JPH0721021B2 - Olefin polymerization catalyst - Google Patents

Description

TECHNICAL FIELD The present invention relates to an olefin polymerization catalyst.
The catalyst of the present invention is capable of polymerizing olefins which are excellent in the sustainability of the polymerization activity, and can carry out the polymerization operation by raising the polymerization temperature.

BACKGROUND ART In recent years, many proposals have been made for producing a highly stereoregular polymer of an α-olefin having 3 or more carbon atoms, using a solid component containing titanium, magnesium and halogen as essential components. According to the conventional proposal method, in actual polymerization, in addition to the above solid component and organoaluminum compound, it is necessary to use an electron donating compound at the time of polymerization in order to increase the stereoregularity of the product polymer. was there.

The use of the electron-donating compound as the third component complicates the catalyst system and makes it difficult to control the product performance. Further, due to the reaction between the organoaluminum compound and the electron-donating compound as the third component, there are problems such as low persistence of the polymerization rate, inability to raise the polymerization temperature, and difficulty in controlling the molecular weight of the polymer. can give. Therefore, it is desired to develop a catalyst system that can produce a highly stereoregular polymer with a high catalyst yield without using an electron-donating compound as the third component.

As a solution to this problem, Japanese Patent Laid-Open No. 58-138715 has been proposed. The present proposal proposes a titanium composite (1) containing tetravalent titanium, magnesium, halogen and an electron donor as essential components, and an organosilicon compound (2) having a Si—O—C bond, as an organoaluminum compound. Or a treatment of the titanium composite with an organoaluminum compound, followed by polymerization with a solid component obtained by reacting the organosilicon compound with a catalyst system formed of organoaluminum.

This proposal has yielded polymers with somewhat high stereoregularity, but is insufficient to cover all areas in which product polymers are currently used. In addition, since organoaluminum is used in the production of the solid component, deterioration of the catalyst over time, restrictions on the amount ratio of the solid component and the organoaluminum compound used at the time of polyolefin polymerization, stereoregularity of the polymer to be formed, molecular weight, etc. There are many points to be solved, such as changes over time.

SUMMARY OF THE INVENTION The present invention provides an olefin polymerization catalyst characterized by combining the following components (A) and (B).

Component (A): Catalyst component obtained by contacting the following component (a), component (b) and component (c), component (a): magnesium dihalide and general formula Ti
(OR ¹ ) _4- nXn (provided that R ¹ is a hydrocarbon residue having 1 to 10 carbon atoms, X is halogen, and n is a number of 0 ≦ n ≦ 4) is an essential component. A solid component obtained by bringing them into contact with each other, component (b): a silicon compound having a Si-O-C bond, component (c): a silicon compound having a Si-H bond, component (B): an organoaluminum compound .

The present invention also provides an olefin polymerization catalyst characterized by combining the following components (A) and (B).

Component (A): Catalyst component obtained by contacting the following component (a), component (b) and component (c), component (a): magnesium dihalide and general formula Ti
(OR ¹ ) _4- nXn (provided that R ¹ is a hydrocarbon residue having 1 to 10 carbon atoms, X is halogen, and n is a number of 0 ≦ n ≦ 4) is an essential component. A solid component obtained by contacting as a component, component (b): a silicon compound having a Si-O-C bond, component (c): a silicon compound having a Si-H bond, component (d): an aluminum halogen compound Component (B): Organoaluminum compound.

EFFECTS OF THE INVENTION According to the present invention, the problems of the above-mentioned prior art can be solved. Further, as compared with known catalysts such as a catalyst using an electric donating compound as the third component, it has excellent characteristics such as good sustainability of polymerization activity and high polymerization temperature. These characteristics are extremely important for industrial production, and a significantly advantageous industrial production is possible.

DETAILED DESCRIPTION OF THE INVENTION (Catalyst) The catalyst of the present invention is characterized by combining the component (A) and the component (B).

Component (A) Magnesium dihalide used in the production of the component (A) used in the present invention and the general formula Ti (OR ¹ ) _4- nXn (wherein R ¹ is a hydrocarbon residue having 1 to 10 carbon atoms, X is halogen,
Known components can be used as the component (a), which is a solid component obtained by contacting with a titanium compound represented by the formula (n is 0 ≦ n ≦ 4) as an essential component.

