JPH11240908A - Cyclopentadienylzirconium(iv)silylalkylthiolate complex and catalyst for olefinic or styrene-based polymerization using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new cyclopentadienylzirconium(IV)silylalkyl thiorate complex and obtain a catalyst for polymerization of olefinic or styrene-based monomer having high activity. SOLUTION: This cyclopentadienylzirconium(IV)silylalkylthiolate complex is represented by the formula L<1> a L<2> b ZrXc [L<1> is a silylalkylthio group; L<2> is cyclopentadmenyl group or a substituted cyclopentadienyl group; X is a halogen atom or an alkyl group; (a) and (b) are each 1 or 2 and (a+b+c=4)]. This catalyst component for polymerization of olefinic or styrene-based monomer comprises the cyclopentadienylzirconium(IV)silylalkylthiolate complex.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel cyclopentadienyl zirconium (IV) silylalkylthiolate complex, a catalyst component for polymerization of an olefin or styrene monomer, and an olefin or styrene containing the same. The present invention relates to a catalyst for polymerizing a monomer.

[0002]

2. Description of the Related Art Zirconium (IV) cyclopentadienyl complex is effective as a catalyst component for olefin polymerization, and various complexes have already been used as olefin polymerization catalysts. On the other hand, among the zirconium (IV) complexes, several synthesis examples of a complex having thiolate as a ligand are known. For example, [(THF) Li] ₂ Z
The synthesis of r (SCMe ₃ ) ₆ is described in Inorg. Chem. , 1
996, 35, 4391-4395.
However, a zirconium complex having both a cyclopentadienyl group and a thiolate ligand is not yet known, and such a complex has never been applied to a polymerization catalyst for an olefin-based or styrene-based monomer.

[0003]

SUMMARY OF THE INVENTION The present invention provides a zirconium complex having a novel cyclopentadienyl group and a thiolate ligand and a zirconium complex having a novel cyclopentadienyl group and a thiolate ligand. It is an object of the present invention to provide a highly active olefin-based or styrene-based monomer polymerization catalyst.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies on zirconium (IV) complexes, and as a result, have found cyclopentadienyl zirconium (IV) silylalkylthiolate complexes, and combined the present complexes with aluminoxanes. The inventors have found that the catalyst used in combination has a high activity and that the polymerization reaction of the olefin-based or styrene-based monomer proceeds, and has reached the present invention. That is, the present invention
The following formula (1): L ¹ _a L ² _b ZrX _C (1) (where L ¹ is a silylalkylthio group, L ² is a cyclopentadienyl group or a substituted cyclopentadienyl group, and X is A halogen atom or an alkyl group, a
And b are each 1 or 2, and a + b + c
= 4. A) cyclopentadienyl zirconium (IV) silylalkylthiolate complex represented by the formula:
A catalyst component for polymerization of an olefin or styrene monomer comprising the cyclopentadienyl zirconium (IV) silylalkylthiolate complex; and an olefin comprising the cyclopentadienyl zirconium (IV) silylalkylthiolate complex and aluminoxane; It is a catalyst for polymerization of styrene monomers.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Cyclopentadienyl zirconium (IV) silyl alkyl thiolate complex The cyclopentadienyl zirconium (IV) silyl alkyl thiolate complex of the present invention is represented by the following formula (1). L ¹ _a L ² _b ZrX _C (1) (wherein, L ¹ is a silylalkylthio group, L ² is a cyclopentadienyl group or a substituted cyclopentadienyl group, and X is a halogen atom or an alkyl group. And
a and b are each 1 or 2, and a + b +
c = 4. In the silylalkylthio group of the ligand L1 in the formula (1), ¹ to 3 hydrogen atoms bonded to a silicon atom of the silyl group are an alkyl group having 1 to 4 carbon atoms, for example, a methyl group, It is preferably substituted with an ethyl group, a propyl group, a butyl group, a phenyl group which may have a substituent or the like, and particularly preferably a group substituted with a methyl group. The alkyl group to which the silyl group is bonded is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, and the like. Particularly, a methyl group is preferable. Preferred examples of the silyl alkyl thio group such as tris (trimethylsilyl) methanethio group (hereinafter, sometimes referred to as ST _Si.), Tris (triphenylsilyl) methanethio group.

