JPS63182308A - Olefin polymerization catalyst - Google Patents

Abstract

PURPOSE:To obtain the title catalyst which can give a highly stereoregular polymer in a high catalystic activity, by combining a specified solid catalyst component with an organoaluminum compound. CONSTITUTION:A solid catalyst compound (A) is obtained by contacting a solid component (a) essentially consisting of Mg, Ti and a halogen, obtained by couplverizing a magnesium halide with a titanium compound and, optionally, an electron donor and having a Ti to Mg atomic ratio of 1X10<-2>-1, a halogen to Mg atomic ratio of 0.5-4 and an electron donor to Mg molar ratio <=1 with a 1:1 complex (b) of a Ti compound of formula I (wherein X is halogen, R<1> and R<4> are each a hydrocarbon residue, R<2> is a branched hydrocarbon residue, R<3> is R<2> or a different hydrocarbon residue, and 1<=m<=3) with an Si compound of formula II. Component A is combined with an organoaluminum compound (B) of formula III or IV (wherein R<5-6> are each a 1-20C hydrocarbon residue or H, R<7> is a hydrocarbon residue, 0<=n<3 and 0<m<3) at a B to A weight ratio of 0.1-1,000 to obtain the title olefin polymerization catalyst.

Description

[Detailed description of the invention] [Background of the invention] Technical field The present invention relates to a catalyst for olefin polymerization.

More specifically, when the present invention is applied to the polymerization of olefins, especially a-olefins having 3 or more carbon atoms, by using a specific catalyst, it is possible to produce a highly stereoregular polymer under stable polymerization conditions, which is advantageous for industrial production. This makes it possible to manufacture

BACKGROUND OF THE INVENTION Conventionally proposed olefin polymerization catalysts consisting of a solid catalyst component containing titanium, magnesium, and halogen as essential components and organoaluminum have extremely high activity, but the problem is the steric controllability of the product polymer. In some cases, it was necessary to use electron-donating compounds during polymerization.

However, such catalysts that use an electron-donating compound as the third component (external donor) have problems such as a decrease in the polymerization rate and an increase in the polymerization temperature due to the reaction between the organoaluminum compound and the electron-donating compound. Since the above reaction is promoted, it is restricted to increase the polymerization amount (improve production efficiency) by increasing the polymerization temperature.
There is a problem in that it is difficult to control the performance of the product polymer, including the molecular weight control of the product polymer.

Therefore, it is desired to develop a catalyst system that can solve the above problems and produce highly stereoregular polymers at high catalytic yields without using an electron-donating compound as a third component (external donor). .

Prior art JP-A-58-138715 discloses a titanium composite (i) containing tetravalent titanium, magnesium, halogen and an electron donor as essential components without using an external donor.
and an organosilicon compound (2) having a 5i-0-C bond
and a solid component obtained by reacting the titanium complex in the presence of an organoaluminum compound, or by treating the titanium complex with an organoaluminum compound and then reacting it with the organosilicon compound, and a titanium complex formed from an organoaluminium. A method of polymerizing with a catalyst system is disclosed.

However, although this proposal has made progress in resolving the above problems, there are limits to the performance of the resulting product polymer.
Furthermore, there are still many points that need to be improved, such as deterioration of the catalyst over time and restrictions on the ratio of the titanium component to the organoaluminum compound used during polymerization.

[Summary of the invention]

Summary The present inventors have worked hard to improve conventional catalyst systems and prior art, and have completed a catalyst composed of specific components (A) and (B), thereby solving the problems.

That is, the olefin polymerization catalyst according to the present invention is composed of the following components (A) and (B).

Component (A) Component (i): A solid component containing magnesium, titanium and 710 gen as essential components, and component (i1)
General formula % formula %) (However, X is) 10 gen, R1 is a hydrocarbon residue,
R2 is a branched hydrocarbon residue, R3 is the same or different hydrocarbon residue as R2, R4 is a hydrocarbon residue,
A complex of a titanium compound and a silicon compound, where n is a number of 1≦n≦4, and m is a number of 1≦m≦3. does not indicate that 1=1), a solid catalyst component obtained by contacting

Ingredient (B) Organoaluminum compound.

