JPH09316121A - Catalyst for polymerizing olefin or styrene monomer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel cyclopentadienyltitanium (IV) phosphinoalkylthiolate complex and to provide a highly active catalyst for polymerizing an olefin or styrene monomer. SOLUTION: This invention provides a novel cyclopentadienyltitanium (IV) phosphinoalkylthiolate complex represented by the formula: L<1> a L<2> b TiXc (wherein L<1> is phosphinoalkylthio, provided that the P atom may be coordinated with the Ti atom to form a ring; L<2> is substituted or unsubstituted cyclopentadienyl; X is a halogen or an alkyl; a and b are each 1, 2 or 3; 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) phosphinoalkyl thiolate complex, a catalyst component for polymerization of an olefinic or styrenic monomer comprising the same, and an olefinic compound containing the same. The present invention relates to a catalyst for polymerizing a styrene-based 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) phosphinoalkyl 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 catalyst for the polymerization of highly active olefinic or styrenic monomers.

[0007]

The present inventors have found a novel cyclopentadienyl titanium (IV) phosphinoalkyl thiolate complex, and when it is used as a catalyst component, the polymerization reaction with high activity is achieved. The inventors have found that it will progress and have reached the present invention.

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

[0009]

## STR00002 ## L ¹ _a L ² _b TiX _c (1) (In the above formula, L ¹ is a phosphinoalkylthio group, in which the P atom can also be coordinated with Ti to form a cyclic structure. L ² is a cyclopentadienyl group or a substituted cyclopentadienyl group; X is a halogen atom or an alkyl group; a and b are 1, 2 or 3 and a + b + c = 4) It is a cyclopentadienyl titanium (IV) phosphinoalkyl thiolate complex represented by.

Secondly, the present invention is a catalyst component for polymerization of olefinic or styrenic monomers, which comprises the above cyclopentadienyltitanium (IV) phosphinoalkylthiolate complex.

Thirdly, the present invention is a catalyst for polymerization of olefinic or styrenic monomers, which comprises (A) the above cyclopentadienyltitanium (IV) phosphinoalkylthiolate complex and (B) aluminoxane. .

[0012]

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

In the phosphinoalkyl thiolate represented by the ligand L ^{1, 1} to 2 hydrogen atoms bonded to the phosphorus atom of the phosphino group are alkyl groups having 1 to 8 carbon atoms, such as methyl group and ethyl group. It is preferably substituted with a group, a propyl group, a butyl group, a phenyl group which may have a substituent or the like, and particularly preferably a methyl group. Further, the alkyl group to which the phosphino group is bonded is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, for example, methyl, ethyl,
It is n-propyl, 1-methylethyl (isopropyl), 2-methylethyl, n-butyl and the like, and particularly preferably an alkyl group having 2 to 3 carbon atoms. Specific preferred examples of the phosphinoalkylthio group include, for example, 2-dimethylphosphinoethanethio group (hereinafter sometimes referred to as dmsp), 2-diphenylphosphinoethanethio group, 2-dimethylphosphinopropanethio group, 2 -Diphenylphosphinopropanethio group, 2-dimethylphosphino (1-methylethane) thio group, 2-dimethylphosphino (2-methylethane) thio group,
2-diphenylphosphino (1-methylethane) thio group, 2-
A diphenylphosphino (2-methylethane) thio group etc. are mentioned. A 2-dimethylphosphinoethanethio group is preferred.

In the ligand L ¹ , the S atom is bonded to Ti, but the P atom can also be coordinated with Ti to form a ring structure.

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.

In the ligand X, examples of the halogen atom include chlorine, bromine, iodine and fluorine. Of these, 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 a preferred embodiment, the ligand L ² is a cyclopentadienyl group; a is 2, b is 2 and c is 0.

In another preferred embodiment, the ligand L ² is a substituted cyclopentadienyl group (particularly a pentamethylcyclopentadienyl group); a is 3, b is 1 and c Is 0.