In the substituted cyclopentadienyl group of the ligand L ² in the formula (1), examples of the substituent include an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms. No. The types of the substituents may be the same or different, and the number and position of the substituents are arbitrary. Specifically, examples of the substituted cyclopentadienyl group having one type of substituent include a methylcyclopentadienyl group, a dimethylcyclopentadienyl group, a trimethylcyclopentadienyl group, and a tetramethylcyclopentadienyl group. Group, pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, diethylcyclopentadienyl group, triethylcyclopentadienyl group, tetraethylcyclopentadienyl group, pentaethylcyclopentadienyl group, propylcyclopentadiene Enyl group, dipropylcyclopentadienyl group, butylcyclopentadienyl group, dibutylcyclopentadienyl group, pentylcyclopentadienyl group, dipentylcyclopentadienyl group, hexylcyclopentadienyl group, dihexylcyclopentadienyl Group, heptyl cyclopentadienyl group, diheptyl cyclopentadienyl group, octyl cyclopentadienyl group, dioctyl cyclopentadienyl group and the like.

The substituted cyclopentadienyl groups having different substituents include, for example, methylethylcyclopentadienyl group, methylpropylcyclopentadienyl group, methylbutylcyclopentadienyl group, methylhexylcyclopentadienyl group. Enyl group, methyloctylcyclopentadienyl group, ethylpropylcyclopentadienyl group, ethylbutylcyclopentadienyl group, dimethylethylcyclopentadienyl group, trimethylethylcyclopentadienyl group, tetramethylethylcyclopentadienyl Group, dimethylpropylcyclopentadienyl group, dimethylbutylcyclopentadienyl group and the like. Among the substituted cyclopentadienyl groups having these substituents, a pentamethylcyclopentadienyl group is preferred.

In the combination of the ligand L ¹ and the ligand L ^{2 in} the formula (1), when the number of the ligands L ¹ , that is, a is 2, the ligand L ² is not substituted It is preferably a cyclopentadienyl group, and when a is 1, L ² is preferably a substituted cyclopentadienyl group, particularly preferably a pentamethylcyclopentadienyl group.

[0009] The ligand X is a halogen atom or an alkyl group. Examples of the halogen atom include chlorine, bromine, iodine and fluorine, and among them, chlorine is preferred. Examples of the alkyl group include an alkyl group having 1 to 8 carbon atoms, preferably a methyl group or an ethyl group.

In the combination of these ligands, L ¹ is a tris (trialkylsilyl) methanethio group,
² is a substituted cyclopentadienyl group, X is a halogen atom, a is 1 and b is 1, a cyclopentadienyl zirconium (IV) silylalkylthiolate complex and L ¹ is tris (trialkylsilyl) A) a cyclopentadienyl zirconium (IV) silylalkylthiolate complex in which L is a methanethio group, L ² is a cyclopentadienyl group, X is a halogen atom, a is 2 and b is 1;

2. Production of cyclopentadienyl zirconium (IV) silylalkylthiolate complex The above-mentioned cyclopentadienylzirconium (IV) silylalkylthiolate complex is, for example, a halogen-containing zirconium (IV) complex, that is, L ² _b ZrX _4-b (formula In the formula, L ² and X are the same as those in the compound described above.)
It can be produced by reacting with a metal salt of a silylalkylthiol (thiolate) in the presence of an organic solvent.

Examples of usable solvents include alkanes having 5 to 10 carbon atoms (pentane, hexane,
Heptane, octane, etc.), aromatic hydrocarbons (eg, benzene, toluene, xylene, etc.).

The metal of the silylalkylthiol metal salt (thiolate) includes, for example, alkali metals.
It is preferably lithium, sodium or potassium, and particularly preferably lithium.

The reaction between the halogen-containing zirconium (IV) complex and the silylalkylthiol metal salt is preferably performed at a temperature of -80 ° C to 50 ° C for 10 minutes to 20 hours. The amounts of the halogen-containing zirconium (IV) complex and the silylalkylthiol metal salt are preferably 1 to 10 mol of the silylalkylthiol metal salt per 1 mol of the halogen-containing zirconium (IV) complex.

3. Polymerization of Olefin or Styrene Monomer The cyclopentadienyl zirconium (IV) silylalkylthiolate complex of the present invention can be used as a catalyst component for the polymerization of olefin or styrene monomers. Further, in the present invention, when a polymerization catalyst obtained by using a cyclopentadienyl zirconium (IV) silylalkylthiolate complex (component A) in combination with an aluminoxane (component B) is used, polymerization of an olefin-based or styrene-based monomer is performed. It can be performed with high activity.

The aluminoxane as the component B is a compound known per se, but is usually represented by the following formula (2) or (3):
It is a compound represented by these.

Embedded image (In the formula, R independently represents a hydrocarbon group having 1 to 8 carbon atoms.)

[0017]

Embedded image (In the formula, R represents a hydrocarbon group having 1 to 8 carbon atoms.)

In the formulas (2) and (3), examples of the hydrocarbon group include an alkyl group, an alkyl-substituted or unsubstituted phenyl group, and a phenyl-substituted alkyl group.

