selected from groups coordinated by Group B element, or monovalent polydentate ligand selected from triso group, cycloalkadienyl group, and hetero 5-membered ring ligand M: Period Transition metal element of Group 3A, 4A, 5A of the Table n: integer of (group number to which M belongs-1) Hereinafter, the present invention will be described in more detail. In the transition metal compound represented by the general formula (I), polystyrene and polystyrene having a substituent on the benzene ring can be used as Q. At this time, either a crosslinked body or a non-crosslinked body can be used as Q, but a crosslinked body having a crosslinking degree of 1 to 20% is preferably used. The polystyrene having a substituent on the benzene ring is C ₁ to C.
₂₀ (halogenated) hydrocarbon groups and those having a halogen atom as a substituent can be used, and specifically, for example, methylated polystyrene, ethylated polystyrene, chloromethylated polystyrene, bromomethylated polystyrene, 1-
Methyl-3-bromopropylated polystyrene, 1-methyl-8-octylated polystyrene, chlorinated polystyrene, brominated polystyrene and the like can be mentioned. At this time, the content of the substituent with respect to the benzene ring can be any value. The powder properties of the crosslinked product are as follows: particle size 0.1 to 1000 μm, surface area 0.1 to 1000 m ² /
Those selected from a wide range of g can be used.

Z is a group that connects Q and L by a covalent bond, and is specifically a C _{1 to} C ₂₀ hydrocarbon group, a group containing Si, a group containing Ge, or a group containing Sn. Examples of the C _{1 to} C ₂₀ hydrocarbon group include methylene group, ethylene group, trimethylene group, tetramethylene group and the like as linear alkylene group, and methylmethylene group, dimethylmethylene group, diethylmethylene group as side chain alkylene group. Group, diphenylmethylene group, 1-methylethylene group, 1,1-
Dimethylmethylene group, 1-methyltrimethylene group, 1,
A 1-dimethyltrimethylene group, a 1-methyltetraethylene group, a 1-methylpentamethylene group, a 1-methylhexamethylene group, a 1-methylheptamethylene group, a 1-methyloctamethylene group or the like is used as a cycloalkylene group.
Examples thereof include a 3-cyclopentalene group, a 1,3-cyclohexylene group, a 1,4-cyclohexylene group and a norbornylene group.

Examples of the group containing Si include a silylene group,
Examples of the group containing Ge include a dimethylsilylene group, a diethylsilylene group and a diphenylsilylene group, and examples of the group containing Ge include a germylene group, a dimethylgermylene group, a diethylgermylene group,
Examples of the group containing Sn such as a diphenylgermylene group include a stannylene group, a dimethylstannylene group, a diethylstannylene group, and a diphenylstannylene group. L is a cycloalkadienyl group having A as a substituent. That is, any carbon atom in L and A must be linked by a covalent bond.

Examples of the cycloalkadienyl group include
Cyclopentadienyl group, indenyl group, tetrahydro
Indenyl group, fluorenyl group, etc., and their C₁
~ C ₁₂Groups having an alkyl substituent of, for example, methyl
Lopentadienyl group, methylindenyl group, methylteto
Lahydroindenyl group, methylfluorenyl group, ethyl
Cyclopentadienyl group, butylcyclopentadienyl
Group, dimethylcyclopentadienyl group, trimethylcyclo
Lopentadienyl group, tetramethylcyclopentadienyl group
Group, pentamethylcyclopentadienyl group, etc.
be able to.

L'is a monodentate or polydentate monovalent ligand, and a monodentate ligand that can be used is a hydrogen atom, a C _{1 to} C ₁₂ hydrocarbon group, or a periodic table 5B or 6B.・ 7
The tridentate group (tridentate) and the cycloalkadienyl group / hetero five-membered ring ligand (pentidentate) can be used as the group coordinated with the group B element and the polydentate ligand. The n L's selected from these groups or groups of atoms may be different or the same.

Regarding the monodentate ligand, examples of the C ₁ -C ₁₂ hydrocarbon group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and the like. Specifically, the alkyl group includes a methyl group and an ethyl group. Group, n-propyl group,
Examples thereof include an isopropyl group and the like, a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, an aryl group such as a phenyl group and a tolyl group, and an aralkyl group such as a benzyl group.