Effects According to the present invention, the problems of the above-mentioned prior art can be solved. In addition, compared to known catalysts such as catalysts that use electron-donating compounds as the third component, the catalyst of the present invention has better sustainability of polymerization activity, the ability to raise the polymerization temperature, and the molecular weight of the resulting polymer. that the control of the
It has the following characteristics.

[Detailed description of the invention]

Catalyst The catalyst of the present invention is composed of a specific component (A) and a component (B). Here, "consisting of component (A) and component (B)" does not mean excluding a third component that does not unduly impair the effects of the present invention or a third component that has an advantageous effect on the present invention. I want you to understand something.

Component (A) Component (A) of the catalyst used in the present invention is the above-mentioned component (
It is a solid catalyst component obtained by bringing i) into contact with component (i1).

(i) Component (i) Component (i) is a solid component containing titanium, magnesium and metal as essential components.

In 22, "containing as an essential component" means not only when component (i) consists only of these three specific components, but also as long as the effects of these three components are at least maintained or not unduly impaired. , meaning that it may contain additional ingredients.

Such solid components are known. For example, JP-A-5
No. 3-45688, No. 54-3894, No. 54-31
No. 092, No. 54-39483, No. 54-94591
No. 54-118484, No. 54-131589, No. 55-75411, No. 55-90510, No. 5
No. 5-90511, No. 55-127405, No. 55-
No. 147507, No. 55-155003, No. 56-1
No. 8609, No. 56-70005, No. 56-7200
No. 1, No. 56-86905, No. 56-90807,
No. 56-155206, No. 57-3803, No. 57
-34103, 57-92007, 57-12
No. 1003, No. 58-5309, No. 58-5310, No. 58-5311, No. 58-8706, No. 58-
No. 27732, No. 58-32604, No. 58-326
No. 05, No. 58-67703, No. 58-117206
No. 58-127708, No. 58-183708, No. 58-183709, No. 59-149905,
Those described in each publication, No. 59-149905, etc. are used.

Examples of the magnesium compound serving as a magnesium source used in the present invention include magnesium halide, dialkoxymagnesium, alkoxymagnesium halide, magnesium oxyhalide, dialkylmagnesium, magnesium oxide, magnesium hydroxide, magnesium carboxylate, and the like.

In addition, the titanium compound serving as a titanium source has the general formula Ti(O
R)

) can be mentioned.

Specific examples include TLCI TiBr4.4ゝTi (OC2H5)C13, Tl (OC2H5)2C12, Tl (OC2H5)3C1, Ti (0-1C3H7)C13, Ti (0-nC4H9)C13, Ti (O-nC4H9) 2C12, Ti (OCH) B r 3, Ti (OCH) (OC4H9) 2C1, Ti (On
C4H9) 3 C1-T i (OCR) Cl 3
, T i (0-1C4H9)2CI 2, Ti (OC
5H11) C13, Ti (OC6H13)C13, Ti (OC2H5)4, Ti(On C3H7) 4, T1 (0-nC4H9)4, T I (0-iC4H9) 4, Ti (0-nC6H13) 4, Ti (0-nC8H,7) 4, TiC0CH2CH(C2H5)c4H9]4, etc.

Further, a molecular compound obtained by reacting TIX'4 (herein, X' represents a halogen) with an electron donor described later can also be used. As a specific example, T iC14・CH3C
OC2H5, TsCl4・CH3CO2C2H5, TiCl4
φC6H5NO2, TLCI @CH3COCl.

TiCl4・C6H5COCl.

Examples include TiC1411C6H5C02c2H5, TiCl4Fist CICOC2H5, TIC14・C4H40, and the like.

Halogen is usually supplied from the above-mentioned magnesium and/or titanium halogen compounds, but it can also be supplied from known halogenating agents such as aluminum halides, silicone halides, and phosphorus halides. can.

Halogens contained in catalyst components include fluorine, chlorine, bromine,
It may be iodine or a mixture thereof, with chlorine being particularly preferred.

