JPH09316120A - Catalyst for polymerizing olefin or styrene monomer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel cyclopentadienyltitanium (IV) silylalkylthiolate complex and to provide a highly active catalyst for polymerizing an olefin or styrene monomer. SOLUTION: This invention provides a novel cyclopentadienyltitanium (IV) silylalkylthiolate complex represented by the formula: L<1> a L<2> b TiXc (wherein L<1> is silylalkylthio; L<2> is substituted or unsubstituted cyclopentadienyl; X is a halogen or an alkyl; a and b are each 1 or 2; and a+b+c=4), a catalyst component for polymerizing an olefin or styrene monomer, comprising the above complex, and a catalyst for polymerizing an olefin or styrene monomer, comprising the above complex and an aluminoxane.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel cyclopentadienyl titanium (IV) silylalkyl thiolate complex, a catalyst component for polymerization of an olefinic or styrenic monomer comprising the same, and an olefinic or styrene containing the same. The present invention relates to a catalyst for polymerizing a base monomer.

[0002]

The cyclopentadienyl complex of Ti (IV) is effective as an olefin polymerization catalyst component, and various complexes have already been used as olefin polymerization catalysts. For example, in JP-A-63-39905, (R _m
-A) TiR ¹ R ² R ³ [where R = methyl; A = cyclopentadienyl; R ¹ , R ² , R ³ = C ₁ -C ₆ alkyl, (R _m -A), halogen or hydrogen. M = 0,
1 or 2] is used for the copolymerization of ethylene.

On the other hand, among the cyclopentadienyl complexes of Ti (IV), some synthetic examples of complexes having thiolate as a ligand are known. For example, chloro (η ⁵
-Cyclopentadienyl) (1,3-propanedithiolate) titanium (IV) was synthesized by Inorg. Chem., 32 , 347-3.
56 (1993). However, it has not yet been known to apply such a complex to the polymerization of olefinic or styrenic monomers.

The first object of the present invention is to provide a novel cyclopentadienyl titanium (IV) silylalkyl thiolate complex.

The second object of the present invention is to provide a catalyst component for the polymerization of highly active olefinic or styrenic monomers.

A third object of the present invention is to provide a highly active catalyst for olefin-based or styrene-based monomer polymerization.

[0007]

The present inventors have found a novel cyclopentadienyltitanium (IV) silylalkyl thiolate complex, and when it is used as a catalyst component, it exhibits high activity in olefinic or The present invention has been achieved by finding that the polymerization reaction of styrene-based monomers proceeds.

That is, the present invention is firstly the following formula (1):

[0009]

Embedded image L ¹ _a L ² _b TiX _c (1) (wherein L ¹ is a silylalkylthio group;
² is a cyclopentadienyl group or a substituted cyclopentadienyl group; X is a halogen atom or an alkyl group; a and b are 1 or 2 respectively, and a
+ B + c = 4), which is a cyclopentadienyl titanium (IV) silylalkyl thiolate complex.

Secondly, the present invention is a catalyst component for polymerization of an olefin-based or styrene-based monomer, which comprises the above-mentioned cyclopentadienyl titanium (IV) silylalkyl thiolate complex.

Thirdly, the present invention is an olefin-based or styrene-based monomer polymerization catalyst comprising (A) the above cyclopentadienyltitanium (IV) silylalkylthiolate complex and (B) aluminoxane.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The cyclopentadienyl titanium (IV) silylalkyl thiolate complex represented by the above formula (1) will be described.

In the silylalkyl thiolate represented by the ligand L ^{1, 1} to 3 hydrogen atoms bonded to the silicon atom of the silyl group are alkyl groups having 1 to 4 carbon atoms, such as a methyl group and an ethyl group. , A propyl group, a butyl group, or a phenyl group which may have a substituent, and the like are preferable, and a methyl group is particularly preferable. Further, the alkyl group to which the silyl group is bonded is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and examples thereof include methyl, ethyl, propyl, butyl, and the like. preferable. Specific preferred examples of the silylalkylthio group include a tris (trimethylsilyl) methanethio group (hereinafter sometimes referred to as ST _Si ) and a tris (triphenylsilyl) methanethio group.