The group coordinating with elements of groups 5B, 6B, and 7B of the periodic table is an amide group such as a methylamide group or a butylamide group as a group coordinating with a nitrogen atom, and a butylphosphide group as a group coordinating with a phosphorus atom. -Phosphide groups such as phenylphosphide groups are coordinated with oxygen atoms, alkoxy groups such as methoxy and ethoxy groups, aryloxy groups such as phenoxy groups, etc., and methyl sulfide as groups coordinated with sulfur atoms. Group, a sulfide group such as an ethyl sulfide group is an alkoxy group, an aryloxy group, a phosphide group, a sulfide group, and the like, and a fluorine atom, a chlorine atom, a bromine atom, and a chlorine atom are preferable as a group that coordinates with a halogen atom. it can.

Regarding the polydentate ligand, the triso group means a group represented by the following general formula (II).

[0014]

[Chemical 1]

T: group or atom selected from C and BR ₁ L ₁ , L ₂ and L ₃ : group selected from Chemical formula 2 and Chemical formula 3

[0016]

[Chemical 2]

[0017]

[Chemical 3]

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ : Alkyl group, aryl group, aralkyl group, hydrogen atom, halogen atom, alkylsilyl group, alkylgermyl group, alkylstannyl A group or atom selected from the group of groups W: an atom selected from the group of O, S and Se For example, when L _{1 to} L ₃ are pyrazolyl groups and X is BR _1, a trispyrazolyl borate ligand, L _{1 to} L _{When 3} is a phosphoryl group and X is C, it is called a trisphosphorylmethanide ligand.

Specific examples of the triso group include, for example, trispyrazolyl borate, hydrotrispyrazolyl borate, isopropylpyrazolyl borate, hydrotris (3-isopropylpyrazolyl) borate, hydrotris (3,5-dimethylpyrazolyl) borate, hydrotris (3,5). -Diphenylpyrazolyl) borate, hydrotris (3-isopropyl-4-bromopyrazolyl)
Borate, bis (3,5-dimethylpyrazolyl) (pyrazolyl) borate, etc. as trisphosphonylmethanide, tris (diphenyloxophosphoranyl) methanide,
Tris (dicyclohexyloxophosphoranyl) methanide, tris (diphenylthiophosphoranyl) methanide,
Examples thereof include tris (diphenylselenophosphoranyl) methanide and bis (diphenyloxophosphoranyl) (diphenylthiophosphoranyl) methanide.

Examples of the cycloalkadienyl group include
Cyclopentadienyl group, indenyl group, tetrahydro
Indenyl group, fluorenyl group, etc., and their C₁
~ C ₁₂Groups having an alkyl substituent of, for example, methyl
Lopentadienyl group, methylindenyl group, methylteto
Lahydroindenyl group, methylfluorenyl group, ethyl
Cyclopentadienyl group, butylcyclopentadienyl
Group, dimethylcyclopentadienyl group, trimethylcyclo
Lopentadienyl group, tetramethylcyclopentadienyl group
Group, pentamethylcyclopentadienyl group, etc.
be able to.

The 5-membered heterocyclic ring ligand has the following general formula (III)
Means a ligand represented by. [E _n (CR) _5-n ] ^- (III) E: Atom selected from the group of N, P, As, Sb, Bi R: hydrogen atom, C ₁ -C ₁₂ hydrocarbon group, alkoxy group, aryl A group selected from the group consisting of an oxy group, a silyl group, a siloxy group, an amino group, a thiol group, and a phosphine group n: any number of 1, 2, 3, and 4 Specific examples of the hetero 5-membered ring ligand include For example, when E is N, pyrrolyl group, methylpyrrolyl group, ethylpyrrolyl group, pyrazolyl group, methylpyrazolyl group, dimethylpyrazolyl group, imidazolyl group, triazolyl group, tetrazolyl group, indolyl group, indazolyl group, purinyl group,
A carbazolyl group, a phosphoryl group, a diphosphoryl group, and a trisphosphoryl group as an example of E being P, an assoryl group as an example of As as E, a styboryl group as an example of E as Sb, and a bismolyl group as an example of E as Bi. Can be mentioned.