For example, JP-A-53-45688, JP-A-54-3894, and JP-A-54-310.
No. 92, No. 54-39483, No. 54-94591, No. 54-118484
No. 54-131589, No. 55-75411, No. 55-90510,
55-90511, 55-127405, 55-147507, 5
5-155003, 56-18609, 56-70005, 56-7
2001, 56-86905, 56-90807, 56-155206
No. 57, No. 57-3803, No. 57-34103, No. 57-92007, No.
57-121003, 58-5309, 58-5310, 58-53
No. 11, No. 58-8706, No. 58-27732, No. 58-32604,
58-32605, 58-67703, 58-117206, 58
-127708, 58-183708, 58-183709, 59-
Those described in the prior art such as 149905 and 59-149906 can be used.

As the above-mentioned component (a), it is possible to use other components such as silicon, aluminum and boron in addition to the above essential components, and these may remain in the component (a).

Magnesium dihalide is used as the magnesium source used to produce component (a).

As a titanium source, a general formula Ti (OR ¹ ) _4- nXn (wherein R ¹ is a hydrocarbon residue, preferably having about 1 to 10 carbon atoms, X represents halogen, and n represents A titanium compound represented by the formula 0 ≦ n ≦ 4 is shown. As a specific example, TiCl ₄ , TiBr ₄ ,
Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₃ Cl, T
_{i (O-iC 3 H 7} ) Cl 3, Ti (O-nC 4 H 9) Cl 3, Ti (O-nC 4
_{H 9) 2 Cl 2, Ti} (OC 2 H 5) Br 3, Ti (OC 2 H 5) (OC 4 H 9) 2 C
_{l, Ti (O-nC 4} H 9) 3 Cl, Ti (O-C 6 H 5) Cl 3, Ti (O-
iC ₄ H ₉ ) ₂ Cl ₂ , Ti (OC ₅ H ₁₁ ) Cl ₃ , Ti (OC ₆ H ₁₃ ) Cl ₃ , Ti
(OC ₂ H ₅ ) ₄ , Ti (O-nC ₃ H ₇ ) ₄ , Ti (O-nC
_{4 H 9) 4, Ti (} O-iC 4 H 9) 4, Ti (O-nC 6 H 13) 4, Ti
_{(O-nC 8 H 17)} 4, Ti _{[OCH 2 CH (C 2 H 5} ) C 4 H 9 ] is _4, and the like.

Further, it may be a molecular compound obtained by reacting Ti∅X ^' ₄ (where X'represents halogen) with an electron donor.

Specific examples include TiCl ₄ CH ₃ COC ₂ H ₅ and TiCl ₄ CH ₃ CO ₂ C ₂ H
₅ , TiCl ₄ / C ₆ H ₅ NO ₂ , TiCl ₄ / CH ₃ COCl, TiCl ₄ / C ₆ H ₅ COC
l, TiCl ₄・ C ₆ H ₅ CO ₂ C ₂ H ₅ , TiCl ₄・ ClCOC ₂ H ₅ , TiCl ₄・ C ₄ H
₄ O, etc.

As the halogen source of the halogen contained in the component (a), the halogen contained in the compounds such as the above-mentioned halogen source and titanium source is usually used, but other known halogenating agents can also be used.

An electron donor can be used when producing this component (a). As the electron donor, alcohols,
Oxygen-containing electron donors such as phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides and acid anhydrides, and ammonia-containing amines such as amines, nitriles and isocyanates. A nitrogen electron donor etc. can be illustrated.