In addition to the above-mentioned essential components, the solid components used in the present invention include Si
CI CHS t C13, methylhide 4ゝ
Silicon compounds such as 30 diene polysiloxane, Al(0-
IC3H8)3, AlCl3, AlBr Al(OC
2H5)3. It is also possible to use other components such as aluminum compounds such as 3ゝAl (OCH3)2C1 and boron compounds such as B(OCH5)3.3 3ゝB(OC6H5)3. It may also remain in the solid component as a component such as boron.

Furthermore, when producing this solid component, it is also possible to produce it using an electron donor as an internal donor.

Electron donors (internal donors) that can be used in the production of this solid component include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid Oxygenated electron donors such as anhydrides, ammonia, amines, nitriles,
Examples include nitrogen-containing electron donors such as isocyanates.

More specifically, (a) methanol, ethanol, propatool, pentanol, hexanol, octatool, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropylbenzyl alcohol and the like having 1 to 18 carbon atoms; alcohols, (b) phenols having 6 to 25 carbon atoms which may have an alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, cumylphenol, nonylphenol, naphthol, (c) acetone, methyl ethyl ketone ,
Ketones having 3 to 15 carbon atoms such as methyl isobutyl ketone, acetophenone and benzophenone; (d) Aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde and naphthaldehyde; (e) Methyl formate, methyl acetate, ethyl acetate, vinyl acetate,
Propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl viniferate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, Ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, Ethyl anisate, ethyl ethoxybenzoate,
2 to 2 carbon atoms such as diethyl phthalate, dibutyl phthalate, dihebutyl phthalate, γ-butyrolactone, α-parerolatkone, coumarin, phthalide, ethylene carbonate, etc.
0 organic acid esters, (f) inorganic acid esters such as silicic acid esters such as ethyl silicate, butyl silicate, and phenyltriethoxysilane, (t) acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid Acid halides having 2 to 15 carbon atoms such as chloride, phthaloyl chloride, and isophthaloyl chloride; (3) 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, aluminum ether, tetrahydrofuran, anisole, and diphenyl ether;
ethers, (su) acetic acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide, (nu) methylamine, ethylamine, diethylamine, tributylamine,
Examples include amines such as piperidine, tribenzylamine, aniline, pyridine, picoline, and tetramethylethylenediamine, and nitriles such as (l)acetonitrile, benzonitrile, and tolnitrile.

Two or more types of these electron donors can be used.

The quantitative ratio of the constituent components of this solid component is within the range of 1×10''2 to 1 in Ti/Mg atomic ratio, and in the range of 0.5 to 4 in halogen/Mg atomic ratio, and in some cases It is preferable that the contained electron donor/Mg molar ratio is in the range of 1 or less.

When silicon, aluminum and boron compounds are contained, the molar ratio of these compounds to the amount of the magnesium compound used is within the range of 1 x 10-3 to 100, preferably in the range of 1 x 10-2 to 1. It is within.

The solid component used in the method of the present invention can be produced by a known method, but the following production method is particularly preferred.

(a) A method of producing activated magnesium halide, an electron donor, and a titanium compound by simultaneously or gradually co-pulverizing or contacting them in a liquid state. A halogenating agent may be further brought into contact with this.

(b) Add an electron donor and a titanium compound to the precipitate obtained by reacting a halogenating agent, a reducing agent, etc. with or without an electron donor to a magnesium compound in a homogeneous state. A method for producing a catalyst by contacting

(c) A method of producing a catalyst by reacting an organomagnesium compound such as a Grignard reagent with a halogenating agent, a reducing agent, etc., and then contacting the compound with an electron donor and a titanium compound.

(d) A method for producing a catalyst by contacting an alkoxymagnesium compound with a halogenating agent and/or a titanium compound in the presence or absence of an electron donor.

As the catalyst component (i) used in the present invention, the solid component obtained as described above can be used as it is, or the solid component can be prepolymerized by contacting it with an olefin in the presence of an organoaluminum compound. It can also be used as Moreover, when this component (i) is prepolymerized, it is preferable that component (If) is brought into contact after being prepolymerized.