M is a transition metal element of the 3A, 4A and 5A groups of the periodic table, for example, Zr, Hf, Ti, Sc, Y and L.
Examples thereof include a, Yb, Sm, V, Nb and Ta, but Zr, Hf and Ti are preferable. n is an integer that satisfies n = (group number to which M belongs-1). The catalyst represented by the general formula (I) can be generally synthesized by the following method. <In the case of QLML ′ _n type> (Synthesis method A) Q + X ₂ → QX + HX QX + LM ′ → QL + XM ′ QL + RM ′ → QLM ′ + RH QLM ′ + ML ′ _{n + 1} → QLML ′ _n + L′ M ′ (Synthesis method B) Q + X ₂ → QX + HX QX + RM '→ QM' + RX QM '+ LX → QL + M'X QL + RM' → QLM '+ RH QLM' + ML _{n + 1} → QLML ' _n + L'M'<QZLML' _n type> (Synthesis method A) Q + YZX QZX + HY QZX + LM '→ QZL + XM' QZL + RM '→ QZLM' + RH QZLM '+ ML' _{n + 1} → QZLML ' _n + L'M' (Synthetic method B) Q + YZ → QZ + M + LQ + Q'R '+ QQMZ + H'R → QZLM '+ RH QZLM' + ML ' _{n + 1} → QZLML' _n + L'M 'where X is a halogen atom (F, Cl, Br, I, etc.),
M'is an alkali metal atom (Li, Na, K, Rb, F
r, Cs and the like), R represents a C _{1 to} C ₁₂ hydrocarbon group (alkyl group, aryl group, aralkyl group, etc.), and Y represents a hydroxy group, an alkoxy group, a thioalkyl group, a halogen group and the like. All reactions are carried out in an organic solvent such as hydrocarbons, halogenated hydrocarbons, ethers, etc. under an inert gas in the temperature range from −78 ° C. to the boiling point of the solvent for 1 to 200 hours under appropriate conditions. Select and do. When an oxygen-containing solvent is used in the reaction, the oxygen-containing solvent is removed by thoroughly washing with a solvent containing no oxygen atom after the reaction.
The amount of M contained in the catalyst generated at this time can take a value in the range of 0.01 mmol to 10 mmol per 1 g of the catalyst. Specific examples of the synthesis by this method include, for example, Journal of American Chemical Society.
EARTY (J. Am . Chem . Soc .) 1975
Vol. 97, page 2128, Z: Methylene group, L: Cyclopentadienyl group, M: Ti, L ': Chlorine atom, Journal of Organometallic Chemist.
Lee (J. Organomet. Chem.) 1985
280: 365, Z: methylene group, L: cyclopentadienyl group, M: Zr, L ': chlorine atom and cyclopentadienyl group. The method for synthesizing the present catalyst is not limited to this.

In the polymerization of olefins, the catalyst generally uses aluminoxane as a cocatalyst. Aluminoxane is a chain or cyclic compound represented by the following general formula (IV).

[0024]

[Chemical 4]

Here, R represents a C _{1 to} C ₁₂ hydrocarbon group (alkyl group, alkenyl group, aryl group, aralkyl group), and n takes a numerical value in the range of 2 to 20. Further, the hydrocarbon group may be spread over a plurality of types in the same molecule.
Specific examples of the aluminoxane that can be used as a cocatalyst for this catalyst include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, phenylaluminoxane, methylethylaluminoxane, methylbutylaluminoxane, and methylphenylaluminoxane. But,
Aluminoxane containing a methyl group is preferred.

As the cocatalyst, an ion pair type compound represented by the following general formula (V) can be used instead of the aluminoxane. [C] ⁺ [A] ⁻ (V) Here, [C] ⁺ is a proton, carbenium ion, tropyrylium ion, silyl cation, ammonium ion, phosphonium ion, oxonium ion, sulfonium ion, ferrocenium ion, transition Metal elements (Fe, Co, Ni, Cu, Mo, Ru, Rh, Pd,
Ag, Au, Hg, etc.), and [A] ⁻ represents a non-coordinating anion.

Specific examples of the ion pair type compound that can be used as a co-catalyst for the present catalyst include dimethylanilinium tetraphenylborate, dimethylanilinium tetrakis (pentafluorophenylborate), and anilinium tetrakis (pentafluorophenylborate). ), Triphenylcarbenium phenylborate, triphenylcarbenium tetrakis (difluoromethylborate), triphenylcarbenium tetrakis (fluorophenylborate), triphenylcarbenium tetrakis (pentafluorophenylborate), tropyrylium tetrakis (pentafluorophenyl) Borate), ferrocenium tetraphenyl borate, ferrocenium tetrakis (pentafluorophenyl borate), dimethy Ferrocenium tetrakis (pentafluorophenyl borate), Ag (I) tetraphenyl borate, Ag (I) tetrakis (pentafluorophenyl borate) and the like can be mentioned, but preferably dimethylanilinium tetrakis (pentafluorophenyl borate). , Triphenylcarbenium tetrakis (pentafluorophenyl borate), tropylium tetrakis (pentafluorophenyl borate)
Is.