More specifically, it has 1 to 18 carbon atoms such as methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol and isopropylbenzyl alcohol.
Alcohols of 6 to 25 carbon atoms which may have an alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, cumylphenol, nonylphenol and naphthol; acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone , C3 to C15 ketones such as benzophenone; C2 to C15 such as acetaldehyde, propionaldehyde, octyl aldehyde, benzaldehyde, tolualdehyde and naphthaldehyde
Aldehydes of methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, methacrylic acid Methyl, 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 benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, diethyl phthalate, dibutyl phthalate,
Organic acid esters having 2 to 20 carbon atoms such as diheptyl phthalate, γ-butyrolactone, α-parerolactone, coumarin, phthalide and ethylene carbonate; ethyl silicate, butyl silicate, silicates such as phenyltriethoxysilane Inorganic acid esters; acetyl chloride,
Benzoyl chloride, toluic acid chloride, anisic acid chloride, phthaloyl chloride, iso-phthaloyl chloride and other acid halides having 2 to 15 carbon atoms; methyl ether, ethyl ether, isopropyl ether, butyl ether, aluminum ether, tetrahydrofuran, anisole, diphenyl ether, etc. C2 to C20 ethers; acetic acid amides, benzoic acid amides, toluic acid amides and other acetic acid amides; methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethyl Amines such as ethylenediamine; Nitriles such as acetonitrile, benzonitrile, tolunitrile;
And so on. Two or more kinds of these electron donors can be used.

The amount of each of the above-mentioned components used is within the known range and may be arbitrary as long as the effect of the present invention is recognized, but it is generally within the following range.

The titanium compound may be used in a molar ratio of 1 × 10 ^{-4 to} 1000, preferably 0.01 to 10, with respect to the amount of the magnesium compound used. When using a compound having a halogen source, a titanium compound and / or
Or, regardless of whether the magnesium compound does not contain halogen, the molar ratio may be within the range of 1 × 10 ^{-2 to} 1000 with respect to the amount of magnesium used, preferably 0.1.
Within the range of ~ 100.

The amount of the electron-donating compound used may be in the range of 1 × 10 ⁻³ to 10 and preferably in the range of 0.01 to 5 with respect to the amount of the magnesium compound used.

The component (a) is produced, for example, by the following production method using the above-mentioned titanium source, magnesium source and halogen source, and optionally other components such as an electron donor.

I. A method of contacting a magnesium halide, an electron donor and a titanium-containing compound.

B. A method in which alumina or magnesia is treated with a phosphorus halide compound, and magnesium halide, an electron donor and a titanium halogen-containing compound are brought into contact therewith.

C. A method of bringing a titanium halogen compound and / or a silicon halogen compound into contact with a solid component obtained by contacting a magnesium halide with a titanium tetraalkoxide and a specific polymer silicon compound.

As the polymer silicon compound, those represented by the following formula are suitable.

(Here, R is a hydrocarbon residue having about 1 to 10 carbon atoms, and n is the degree of polymerization such that the viscosity of the polymer silicon compound is about 1 to 100 centistokes). In particular,
Methyl hydrogen polysiloxane, ethyl hydrogen polysiloxane, phenyl hydrogen polysiloxane, cyclohexyl hydrogen polysiloxane, 1,3,5,7-tetramethyl cyclotetrasiloxane,
Examples include 1,3,5,7,9-pentamethylcyclopentasiloxane.

D. A method in which a magnesium compound is dissolved with titanium tetraalkoxide and an electron donor, and a titanium compound is brought into contact with a solid component precipitated with a halogenating agent or a titanium halogen compound.

E. A method of reacting an organomagnesium compound such as a Grignard reagent with a halogenating agent, a reducing agent, etc., and then contacting this with an electron donor and a titanium compound.

F. A method of bringing a halogenating agent and / or a titanium compound into contact with an alkoxy magnesium compound in the presence or absence of an electron donor.

Component (b) used to produce component (A) is Si
It is a silicon compound having a —O—C bond.