When component (i) is prepolymerized, this component (
There are no particular restrictions on the conditions for prepolymerization of olefins for producing +), but the following conditions are generally preferred. Polymerization temperature is 0 to 80°C, preferably 10 to 60°C
It is. The amount of polymerization is 0.0 per gram of solid component.
It is preferable to polymerize 01 to 50 grams of olefins, more preferably 0.1 to 10 grams of olefins.

As the organoaluminum component during prepolymerization, commonly known components can be used.

Specific examples include Al (C2H5)3, Al (is
OC4H9)3, Al (C5H13)3, AI (
CH) AI (C1oH2,) 3.8 1
7 3' AI (C2H5)2CI- AI (isoC4H9)2CI.

Al　(C2H5)2H1 AI (i5oC4H9)2H.

Examples include AI (CH) (QC2H5). Among these, preferred is Al (CH) Al (lC4H9)3253
Yes.

Further, a combination of trialkylaluminum and alkyl aluminum halide, a combination of trialkylaluminum, alkyl aluminum halide, and alkyl aluminum ethoxide, etc. are also effective.

To give a specific example, Al (C2H5)3 and Al (C2
H5) Combination of 2C1, combination of Al (LsoC4H9) 3 and Al (iSOC4H9)2C1, AI (C2
Combination of H5)3 and Al (C2H5)1.5C11,5・AI(C
H) and Al (C2H5)2C1 and AI (CH)
(QC2H5) can be used in combination.

The amount of organoaluminum component used during prepolymerization is AI/Ti (molar ratio) with respect to the Ti component in the homogeneous component (A).
and is 1 to 20, preferably 2 to 10. In addition to these, known electron donors such as alcohols, esters, and ketones can also be added during prepolymerization.

The olefins used specifically for prepolymerization include ethylene,
Propylene, 1-butene, 1-hexene, 4-methyl-
Examples include pentene-1. Further, it is also possible to coexist with a prepolymerization condition element.

In this way, the solid component containing titanium, magnesium and halogen as essential components was brought into contact with olefins in the presence of an organoaluminum compound.
ffi combined component (i) is obtained.

(2) Component (i1) Component (i1) that is brought into contact with the above component (i) in order to produce component (A) of the catalyst used in the method of the present invention is a titanium compound and a silicon compound represented by the following general formula. It is a complex with

(However, X is a halogen, R1 is a hydrocarbon residue, R
2 is a branched hydrocarbon residue, R3 is the same or different hydrocarbon residue as R2, R4 is a hydrocarbon residue, n
(indicates the number of 1≦n≦4, and m indicates the number of 1≦m≦3, respectively) The fact that both compounds form a complex indicates that the Ti/X ratio of the starting material is determined by compositional analysis of the product. Consistent with that and by gas chromatographic analysis of the product, R2R3S
L (OR') is the structure and quantity 3-m
This can be confirmed from the fact that it has not changed physically from the starting material.

Here, the titanium compound for constituting the component (I) has the general formula Ti(OR) X represents halogen, n is 1≦n≦4
Indicates the number of ) are titanium compounds represented by: Specific examples include TlC14, TiBr4, Tl(OC2H5)C13, Ti(OC2H5)2C12, T1(OC2H5)3C11 Ti(0-1C3H7)C13, Ti(0-nC4H9)C13, Ti(0- nC4H9)2C12, Ti(OC2H5)B"3, Ti(OCH)(OC4H9)2C1°T 1(0-n
C4H9)3C1-Ti(0-C6H5)C13, Ti(0-1C4H9)2C12, Ti(OC5H1,)C13, Ti(OC6H13)C13, Tl(OC8H17) 2c 12, Ti(OC
1oH21) C13, etc. Among these, TiCl4, T i B r 4, Ti (
OC2H5)C13, etc.

The silicon compound for constituting the complex has the general formula (however,
R2 is a branched hydrocarbon residue, R3 is the same or different hydrocarbon residue as R2, R4 is a hydrocarbon residue,
m is a silicon compound represented by a number of 1≦m≦3, respectively.