The aluminoxane of the component B can be produced by a known production method. For example, it can be produced by reacting an organic aluminum compound represented by AlR ₃ with water. Examples of such an organoaluminum compound include trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, triphenylaluminum and the like, with trimethylaluminum being particularly preferred. As the water to be reacted with the organoaluminum compound, water of crystallization such as iron sulfate and copper sulfate can be used in addition to ordinary water.

The polymerization catalyst comprising the cyclopentadienyl zirconium (IV) silylalkylthiolate complex (component A) and the aluminoxane (component B) according to the present invention comprises
Is equivalent to 1 mole of component B in terms of aluminum atom.
10 ⁶ moles, preferably used so as to contain a 10 to 10 ⁴ moles.

The method for preparing the polymerization catalyst of the present invention is not particularly limited. For example, a method of physically mixing component A and component B, a method of mixing in a suitable solvent (for example, a solvent inert to both component A and component B, for example, benzene, toluene, xylene and the like), A method of mixing in the monomer to be polymerized (in the case of a liquid) can be used. Alternatively, the components A and B can be separately introduced into the polymerization tank and used without being mixed.

The polymerization catalyst of the present invention is used for polymerizing an olefin or styrene monomer. As the olefin-based monomer, an olefin having 2 to 10 carbon atoms is preferable. When the catalyst of the present invention is used as an olefin polymerization catalyst, it is effective for homopolymerization of olefins, copolymerization of two or more different olefins, or copolymerization of olefins with diolefins having 3 to 10 carbon atoms. . The catalyst of the present invention is particularly useful for homopolymerization of ethylene, ethylene and an α-olefin having 3 to 8 carbon atoms (for example, propylene, 1-butene, 4-methyl-1-
It can be effectively used for copolymerization with pentene, 1-hexene, 1-octene, etc. (which may be either random copolymerization or block copolymerization).

Examples of the styrene monomer include styrene and styrene derivatives such as α-methylstyrene, vinyltoluene, ethylstyrene, butylstyrene, dimethylstyrene and the like. The catalyst of the present invention can be used for homopolymerization or copolymerization of two or more thereof. The catalyst of the present invention is particularly preferably used for homopolymerization of ethylene or styrene and for copolymerization of ethylene and an α-olefin.

When the catalyst of the present invention is used for polymerizing an olefin-based or styrene-based monomer, the polymerization reaction may be performed in either a gas phase or a liquid phase. When polymerizing in a liquid phase, it can be carried out in an inert hydrocarbon or a liquid monomer. As the inert hydrocarbon, for example, butane,
Isobutane, pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene and the like.

The polymerization temperature is usually from -80 ° C to 150 ° C, preferably from 30 to 120 ° C. The polymerization pressure is, for example, 1
気 圧 60 atm. Further, in order to control the molecular weight of the obtained polymer, a known molecular weight regulator, for example, hydrogen or the like can be present in the polymerization system. The polymerization reaction is carried out continuously or batchwise, and the operating conditions may be conventional conditions. Further, the polymerization reaction may be performed in a single step, or the polymerization conditions may be changed or the type of the monomer used may be changed.
It may be performed in multiple steps.

[0026]

The present invention will be described specifically with reference to the following examples. In the examples, percentages (%) are% by weight, unless otherwise specified. Example 1 (1) Dichloro (η ⁵ -pentamethylcyclopentadienyl) ｛tris (trimethylsilyl) methanethiolate｝ zirconium (IV) (hereinafter Cp ^* ZrCl ₂ (ST
_Si ). In a 100 ml flask, 800 mg (3.02 mmol) of trimethylsilylmethanethiol (referred to as T _Si SH) was dissolved in 20 ml of hexane, and cooled to 0 ° C while hexane of butyllithium (3.04 mmol) was dissolved in hexane. The solution was added dropwise. This is stirred at room temperature for 3 hours,
Lithium salt of trimethylsilylmethanethiol (LiS
Called T _Si . ) Was prepared. Another ten
In 0ml flask, trichloro - (. Referred to as _{^{Cp * ZrCl 3 (ether) 0.7}} ). (Η 5 pentamethylcyclopentadienyl) ether complex compound of zirconium (IV) (J.Organomet.Chem, 20
5 , 319 (1981). ) 1154
mg (3.00 mmol) was suspended in 30 ml of hexane, and the hexane solution of LiST _Si prepared above was added thereto. Soon the suspension became a pale yellow solution and gradually began to give a white powder. The mixture was stirred in a chamber for 4 hours, and then the insoluble matter was removed by centrifugation to obtain a pale yellow solution. By concentrating this and then cooling,
645 mg (0.86 mmol) of Cp ^* ZrCl ₂ (ST _Si ) were obtained as pale yellow crystalline powder. The yield was 38%. ^The structure was determined by ¹ H-NMR measurement, X-ray crystallography, and the like, and it was found that this crystal had the following structure.