Specific examples include (CH ₃ ) Si (OCH ₃ ) ₃ and (CH ₃ ) Si (OC
_{2 H 5) 3, (C} 2 H 5) 2 Si (OCH 3) 2, (n-C 6 H 11) Si (O
_{CH 3) 3, (C 2} H 5) Si (OC 2 H 5) 3, (n-C 10 H 21) Si
_{(OC 2 H 5) 3,} (CH 2 = CH) Si (OCH 3) 3, Cl (CH 2) 3 Si
(OCH ₃ ) ₃ , Si (OCH ₃ ) ₄ , (C ₂ H ₅ ) ₂ Si (OC ₂ H ₅ ) ₂ ,
_{(C 17 H 35) Si (} OCH 3) 3, Si (OC 2 H 5) 4, (C 6 H 5) Si
_{(OCH 3) 3, (C} 6 H 5) 2 Si (OCH 3) 2, (C 6 H 5) (CH 3)
_{Si (OCH 3) 2, (} C 6 H 5) Si (OC 2 H 5) 3, (C 6 H 5) 2 Si
(OC ₂ H ₅ ) ₂ , NC (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ , (C ₆ H ₅ ) (CH
_{3) Si (OC 2 H 5} ) 2, (n-C 3 H 7) Si (OC 2 H 5) 3, (C
_{H 3) Si (OC 3 H} 7) 3, (C 6 H 5) (CH 2) Si (OC 2 H 5) 3, _{(CH 3) 3 C-Si} (OCH 3) 3, (CH 3) 3 C-Si (OC 2 H 5) 3
_{(C 2 H 5) 3 C} -Si (OC 2 H 5) 3, Examples thereof include silicon compounds having a Si-O-C bond but not having a Si-H bond.

The component (C) used in the present invention is a silicon compound having a Si-H bond. Specific examples include HSiCl ₃ and H ₂ SiC.
l ₂ , H ₃ SiCl, H (CH ₃ ) SiCl ₂ , H (C ₂ H ₅ ) SiCl ₂ , (C ₂ H
₅ ) ₃ SiH, H (CH ₃ ) ₂ SiCl, (C ₂ H ₅ ) ₂ SiH ₂ , H (CH ₃ ) S
i (OCH ₃ ) ₂ , HSi (OCH ₃ ) ₃ , H ₂ Si (OC ₂ H ₅ ) ₂ , H (C
H ₃ ) ₂ SiN (CH ₃ ) ₂ , (ClCH ₂ CH ₂ O) ₂ Si (CH ₃ ) H, (CH
_{3) (C 2 H 5)} 2 SiH, (CH 3) HSi (OC 2 H 5) 2, (CH 3) HSi
(NCH ₃ ) ₂ , (C ₆ H ₅ ) SiHCl ₂ , (C ₆ H ₅ ) SiH ₃ , HSi (OCH
₂ CH ₂ Cl) ₃ , CH ₃ (CH ₂ ) ₃ SiH (CH ₃ ) ₂ , HSi (OC ₂ H ₅ )
₃ , (CH ₃ ) ₂ HSiN (C ₂ H ₅ ) ₂ , HSi (N (CH ₃ ) ₂ ) ₃ ,
(C ₆ H ₅ ) (CH ₃ ) SiH ₂ , (C ₆ H ₅ ) (CH ₃ ) ₂ SiH, CH ₃ (C
H ₂ ) ₇ SiH ₃ , (CH ₃ CH ₂ CH ₂ ) ₃ SiH, (C ₆ H ₅ ) ₂ SiH ₂ , (C ₆ H
₅ ) ₂ SiH (CH ₃ ), (n-C ₅ H ₁₁ O) ₃ SiH, (C ₆ H ₅ ) ₃ SiH,
H (CH ₃ ) ₂ SiOSi (CH ₃ ) ₂ H, H (CH ₃ ) ₂ SiNHSi (CH ₃ ) _{2
H, (CH 3) 3 SiOSi} (CH 3) 2 H, H (CH 3) 2 Si (C 6 H 4) Si
(CH ₃ ) ₂ H, (CH ₃ SiO) ₃ SiH, (CH ₃ SiO) ₃ SiH, Examples thereof include methylhydrogenpolysiloxane and ethylhydrogensiloxane.

The component (A) of the catalyst of the present invention is obtained by contacting the above-mentioned component (a), component (b) and component (c), and the component (a) obtained by adding the following component (d) to these components. ) ~
It can also be produced by the contact of (d).

The component (d) used in the present invention is an aluminum halogen compound. Specifically, inorganic aluminum halides such as AlCl ₃ and AlBr ₃ , Al (OC ₂ H ₅ ) Cl ₂ , Al (OC
_{H 3) 2 Cl, Al (} OC 2 H 5) 2 ClAl (OiCH 3) Cl 2, Al (O-nC 4
H ₉ ) Cl ₂ , Al (OC ₆ H ₅ ) Cl ₂ , Al (OC ₈ H ₁₉ ) Cl ₂ , Al (O-
Examples include nC ₄ H ₉ ) ₂ Cl, Al (OC ₂ H ₅ ) Br ₂ , and other aluminum halides having a hydrocarbon residue having about 1 to 10 carbon atoms.