Here, R2 is preferably branched from the carbon atom adjacent to the silicon atom. In that case, the branching group may be an alkyl group, a cycloalkyl group or an aryl group (for example,
A phenyl group or a methyl-substituted phenyl group) is preferable. More preferably, R2 is such that the carbon atom adjacent to the silicon atom, that is, the α-position carbon atom, is secondary or tertiary.
It is a carbon atom of class.

Particularly preferred are those in which the carbon atom bonded to the silicon atom is tertiary. The number of carbon atoms in R2 is usually 3 to 20, preferably 4 to 10. R3 is usually a branched or linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. R4 is usually an aliphatic hydrocarbon group, preferably a chain aliphatic hydrocarbon group having 1 to 4 carbon atoms.

Specific examples of silicon compounds are shown below.

(CH) C-5t (OCH3) 2, (CH)
C-8t (OCH3) 2, (CH) C-8i(
OC2H5)2, (CH) C-5L (OCH3)
2, CH3 CH3 (CH3)3cm81 (ocH3)3, (CH)C-8
i(oc2H5)3, (CH)c-8i(oc2H5)3. CH3 H3 etc.

Conditions for producing a complex from a titanium compound and a silicon compound may be arbitrary as long as the effects of the present invention are observed, but are generally preferably within the following range. The contact temperature is -50°C to 100°C, more preferably 0°C to 50°C.
℃. Examples of the contacting method include a mechanical method using a rotary ball mill, a vibration mill, etc., and a method of contacting by stirring in the presence of an inert diluent. Examples of the inert diluent used at this time include aliphatic or aromatic hydrocarbons, halohydrocarbons, and polysiloxanes.

The working mm ratio of the titanium compound (A) and the silicon compound (B) is the molar ratio (A/B) "C' I X 10-2~1
It is preferably within the range of 0, preferably 0. It is within the range of 1 to 5.

The amount of the complex of titanium and silicon compound to be used is preferably within the range of 1 x 10-2 to 100 in terms of molar ratio to the amount of the magnesium compound constituting component (i), preferably 0.
．． It is within the range of 1 to 10.

When using an electron-donating compound, the amount used is the component (i
) with respect to the amount of magnesium compound used, the molar ratio is 1
x10-3 to 10, preferably 0.01
It is within the range of ~5.

Component (A) is a complex consisting of component (i) which has the above-mentioned magnesium, titanium, and halogen as essential components, and titanium and a silicon compound. It can be produced, for example, by the following production method using component (i1) and, if necessary, other components such as an electron-donating compound.

(a) A method of bringing magnesium halide and a titanium-containing compound into contact with a complex of a titanium compound and a silicon compound (hereinafter abbreviated as titanium-silicon complex), and, if necessary, an electron-donating compound.

(b) A method of treating alumina or magnesia with a halogenated phosphorus compound and contacting it with a magnesium halide, a titanium halogen-containing compound, a titanium-silicon complex, and, if necessary, an electron-donating compound.

(c) A solid component obtained by contacting a magnesium halide with a titanium tetraalkoxide and a specific polymeric silicon compound is added with a titanium halogen compound and/or a silicon halogen compound, a titanium-silicon complex, and, if necessary, an electron donor. A method of bringing compounds, etc. into contact.

(d) A solid component obtained by dissolving a magnesium compound with a titanium tetraalkoxide and an electron-donating compound and precipitating it with a halogenating agent or a titanium halogen compound,
A method of contacting titanium-silicon complexes.

(e) A method in which an organomagnesium compound such as a Grignard reagent is reacted with a halogenating agent, a reducing agent, etc., and then brought into contact with a titanium-silicon complex, a titanium-containing compound, and, if necessary, an electron-donating compound.

(v) A method of contacting an alkoxymagnesium compound with a halogenating agent and/or a titanium compound or a titanium-silicon complex.