The above cyclopentadienyltitanium (I
V) phosphinoalkyl thiolate complexes are, for example, halogen-containing Ti (IV) complexes, ie L ² _b TiX _{c + a} ,
It can be produced by reacting with a metal salt (thiolate) of phosphinoalkylthiol in the presence of an organic solvent. Examples of the organic solvent that can be used include tetrahydrofuran (THF), ethyl ether, benzene and the like. Examples of the metal of the phosphinoalkyl thiol metal salt (thiolate) include alkali metals,
Lithium, sodium or potassium is preferable, and lithium is particularly preferable. Halogen-containing Ti
The reaction of the (IV) complex with the phosphinoalkylthiol 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 phosphinoalkylthiol metal salt (thiolate) are the same as the halogen-containing Ti (I)
V) It is preferable to use 1 to 10 mol of the phosphinoalkyl thiol metal salt per 1 mol of the complex.

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

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

Component B aluminoxanes are known per se and are usually of the formula (2):

[0023]

Embedded image Alternatively, the following equation (3):

[0024]

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 polymerizing an olefinic or styrenic monomer, the polymerization reaction may be carried out in either a gas phase or a 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.

[0032]

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) Synthesis of 2-dimethylphosphinoethanethiol (Hdmsp) used as a ligand (Me) ₂ PS-SP (Me) ₂ (where Me is a methyl group and The same) 20 g (107 mmol) and reduced iron 36.0 g (644 mmol)
Were uniformly mixed and heated in a flask to produce a liquid compound. Continue refluxing for 15 minutes, then distill,
Transparent liquid product dimethylphosphine [(Me) ₂ P-
12.34 g (101 mmol) of P (Me) ₂ ] was obtained. The yield was 94%.

In a separate flask, add sodium at -78.degree.
4.65 g (202 mmol) and 200 ml of liquid ammonia were added and stirred for 30 minutes. When the sodium was completely dissolved, a deep blue solution was obtained. Where obtained above (M
e) ₂ P-P (Me) ₂ was added dropwise and stirred for 2 hours, whereupon the color of the solution changed to yellow brown. To this, 12.2 g (203 mmol) of ethylene sulfide was added and stirred for 2 hours to obtain a yellow solution. In addition, NH ₄ Cl 1
2.0 g (224 mmol) was added and stirred for 30 minutes, when the solution turned completely white, liquid ammonia was evaporated at room temperature. The residue was extracted with 100 ml of ether, and insoluble materials were removed by filtration. After removing ether from the filtrate by atmospheric distillation, the target product, Hdmsp, was removed by vacuum distillation.
(8.91 g) was obtained (boiling point: 33-34 ° C. at 3 mmHg). The yield is
It was 64%. (2) Bis (η ⁵ -cyclopentadienyl) bis (2-dimethylphosphinoethanethiolate) titanium (IV) (C
p ₂ Ti (dmsp) ₂ ) A 100 ml flask was charged with 20 ml of hexane and 0.37 g (2.9 mmol) of Hdmsp synthesized in (1), and butyllithium (2.9 mmol) was added with stirring. After stirring for 30 minutes, the solvent was distilled off, and the Li salt of 2-dimethylphosphinoethanethiol (Hdmsp) (referred to as Lidmsp)
Was obtained as a white powder. This powder was added to THF 15m under ice temperature.
It was dissolved in 1. Dichlorodi (η ⁵
-Cyclopentadienyl) titanium (IV) (Cp ₂ Ti
A solution of 306 mg (1.23 mmol) (referred to as Cl ₂ ) (manufactured by Aldrich) of THF (45 ml) was added and stirred for 30 minutes, and the color of the solution changed from red to dark purple. After stirring at room temperature for 1 hour, 30 ml of toluene was used for extraction. The extract was concentrated to obtain a solid, which was recrystallized from hexane to give 0.77 of purple crystals of Cp ₂ Ti (dmsp) _2.
g was obtained. The yield was 87%. ¹ H-NMR measurement, X
When the structure was determined by line crystal analysis, etc., this crystal was
It was found to have the following structure (Me represents a methyl group, the same applies below).