When the ligand L ² is a substituted cyclopentadienyl group, examples of the substituent include an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. The types of substituents may be the same or different, and the number and position of the substituents are arbitrary. Specifically, for example, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, Diethylcyclopentadienyl group, triethylcyclopentadienyl group, tetraethylcyclopentadienyl group,
Pentaethylcyclopentadienyl group, propylcyclopentadienyl group, dipropylcyclopentadienyl group, butylcyclopentadienyl group, dibutylcyclopentadienyl group, pentylcyclopentadienyl group, dipentylcyclopentadienyl group , Hexylcyclopentadienyl group, dihexylcyclopentadienyl group, heptylcyclopentadienyl group, diheptylcyclopentadienyl group, octylcyclopentadienyl group, dioctylcyclopentadienyl group and the like. As the substituted cyclopentadienyl group having different substituents,
For example, methylethylcyclopentadienyl group, methylpropylcyclopentadienyl group, methylbutylcyclopentadienyl group, methylhexylcyclopentadienyl group, methyloctylcyclopentadienyl group, ethylpropylcyclopentadienyl group, ethyl Butylcyclopentadienyl group, dimethylethylcyclopentadienyl group, trimethylethylcyclopentadienyl group, tetramethylethylcyclopentadienyl group, dimethylpropylcyclopentadienyl group, dimethylbutylcyclopentadienyl group, etc. To be Of these, a pentamethylcyclopentadienyl group is preferable.

When the number of ligands L ¹ , that is, a is 2,
L ² is preferably an unsubstituted cyclopentadienyl group. Further, when a is 1, L ² is preferably a substituted cyclopentadienyl group, particularly a pentamethylcyclopentadienyl group. Examples of the halogen atom in the ligand X include chlorine, bromine, iodine and fluorine. Of these, chlorine is preferred. As the alkyl group,
Examples thereof include an alkyl group having 1 to 8 carbon atoms, and a methyl group or an ethyl group is preferable.

The above-mentioned cyclopentadienyl titanium (I
V) Silylalkyl thiolate complexes can be prepared, for example, by reacting a halogen-containing Ti (IV) complex, ie L ² _b TiX _{c + a,} with a metal salt (thiolate) of a silylalkylthiol in the presence of an organic solvent. . Examples of the organic solvent that can be used include alkanes having 5 to 10 carbon atoms (pentane, hexane, heptane, octane, etc.), aromatic hydrocarbons (eg, benzene, toluene, xylene, etc.) and the like. Examples of the metal of the silylalkyl thiol metal salt (thiolate) include alkali metals, preferably lithium, sodium or potassium, and particularly preferably lithium. The reaction between the halogen-containing Ti (IV) complex and the silylalkyl thiol metal salt is preferably carried out at a temperature of -80 ° C to 50 ° C for 10 minutes to 20 hours. The halogen-containing Ti (IV) complex and the silylalkyl thiol metal salt (thiolate) are preferably used in a ratio of 1 to 10 mol of the silylalkyl thiol metal salt per mol of the halogen-containing Ti (IV) complex.

The catalyst component for polymerization of the olefinic or styrenic monomer of the present invention comprises the above novel cyclopentadienyltitanium (IV) silylalkyl thiolate complex.

Next, the olefin-based or styrene-based monomer polymerization catalyst of the present invention contains the above-mentioned novel cyclopentadienyltitanium (IV) silylalkyl thiolate complex as the component A, and the aluminoxane as the component B. including.

Component B aluminoxane is known per se and is usually of the formula (2):

[0020]

Embedded image Alternatively, the following equation (3):

[0021]

Embedded image (In the above formula, each R independently represents a hydrocarbon group having 1 to 8 carbon atoms). Examples of the hydrocarbon group include an alkyl group, a phenyl group which is or is not alkyl-substituted, and a phenyl-substituted alkyl group.

The above-mentioned aluminoxane 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, of which trimethylaluminum is particularly preferable. As water to be reacted with the organoaluminum compound, in addition to ordinary water, water of crystallization such as iron sulfate and copper sulfate can be used.

In the catalyst of the present invention, the component B is converted into aluminum atoms in an amount of 1 to 10 ⁶ per 1 mol of the above component A.
Mol, preferably from 10 to 10 ⁴ moles.