Component (A) used in the present invention is 5rC in addition to the above essential components.
I CH5IC13, silicon compounds such as alkylhydrodiene polysiloxane, AI (0-1C3H7)
3. Aluminum compounds such as AI (QCH) AI (OCH3) 2C1゜253ゝA I CI AI B r 3, and B(OCH3)3, B(QCH) B(QC6H5)3, etc. It is also possible to use other components such as boron compounds;
It may remain in the solid component as components such as aluminum and boron.

Ingredient (B) Component (B) is an organoaluminium compound.

Specific examples include R3-nAIXn or RAl(O
R7) (where R5 and R6 are 3-m
s Hydrocarbon residue or hydrogen atom having about 1 to 20 carbon atoms, which may be the same or different, R7 is a hydrocarbon residue, X is halogen, n and m are 0≦n<3, O<m<3, respectively. It is a number. ). in particular,
(a) Trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, etc., (b) diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, ethyl Alkylaluminum halides such as aluminum dichloride, (c) diethylaluminylhamno-1 hydride, diisobutylaluminum hydride, (d) aluminum alkoxides such as diethylaluminum ethoxide, diethylaluminum phenoxide, and the like.

These (a) to (d) organoaluminum compounds include other organometallic compounds, such as R8 and R9, which may have the same or different carbon atoms.
~20 hydrocarbon residues. ) can also be used in combination with an alkyl aluminum alkoxide. For example, a combination of triethylaluminum and diethylaluminum ethoxide, a combination of diethylaluminum monochloride and diethylaluminum ethoxide,
Examples include a combination of ethylaluminum dichloride and ethylaluminum jetoxide, and a combination of triethylaluminum, diethylaluminum ethoxide, and diethylaluminum chloride.

The amount of component (B) used is component (B)/component (A) in weight ratio.
) is in the range of 0.1 to 1000, preferably 1 to 100.

Polymerization In the present invention, polymerization is usually carried out in the liquid phase. Liquid phase polymerization generally involves pentane, hexane,
Slurry polymerization using saturated aliphatic, cyclic, or aromatic hydrocarbons such as heptane, cyclohexane, kerosene, benzene, toluene, etc. alone or in mixtures as a polymerization solvent, and liquid phase non-solvent using the olefin itself of the polymerization monomer as a solvent. It can be carried out by a polymerization method.

Polymerizable olefin monomers include ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4
Examples include α-olefins such as -methylpentene-1. These can be not only homopolymerized, but also random copolymerized with α-olefins, block copolymerized, and copolymerized with conjugated or non-conjugated dienes.

The polymerization temperature is about room temperature to 200°C, preferably 50 to 15°C.
It is appropriate that the temperature is about 0°C and the polymerization pressure is within the range of normal pressure to about 100 kg/cj, preferably about 1 to 50 kg/cj. Hydrogen can then be used as an auxiliary molecular regulator.

After polymerization - the resulting slurry is optionally degassed and
Furthermore, the insoluble polymer and polymerization solvent are separated from the slurry using a device such as a filter, a centrifuge, a countercurrent extraction tower, or a hydrocyclone. Part or all of the solvent separated from the slurry is recycled to the polymerization process and reused.

Experimental Examples Example-1 (Production of component (A)) Dehydrated and deoxygenated n
- 200 ml of hebutane is introduced, then MgC
Introducing 0.1 mol of l2 and 0.2 mol of Ti(O-nC4H9)4, 95
The reaction was carried out at ℃ for 2 hours. After the reaction was completed, the temperature was lowered to 40° C., and then 12 ml of methylhydropolysiloxane (20 centistokes) was introduced and the reaction was allowed to proceed for 3 hours. The solid component produced was washed with n-hebutane. Next, 50 milliliters of rhohebutane purified in the same manner as above was introduced into the flask which had been sufficiently purged with nitrogen, and 0.03 mol of the solid component synthesized above was introduced in terms of Mg atoms. Next, add Si to 25 ml of n-heptane.
40-05 moles of Cl were mixed and introduced into the flask at 30°C for 30 minutes, followed by reaction at 70°C for 3 hours. After the reaction was completed, it was washed with n-hebutane.