[0035]

Embedded image 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 is CDCl
_{Was 3} . The assignment of peaks is shown in the table below.

[0036]

[Table 1] Intrinsic chemical shift values (ppm: TMS _{reference) P-C H 3 (12H} ) 0.98, 1.00 S-CH 2 -C H 2 -P (4H) 1.44 ~1.62 S-C H 2 -CH 2 -P (4H) 3.02 ~3.23 Cp (10H) 6.10 The result of X-ray crystallography is shown below.

[0037]

[Chemical 6] (3) Polymerization of ethylene Into a 1-liter glass autoclave substituted with nitrogen gas, 0.019 mmol of Cp ₂ Ti (dmsp) ₂ obtained in (2) was added, and further methylaluminoxane (manufactured by Tosoh Akzo Co., Ltd.) Was converted into aluminum atom and 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 for a minute. The catalytic activity was 160 g / mmol-Ti.multidot.hour. The number average molecular weight (Mn) of the produced polyethylene was 2.75 × 10 ⁵ , and the molecular weight distribution (Mw / Mn) was 2.27. The molecular weight is measured by gel permeation chromatography (GP
C).

Example 2 A catalyst component Cp ₂ Ti (dms) obtained in (2) of Example 1 was placed in a 1 liter glass autoclave whose atmosphere was replaced with nitrogen gas.
p) ₂ 0.020 mmol, methylaluminoxane (manufactured by Tosoh Akzo Co., Ltd.) in terms of aluminum atoms, 10 mmol, 1-octene 10 ml and toluene 490 ml were added. Ethylene gas was supplied to this container at a rate of 1 kg / cm ² G, and ethylene and 1-octene were copolymerized at 50 ° C. for 2 hours. The catalyst activity was 27 g / mmol-Ti.multidot.hour. The number average molecular weight (Mn) of the produced copolymer was 1.29 × 10 ⁵ , and the molecular weight distribution (Mw / M
n) was 2.03.

Example 3 A catalyst component Cp ₂ Ti (dms) obtained in (2) of Example 1 was placed in a 1 liter glass autoclave purged with nitrogen gas.
p) ₂ 0.020 mmol, methylaluminoxane (manufactured by Tosoh Akzo Co., Ltd.) in terms of aluminum atom, 10 mmol, 350 ml of toluene and 150 ml of styrene were added. The reaction solution was kept at 50 ° C. and polymerized for 2 hours. The catalytic activity was 8 g / mmol-Ti.multidot.hour. The number average molecular weight (Mn) of the produced polystyrene was 5.96 × 10.
⁴ , and the molecular weight distribution (Mw / Mn) was 1.75.

Example 4 (1) η ⁵ -Pentamethylcyclopentadienyltris (2-dimethylphosphinoethanethiolate) titanium
Synthesis of (IV) (designated Cp ^* Ti (dmsp) ₃ ) In a 100 ml flask, 20 ml of hexane and Example 1
0.46 g (3.8 mmol) of Hdmsp synthesized in (1) above was added, and butyllithium (3.8 mmol) was added with stirring. After stirring for 30 minutes, the solvent was distilled off, and the Li salt of 2-dimethylphosphinoethanethiol (Hdmsp) (Lidm
a white powder). This powder was dissolved in 15 ml of THF under ice temperature. In addition to this, separately prepared trichloro (η ⁵ -pentamethylcyclopentadienyl)
Titanium (IV) (referred to as Cp ^* TiCl ₃ ) (Organo
Synthesized according to metallics, 8, 105 (1989). The procedure of the synthesis is shown below. ) 0.36 g (1.23 mmol) THF
When (20 ml) solution was added and stirred for 30 minutes, the color of the solution changed from red to dark red. After stirring for another hour at room temperature, the mixture was extracted with 30 ml of toluene. The extract was concentrated to give a solid, which was recrystallized from hexane to obtain 0.43 g of Cp ^* Ti (dmsp) ₃ purple crystals. The yield was 63%.