[0027]

Embedded image However, in ¹ H-NMR analysis, Vari was used as a measuring device.
An inova 500 (manufactured by Varian) using C ₆ D ₆ as a measuring solvent, the spectrum is shown in FIG. 1, and the assignment of peaks is shown below. Assignment Chemical shift value (Ppm: TMS standard) ST _Si (27H) 0.42 Cp ^* (15H) 1.98 The result of X-ray crystal analysis was as follows.

[0028]

Embedded image In the above, the Zr-S distance was 2.415 Å and the Zr-SC angle was 130.4 °.

(2) Ethylene polymerization Into a 1-liter glass autoclave purged with nitrogen gas, Cp ^* ZrCl ₂ (ST _Si ) 0.0 obtained in (1) was added.
20 mmol was added, and further, 10 mmol of methylaluminoxane (manufactured by Tosoh Akzo Co., Ltd.) in terms of aluminum atom and 500 ml of toluene were added.
Ethylene gas was supplied to this vessel so as to be 1 kg / cm ² G, and ethylene polymerization was performed at 50 ° C. for 1 hour.
The catalytic activity was 190 g / mmol-Zr · h.
The number average molecular weight (Mn) of the produced polyethylene was 1.48 × 10 ⁵ , and the molecular weight distribution (Mw / Mn) was 2.63. The molecular weight was measured by gel permeation chromatography (GPC).

Example 2 Into a 1 liter glass autoclave purged with nitrogen gas, the catalyst component Cp ^* ZrC obtained in (1) of Example 1 was placed.
0.025 mmol of l ₂ (ST _Si ), 10 mmol of methylaluminoxane (manufactured by Tosoh Akzo Co., Ltd.) in terms of aluminum atom, 12 ml of 1-octene and 488 ml of toluene were added. Ethylene gas was supplied to this container so as to be 1 kg / cm ² G, and ethylene and 1-octene were copolymerized at 50 ° C. for 2 hours. The catalytic activity was 40 g / mmol-Zr · h. The number average molecular weight (Mn) of the produced copolymer was 7.80 × 1
0 is ^4, the molecular weight distribution (Mw / Mn) was 2.35.

Example 3 A 1-liter glass autoclave purged with nitrogen gas was charged with the catalyst component Cp ^* ZrC obtained in (1) of Example 1.
0.020 mmol of l ₂ (ST _Si ), 10 mmol of methylaluminoxane (manufactured by Tosoh Akzo Co., Ltd.) in terms of aluminum atom, 400 ml of toluene and 100 ml of styrene were added. Keep the reaction vessel at 50 ° C,
Polymerization was carried out for hours. The catalytic activity was 37 g / mmol-Z
r · hr. The number average molecular weight (Mn) of the produced polymer was 2.81 × 10 ⁵ and the molecular weight distribution (M
(w / Mn) was 2.07.

[0032]

The novel cyclopentadienyl zirconium (IV) silylalkylthiolate complex of the present invention is
When used as a catalyst, the polymerization of olefinic or styrenic monomers, particularly ethylene and styrene, can be carried out with high activity.

[Brief description of the drawings]

FIG. 1 shows Cp ^* ZrCl ₂ (ST _Si ) produced in Example 1.
4 is a spectrum showing the result of ¹ H-NMR analysis of the above.

Claims (7)

[Claims] 1. The following formula (1): L ¹ _a L ² _b ZrX _C (1) (wherein L ¹ is a silylalkylthio group, L ² is a cyclopentadienyl group or a substituted cyclopentadienyl group) X is a halogen atom or an alkyl group;
And b are each 1 or 2, and a + b + c
= 4. A) a cyclopentadienyl zirconium (IV) silylalkylthiolate complex; 2. In the formula (1), L ¹ is a tris (trialkylsilyl) methanethio group, L ² is a substituted cyclopentadienyl group, X is a halogen atom, and a is 1. And b is 1. 3. The complex according to claim 2, wherein the substituted cyclopentadienyl group is a pentamethylcyclopentadienyl group. 4. In the formula (1), L ¹ is a tris (trialkylsilyl) methanethio group, L ² is a cyclopentadienyl group, X is a halogen atom, and a is 2. The complex according to claim 1, wherein b is 1. 5. A catalyst component for polymerizing an olefinic or styrenic monomer, comprising the cyclopentadienyl zirconium (IV) silylalkylthiolate complex according to any one of claims 1 to 4. 6. An olefin or styrene monomer comprising (A) the cyclopentadienyl zirconium (IV) silylalkylthiolate complex according to any one of claims 1 to 4 and (B) an aluminoxane. Catalyst for polymerization. 7. The catalyst according to claim 6, wherein the olefin or styrene monomer is ethylene or styrene.