Next, 0.004 mol of diheptyl phthalate was mixed with 25 ml of n-heptane, and the mixture was introduced into a flask at 70°C for 30 minutes, and reacted at 70°C for 1 hour. After the reaction was completed, it was washed with n-hebutane.

Next, 1415 milliliters of TiC was introduced and 10
The reaction was carried out at 0°C for 6 hours. After the reaction was completed, it was washed with n-hebutane to obtain component (i).

(Synthesis of component (i0 (titanium-silicon complex)) 100 ml of dehydrated and deoxygenated n-hebutane was introduced into a flask that had been sufficiently purged with nitrogen, and 0.1 mol of H3 a-1) was introduced. Then, T iCl
40,' 1 mol was introduced in 30 minutes, and 3
Allowed time to react. After the reaction was completed, it was washed with n-hebutane. When we took out a part and analyzed its composition, we found that TiCl4
- It was 0.86 (a-1).

(Production of component (A)) 100 milliliters of purified n-hebutane was introduced into a flask that had been sufficiently purged with nitrogen, and the above component (i) and component (
0.02 mol of I1) was introduced and reacted at 40°C for 3 hours. After the reaction was completed, it was thoroughly washed with n-heptane to obtain component (A).

(Polymerization of propylene) In a stainless steel autoclave with an internal volume of 1.5 liters equipped with a stirring and temperature control device, 500 ml of thoroughly dehydrated and deoxidized n-heptane was added, and the components (
As B), 75 mg of triethylaluminum and 15 mg of the catalyst component (A) synthesized above were introduced. Next, 60 milliliters of H2 was introduced, the temperature and pressure were increased, and polymerization was carried out under the conditions of a polymerization pressure of 5 kg/cs G, a polymerization temperature of -75°C, and a polymerization time of -2 hours. After the polymerization was completed, the resulting polymer slurry was separated by filtration, and the polymer was dried. 113 grams of polymer were obtained and boiling hebutane extraction tests showed that the total product was 1. 1 (hereinafter abbreviated as T~1.I) is 97.5 weight percent, MFR-4, 3 g/10 min, polymer bulk specific gravity -0
, 44 g/cc.

Comparative Example-1 Component (A) was produced in exactly the same manner as in Example-1 except that TiCl4 was used instead of the titanium-silicon complex. Furthermore, polymerization of propylene was carried out in exactly the same manner. 58 grams of polymer was obtained, T-1
, l-48.6 weight percent, MFR sea bream 29.
6 g/10 minutes, polymer bulk specific gravity -0.31 g/cc.

Example 2 (Production of component (A)) Dehydrated and deoxygenated n was placed in a flask that was sufficiently purged with nitrogen.
- 200 ml of hebutane is introduced, then MgC
Introduced 0.4 mol of l2 and 0.8 mol of T1(O-nC4H9)4, and heated to 95°C.
The mixture was allowed to react for 2 hours. After the reaction was completed, the temperature was lowered to 40° C., and then 48 milliliters of methylhydropolysiloxane (20 centistokes) was introduced, and the reaction was allowed to proceed for 3 hours. The solid component produced was washed with n-hebutane.

Next, 50 milliliters of n-hebutane purified in the same manner as in Example 1 was introduced into a flask which had been sufficiently purged with nitrogen, and 0.24 mol of the solid component synthesized above was introduced in terms of Mg atoms. Next, add SiC to 25 ml of n-hebutane.
140.4 mol was mixed and introduced into a flask at 30°C for 30 minutes, and reacted at 70°C for 3 hours.

Next, 0.024 mol of phthaloyl chloride was mixed with 25 ml of n-hebutane, and the mixture was introduced into a flask at 90°C for 30 minutes, and reacted at 95°C for 1 hour. After the reaction was completed, it was washed with n-hebutane.

Then 08 mol of SiC140 was introduced at 30°C,
The reaction was carried out at 100°C for 6 hours. After the reaction was completed, it was washed with n-heptane.