The catalyst can also be used in addition to the cocatalyst mentioned above, together with (halogenated) alkylaluminum. Specific examples of the (halogenated) alkylaluminum that can be used at this time include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, and tri-n-aluminum.
-Butyl aluminum, triisobutyl aluminum,
Diethyl aluminum chloride, diethyl aluminum hydride, ethyl aluminum dichloride and the like can be mentioned, but trimethyl aluminum, triethyl aluminum and triisobutyl aluminum are preferable.

The polymerization method for olefin polymerization is not particularly limited, and any known liquid phase polymerization method such as suspension polymerization or solution polymerization, or gas phase polymerization method may be used. As a solvent in the liquid phase polymerization method, an inert hydrocarbon such as toluene or hexane may be used, or a polymerization olefin itself such as propylene may be used. The polymerization temperature is usually −50 ° C. to 250 ° C., and the polymerization pressure is 1 to 200.
It is selected in the range of kgf / cm ² . As the polymerization system, any of a batch system, a semi-continuous system and a continuous system can be adopted, and the polymerization can be carried out in two or more stages under different reaction conditions.

The olefins which can be used for the polymerization or copolymerization are α-olefins, and ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-
Methyl-1-pentene and the like can be mentioned. Also α
-In addition to olefins, terminal vinyl compounds having aromatic groups such as styrene and paramethylstyrene as substituents, terminal vinyl compounds having cyclic hydrocarbons such as vinylnorbornene and vinylcyclohexene as substituents, cyclopentene, cyclohexene, cyclooctene-1, Cyclic olefins such as 3-cyclohexadiene and non-conjugated dienes such as 1,5-hexadiene.1,4-hexadiene.1,4-cyclohexadiene and cyclooctadiene can also be used for polymerization or copolymerization.

[0031]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.

[0032]

Example 1 <Catalyst synthesis> 100 ml Schlenk 2 under a nitrogen stream
% Crosslinked chloromethylated polystyrene (Fluka, C
(1 mmol / g) 1 g, 10 ml of THF was added and suspended, and then cyclopentadienyl lithium (Cp
Li) 2 mmol was added and stirred at 30 ° C. for 100 hours. Subsequently, the solution portion was removed by decantation, and after thoroughly washing with THF, 10 ml of THF was added and suspended, 1.2 ml of a butyllithium (BuLi) hexane solution (1.6 mmol / l) was added, and the mixture was added at 5 ° C. at 5 ° C.
Stir for 0 hours. Then, the solution portion was removed again by decantation, and after thoroughly washing with THF, THF1
0 ml was added and suspended, and cyclopentadienyl zirconium trichloride (CpZrCl ₃ , Strem
2 mmol) was added and the mixture was stirred at 30 ° C. for 50 hours. After this, the solution part is removed by decantation, and TH
F, then Z by thoroughly washing with toluene and drying
r and Cl contents are 0.41 mmol / g,
A catalyst (VI) of 0.85 mmol / g was obtained.

QCH ₂ CpZrCpCl ₂ (VI) <Polymerization> 600 ml of dehydrated toluene was put into a sufficiently dried 1.5 l autoclave, and ₁ μmo in terms of Zr was added thereto.
0.5 g of a synthesized catalyst corresponding to 1 and methylaluminoxane (manufactured by Ethyl Corporation, Al 2 mol / l)
Add 8 ml of ethylene and keep ethylene pressure at 10kgf / cm ^2.
Polymerization was carried out at 0 ° C. for 1 hour. After the polymerization, methanol was added to deactivate the catalyst, and then the polymer was dried. The amount of polymer obtained at this time was 30.4 g, and the catalyst activity was 3.
It was 3 × 10 ⁵ g · polymer / g · Zr. For this polymer, GPC (Waters 150-CV
Type) was used to measure the molecular weight and molecular weight distribution, M
The results were w = 9.0 × 10 ⁵ and Mw / Mn = 2.3.

[0034]

Example 2 <Synthesis of catalyst> In Example 1, instead of cyclopentadienyl zirconium trichloride, hydrotrispyrazolyl borate zirconium trichloride (HB) was used.
(Pz) ₃ ZrCl ₃ ) was used in the same manner except that the contents of Zr and Cl were 0.37 mmol /
g, 0.81 mmol / g of catalyst (VII) was obtained. In addition, the synthesis of hydrotrispyrazolyl borate zirconium trichloride was carried out by an inorganic chemist.
Lee (Inorg. Chem.) 1983 Vol. 22 10
It carried out according to the method described on page 64.