[0041]

[Chemical 7] (In the above formula, Me represents a methyl group, and Cp ^* represents a η ⁵ -pentamethylcyclopentadienyl group) The structure was determined by ¹ H-NMR measurement, X-ray crystal analysis, etc., and the crystal had the following structure: Found to have.

[0042]

Embedded image The chart of ¹ H-NMR vector analysis is shown in FIG. The measuring solvent was C ₆ D ₆ . The assignment of peaks is shown in the table below.

[0043]

[Table 2] Intrinsic chemical shift values (ppm: TMS _{reference) P-C H 3 (18H} ) 1.07, 1.08 S-CH 2 -C H 2 -P (6H) 1.68 ~1.89 Cp * (15H) 2.09 S-C H 2 -CH 2 -P ( 6H) 3.30 to 3.57 The results of X-ray crystallography are shown below.

[0044]

Embedded image In the above, the Ti-S (1) distance is 2.424 Å, the Ti-S (3) distance is 2.386 Å, Ti-S (2).
The distance was 2.338 Angstroms. Also, Ti-P
The distance in (1) was 2.625 angstroms. (2) Polymerization of ethylene Instead of Cp ₂ Ti (dmsp) ₂ , the C obtained in (1) above was used.
Polymerization of ethylene was carried out in the same manner as in (3) of Example 1 except that 0.020 mmol of p ^* Ti (dmsp) ₃ was used. The catalytic activity was 49 g / mmol-Ti.multidot.hour. Also,
The number average molecular weight (Mn) of the produced polyethylene is 4.3 ×
10 ⁵ and the molecular weight distribution (Mw / Mn) was 2.65.

[0045]

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

[Brief description of drawings]

FIG. 1 of Cp ₂ Ti (Hdmsp) ₂ produced in Example ¹
It is a chart which shows the result of 1 H-NMR spectrum analysis.

FIG. 2 ^{1 of} Cp ^* Ti (Hdmsp) ₃ produced in Example 4
It is a chart which shows the result of 1 H-NMR spectrum analysis.

Claims (9)

[Claims] 1. The following formula (1): ## STR00001 ## L ¹ _a L ² _b TiX _c (1) (wherein, L ¹ is a phosphinoalkylthio group, wherein the P atom is also coordinated to Ti. L ² is a cyclopentadienyl group or a substituted cyclopentadienyl group; X is a halogen atom or an alkyl group; and a and b are each 1, 2 or 3 and a + b + c = 4), a cyclopentadienyl titanium (IV) phosphinoalkyl thiolate complex. 2. In the above formula (1), L ² is a cyclopentadienyl group; a is 2, b is 2,
The complex according to claim 1, wherein c is 0. 3. The complex according to claim 1, wherein in the formula (1), L ² is a substituted cyclopentadienyl group; a is 3, b is 1 and c is 0. 4. The complex according to claim 3, wherein the substituted cyclopentadienyl group is a pentamethylcyclopentadienyl group. 5. The complex according to claim 3 or 4, wherein one P atom of L ¹ is also coordinated with Ti to form a ring structure. 6. The complex according to claim ¹ , wherein in the formula (1), L ¹ is a 2-dimethylphosphinoethanethio group. 7. A catalyst component for polymerization of an olefin-based or styrene-based monomer, which comprises the cyclopentadienyl titanium (IV) phosphinoalkyl thiolate complex according to any one of claims 1 to 6. 8. An olefin-based or styrene-based monomer comprising (A) a cyclopentadienyltitanium (IV) phosphinoalkylthiolate complex according to any one of claims 1 to 6 and (B) an aluminoxane. Polymerization catalyst. 9. The catalyst according to claim 8, wherein the olefin-based or styrene-based monomer is ethylene or styrene.