Then an internal volume of 1.5 mm containing stirring and temperature control equipment
500 milliliters of sufficiently dehydrated and deoxygenated n-hebutane, 4.2 grams of triethylaluminum, and 20 grams of the solid component obtained above were introduced into a small stainless steel stirred tank. Temperature inside stirring tank 20℃
Then, propylene was introduced at a constant rate and polymerization of propylene was carried out for 30 minutes. After the polymerization was completed, it was thoroughly washed with n-hebutane. When a portion was taken out and the amount of polymerized propylene was examined, it was found that the amount of prepolymerized propylene was 0.96 grams per gram of solid component.

50 milliliters of sufficiently purified n-hebutane was introduced into a flask that had been sufficiently purged with nitrogen, and then 5 grams of the prepolymerized component obtained above was introduced, and then synthesis was carried out in the same manner as in Example 1 (a- 0.01 mol of 1) was introduced and reacted at 30° C. for 2 hours to obtain component (A).

(Polymerization of propylene) Polymerization was carried out under exactly the same conditions as in Example 1, except that the amount of triethylaluminum used as component (B) was changed to 125 milligrams. 13
6 grams of polymer was obtained, having a T-1, l-98,3 weight percent, a VFR-3, 1 g/10 min, and a polymer bulk density of -0,46 g/ec.

Example 3 (Manufacture of component (A)) (Synthesis of component (i)) A thoroughly dried 0.4 liter ball mill that had been purged with nitrogen was filled with 40 stainless steel balls of 12 mφ. 20 g of MgCl2 and 12 ml of ethyl benzoate were introduced into the mixture, and the mixture was ground in a rotary ball mill for 48 hours. After the pulverization was completed, the mixed pulverized composition was taken out from the mill in a dry box. Subsequently, 865 grams of the pulverized composition was introduced into a flask that had been sufficiently purged with nitrogen, and further 25 ml of n-hebutane and 1425 ml of TiC were introduced and reacted at 100 DEG C. for 3 hours.

After the reaction is completed, the component (i
).

(Synthesis of component (i1) (titanium-silicon complex)) 100 ml of dehydrated and deoxygenated n-hebutane was introduced into a flask that was sufficiently purged with nitrogen, and 0.1 mol of CH3 b-1) was introduced. did. Then T iC14
0.1 mol was introduced over 30 minutes and reacted at 20°C for 2 hours. After the reaction was completed, it was washed with n-hebutane. When the composition was analyzed, it was found to be TlC14.0.84 (b-1).

(Production of component (A)) 100 milliliters of purified n-hebutane was introduced into a flask that had been sufficiently purged with nitrogen, and the above component (i) and component (
0.02 mol of II) was introduced and reacted at 30°C for 3 hours. After the reaction was completed, it was thoroughly washed with n-hebutane to obtain component (A).

(Polymerization of propylene) Polymerization was carried out under exactly the same conditions as in Example 1, except that the polymerization temperature was changed to 70°C. 77.4 grams of polymer was obtained, with T-1, 92.4 weight percent, MFR = 9.1 g/10 min, and polymer bulk density -0.43 g/cc.

Examples 4 to 6 In the production of component (A) in Example 1, the synthesis of the titanium-silicon complex was carried out in exactly the same manner except that it was carried out under the conditions shown in Table 1, and the polymerization of propylene was carried out in the same manner. I went to The results are shown in Table-1.

Claims (1)

[Scope of Claims] An olefin polymerization catalyst comprising the following components (A) and (B). Component (A) Component (i): A solid component containing magnesium, titanium and halogen as essential components, and component (ii):
General formula Ti(OR^1)_4_-_nX_n・R^2R^3_
3_-_mSi(OR^4)_m (where, X is a halogen, R^1 is a hydrocarbon residue, R^2 is a branched hydrocarbon residue, and R^3 is the same as R^2) or a different hydrocarbon residue, R^4 is a hydrocarbon residue, n is 1≦n≦
A complex of a titanium compound and a silicon compound represented by the number 4 and m represents the number 1≦m≦3 (however, this general formula indicates that the ratio of both compounds constituting the complex is 1:1). ), a solid catalyst component obtained by contacting Component (B) Organoaluminum compound.