QCH ₂ CpZr (HB (Pz) ₃ ) Cl ₂ (VII) <Polymerization> Polymerization was carried out in the same manner as in Example 1 except that the catalyst synthesized in Example 2 was used as a catalyst to obtain 9.7 g of a polymer. Obtained. At this time, the catalytic activity is 1.0 × 10 ⁵ g · polymer /
It was g · Zr. Example 1 for this polymer
Measure the molecular weight and molecular weight distribution in the same way as
The results were Mw = 1.1 × 10 ⁶ and Mw / Mn = 2.2.

[0036]

Example 3 <Synthesis of catalyst> Synthesis was performed in the same manner as in Example 1 except that cyclopentadienyl titanium trichloride (CpTiCl ₃ ) was used instead of cyclopentadienyl zirconium trichloride, and Ti, Cl Catalysts (VIII) having contents of 0.45 mmol / g and 0.93 mmol / g, respectively were obtained.

QCH ₂ CpTiCpCl ₂ (VIII) <Polymerization> Polymerization was conducted in the same manner as in Example 1 except that the catalyst synthesized in Example 3 was used as a catalyst to obtain 1.1 g of a polymer. At this time, the catalytic activity is 2.3 × 10 ⁴ g · polymer /
It was g · Ti. Example 1 for this polymer
Measure the molecular weight and molecular weight distribution in the same way as
The results were Mn = 8.0 × 10 ⁵ and Mw / Mn = 2.3.

[0038]

Example 4 <Synthesis of catalyst> 1 to 100 ml Schlenk under nitrogen stream
% Cross-linked bromopolystyrene (Fluka, Br1mm
sol / g) 1 g, and hexane 10 ml was added and suspended, and then butyl lithium (BuLi) hexane solution (1.6 mol / l) 2.0 ml was added and the mixture was stirred at 30 ° C. for 30 minutes.
Stir for hr. Subsequently, the solvent was removed by decantation, and after thoroughly washing with THF, 10 ml of THF was added and suspended, and cyclohexenone (C ₅ H
₆ O) 2 mmol was added and the mixture was stirred at 30 ° C. for 50 hours.
Then, the solvent is removed by decantation, and THF
After thoroughly washing with water-containing THF, 10 ml of THF was added to suspend the mixture, 1 ml of a methyllithium (MeLi) ether solution (2 mol / l) was added, and the mixture was stirred at 30 ° C. for 50 hours. Then, the solvent was removed again by decantation, and after thoroughly washing with THF, 10 ml of THF was added to suspend the mixture, and cyclopentadienyl zirconocent trichloride (CpZrCl ₃ , manufactured by Strem) 2 mm
was added and the mixture was stirred at 30 ° C. for 70 hours. After that, the solvent was removed by decantation, and the contents of Zr and Cl were 0.06 mmol / g and 0.13 mmol / g, respectively, by thoroughly washing and drying with THF and then with benzene.
g of catalyst (IX) was obtained.

QCpZrCpCl ₂ (IX) <Polymerization> Polymerization was carried out in the same manner as in Example 1 except that the catalyst synthesized in Example 4 was used as a catalyst to obtain 3.4 g of a polymer. At this time, the catalytic activity is 3.7 × 10 ⁴ g · polymer /
It was g · Zr. Example 1 for this polymer
Measure the molecular weight and molecular weight distribution in the same way as
The results were Mw = 8.1 × 10 ⁵ and Mw / Mn = 2.4.

[0040]

When an olefin is polymerized using the catalyst of the present invention, the polymer is higher per unit weight of transition metal than the conventional supported catalyst in which a transition metal compound and a carrier are covalently bonded. The polyolefin can be obtained in a yield.

Claims (1)

[Claims] 1. A substituent A represented by the following general formula (I):
An olefin polymerization catalyst comprising a transition metal compound having a cycloalkadienyl group L having a ligand as a ligand. ALML ′ _n (I) A: Q or QZ Q: polystyrene and polystyrene having a substituent on the benzene ring Z: C _{1 to} C ₂₀ hydrocarbon group, Si-containing group, Ge-containing group, Sn-containing group Group L that connects Q and L selected by a covalent bond L: A cycloalkadienyl group selected from a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, and a fluorenyl group having A as a substituent L ′: hydrogen Atom, hydrocarbon group, periodic table 5B ・ 6B ・ 7
Monovalent monodentate ligand selected from groups coordinated by Group B element, or monovalent polydentate ligand selected from triso group, cycloalkadienyl group, and hetero 5-membered ring ligand M: Period Table 3A, 4A, 5A group transition metal elements n: (the number of groups to which M belongs-1)