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

The catalyst of the present invention is used to polymerize olefinic or styrenic monomers. The olefin-based monomer is preferably an olefin having 2 to 10 carbon atoms. When the catalyst of the present invention is used as an olefin polymerization catalyst, olefin homopolymerization, copolymerization of two or more different olefins, or olefin and carbon number 3
Effective for copolymerization with ~ 10 diolefins. The catalyst of the present invention is particularly suitable for homopolymerization of ethylene, α-olefin having 3 to 8 carbon atoms with ethylene (eg, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, etc.). It can be effectively used for copolymerization with (which may be either random copolymerization or block copolymerization).

Examples of the styrene-based monomer include styrene and styrene derivatives such as α-methylstyrene, vinyltoluene, ethylstyrene, butylstyrene and dimethylstyrene. The catalyst of the present invention can be used for homopolymerization or copolymerization of two or more kinds.

The catalysts according to the invention are particularly preferably used for the homopolymerization of ethylene or styrene and for the copolymerization of ethylene with α-olefins.

When the catalyst of the present invention is used for the polymerization of olefinic or styrenic monomers, the polymerization reaction may be carried out either in the gas phase or in the liquid phase. When the polymerization is carried out in the liquid phase, it can be carried out in an inert hydrocarbon or a liquid monomer. Examples of the inert hydrocarbon include butane, isobutane, pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene,
Xylene and the like can be mentioned. Polymerization temperature is usually -80 ℃ ~ 1
The temperature is 50 ° C, preferably 30 to 120 ° C. The polymerization pressure is, for example, 1 to 60 atmospheres. Further, in order to control the molecular weight of the obtained polymer, a known molecular weight regulator such as hydrogen can be present in the polymerization system. The polymerization reaction is carried out continuously or batchwise, and the operating conditions thereof may be conventional conditions.
The polymerization reaction may be carried out in one step, or may be carried out in two or more steps by changing the polymerization conditions or the kinds of the monomers used.

[0029]

The present invention will be specifically described with reference to the following examples. In the examples, percent (%) is% by weight unless otherwise specified.

Example 1 (1) Dichloro (η ⁵ -pentamethylcyclopentadienyl) {tris (trimethylsilyl) methanethiolate}
Synthesis of titanium (IV) (designated as Cp ^* TiCl ₂ (ST _Si )) In a 100 ml flask, 0.46 g (1.7 mmol) of trimethylsilylmethanethiol (designated T _Si SH) was dissolved in 10 ml of hexane, and the mixture was dissolved at 0 ° C. A hexane solution of butyl lithium (1.57 mmol) was added dropwise while cooling to. This was stirred at room temperature for 3 hours to prepare a hexane solution of a lithium salt of trimethylsilylmethanethiol (referred to as LiST _Si ).

In a separate 100 ml flask, trichloro (η ⁵ -pentamethylcyclopentadienyl) titanium (IV) (designated Cp ^* TiCl ₃ ) (Organometallic
s, 8, 105 (1989). The procedure of the synthesis is shown below. 0.42 g (1.43 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 dark red solution and gradually began to give a cream powder. After stirring at room temperature for 5 hours, the insoluble matter was removed by centrifugation to obtain a dark red solution. This was concentrated and then cooled to obtain 0.53 g of Cp ^* TiCl ₂ (ST _Si ).
(1.02 mmol) were obtained as red plate crystals. Yield 71
%Met.

[0032]

Embedded image (In the above formula, Me represents a methyl group, Cp ^* represents an η ⁵ -pentamethylcyclopentadienyl group, and the same applies hereinafter.) The structure was determined by ¹ H-NMR measurement, X-ray crystal analysis, and the like. It was found that it had the following structure.

[0033]

[Chemical 6] FIG. 1 shows a chart of ¹ H-NMR svector analysis. The measuring device is HITACHI R-90HS
(Manufactured by Hitachi, Ltd.), and the measurement solvent was C ₆ D ₆
Met. The assignment of peaks is shown in the table below.

[0034]

[Table 1] The results of X-ray crystal analysis are shown below.

[0035]

[Chemical 7] In the above, Ti-S distance is 2.256 Angstroms, Ti
The -SC angle was 129.4 °. (2) Polymerization of ethylene In a 1 liter glass autoclave purged with nitrogen gas, the Cp ^* TiCl ₂ (ST _Si ) 0.03 obtained in (1) was added.
Add 9 mmol, and convert methylaluminoxane (manufactured by Tosoh Akzo Co., Ltd.) into aluminum atoms.
10 mmol and 500 ml of toluene were added. Supply ethylene gas to this container at 1 kg / cm ² G,
Polymerization of ethylene was carried out at 50 ° C for 20 minutes. The catalytic activity is 15
It was 0 g / mmol-Ti.hour. The number average molecular weight (Mn) of the produced polyethylene was 3.47 × 10 ⁵ , and the molecular weight distribution (Mw / Mn) was 2.63. In addition,
The molecular weight was measured by gel permeation chromatography (GPC). Example 2 The catalyst component Cp ^* TiCl obtained in (1) of Example 1 was placed in a 1 liter glass autoclave which had been purged with nitrogen gas.
₂ (ST _Si ) 0.020 mmol, methylaluminoxane (manufactured by Tosoh Akzo Co., Ltd.) converted to aluminum atoms, 10 mmol, 1-octene 25 ml, and toluene 475
ml. Add 1kg / cm ^{2 of} ethylene gas to this container.
It was fed so that it would be G, and ethylene and 1-octene were copolymerized at 50 ° C. for 2 hours. Catalyst activity is 25 g / mmol
-Ti ・ It was time. The number average molecular weight (Mn) of the produced copolymer was 7.11 × 10 ⁴ , and the molecular weight distribution (Mw)
/ Mn) was 2.36.

Example 3 A catalyst component Cp ^* TiCl obtained in (1) of Example 1 was placed in a 1 liter glass autoclave which had been purged with nitrogen gas.
₂ (ST _Si ) 0.020 mmol, methylaluminoxane (manufactured by Tosoh Akzo Co., Ltd.) in terms of aluminum atoms, 10 mmol, toluene 350 ml and styrene 150
ml. The reaction solution was kept at 50 ° C. and polymerized for 2 hours. The catalytic activity was 96 g / mmol-Ti.multidot.hour.
The number average molecular weight (Mn) of the produced polystyrene is
It was 4.17 × 10 ⁵ , and the molecular weight distribution (Mw / Mn) was 1.85.

[0037]

INDUSTRIAL APPLICABILITY When the novel complex of the present invention is used as a catalyst, it can polymerize olefinic or styrenic monomers, especially ethylene and styrene with high activity.

[Brief description of drawings]

FIG. 1 shows Cp ^* TiCl ₂ (S produced in Example 1).
4 is a chart showing the results of ¹ H-NMR spectrum analysis of T _Si ).

Claims (7)

[Claims] 1. The following formula (1): embedded image L ¹ _a L ² _b TiX _c (1) (wherein L ¹ is a silylalkylthio group; L 1
² is a cyclopentadienyl group or a substituted cyclopentadienyl group; X is a halogen atom or an alkyl group; a and b are 1 or 2 respectively, and a
+ B + c = 4), which is a cyclopentadienyl titanium (IV) silylalkyl thiolate complex. 2. In the above 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. , B is 1. The complex according to claim 1. 3. The complex according to claim 2, wherein the substituted cyclopentadienyl group is a pentamethylcyclopentadienyl group. 4. In the above formula (1), L ¹ is a tris (trialkylsilyl) methanethio group; L ² is a cyclopentadienyl group; X is a halogen atom; a is 2; The complex according to claim 1, wherein b is 1. 5. A catalyst component for polymerization of an olefin-based or styrene-based monomer, which comprises the cyclopentadienyl titanium (IV) silylalkyl thiolate complex according to any one of claims 1 to 4. 6. An olefin-based or styrene-based monomer comprising (A) the cyclopentadienyl titanium (IV) silylalkyl thiolate complex according to any one of claims 1 to 4 and (B) an aluminoxane. Polymerization catalyst. 7. The catalyst according to claim 6, wherein the olefin-based or styrene-based monomer is ethylene or styrene.