The contact conditions of the component (a), the component (b) and the component (c), or each of these components and the component (d) may be arbitrary as long as the effect of the present invention is recognized, but generally, The following conditions are preferred. The contact temperature is about -50 to 200 ° C, preferably 0 to 150 ° C. Examples of the contact method include a mechanical method using a rotary ball mill, a vibration mill, a jet mill, a medium agitating pulverizer, etc., and a method of agitating in the presence of an inert diluent. Examples of the inert diluent used at this time include aliphatic or aromatic hydrocarbons and halohydrocarbons, and polysiloxanes.

The amount ratio of the component (a), the component (b) and the component (c) may be arbitrary as long as the effect of the present invention is recognized, but generally, the following range is preferable. The amount ratio of the component (a) and the component (b) is the atomic ratio of silicon of the component (b) to the titanium component constituting the component (a) (silicon / titanium).
It may be in the range of 0.01 to 1000, preferably in the range of 0.1 to 100.

The amount ratio of the component (a) to the component (c) may be in the range of 0.01 to 1000 in terms of atomic ratio of silicon of the component (c) to the titanium component constituting the component (a) (silicon / titanium), preferably It is within the range of 0.1 to 100.

When the component (d) is used in addition to the above components (a) to (c) in the production of the component (A), the quantitative ratio of the components (a) to (d) is as follows. The amount ratio of c) is the same as the case of using these three components described above, and the component (d) additionally used is the atomic ratio of aluminum of the component (d) to the titanium component constituting the component (a) (aluminum /
Titanium) may be in the range of 0.01 to 1000, preferably 0.1
Within the range of ~ 100.

Component (B) Component (B) is an organoaluminum compound. As a specific example, ▲ R ² _3-n ▼ AlXn or ▲ R ³ _3-m ▼ Al
(OR ⁴ ) m (wherein R ² and R ³ may be the same or different and are a hydrocarbon residue or hydrogen having about 1 to 20 carbon atoms, R ⁴ is a hydrocarbon residue, X is halogen, n and m). Is 0n <
3, 0 <m <3. ). Specifically, (a) trimethyl aluminum, triethyl aluminum, triisobutyl aluminum,
Trialkylaluminums such as trihexylaluminum, trioctylaluminum, tridecylaluminum, etc., alkylaluminum halides such as (b) diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride, etc.,
(C) Diethyl aluminum hydride, diisobutyl aluminum hydride, (D) Aluminum alkoxide such as diethyl aluminum ethoxide and diethyl aluminum phenoxide, and the like.

In addition to these organoaluminum compounds of (a) to (c), other organometallic compounds such as ▲ R ⁴ _3-a ▼ Al (OR ⁵ ) a
(1a3, R ⁴ and R ⁵ are hydrocarbon residue of about the same or different carbon atoms which may be 1-20.) The alkyl aluminum alkoxide may be used in combination represented by. For example, combined use of triethyl aluminum and diethyl aluminum ethoxide, combined use of diethyl aluminum monochloride and diethyl aluminum ethoxide, combined use of ethyl aluminum dichloride and ethyl aluminum diethoxide, triethyl aluminum and diethyl aluminum ethoxide and diethyl aluminum chloride Can be used in combination.

(Polymerization) The catalyst system of the present invention is, of course, applied to ordinary slurry polymerization, but is also applied to liquid phase solventless polymerization, solution polymerization, or gas phase polymerization method using substantially no solvent. It
Further, it is also applicable to a system in which continuous polymerization, batch polymerization or preliminary polymerization is carried out.

As a polymerization solvent in the case of slurry polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, or toluene is used alone or as a mixture.

The polymerization temperature is from room temperature to about 200 ° C, preferably 50 to 150 ° C.
In that case, hydrogen can be supplementarily used as a molecular weight regulator at that time. Further, the component (A) and the component (B)
The amount used of is not particularly limited, but is generally preferably within the following range. The weight ratio of the component (B) to the component (A) is 0.1 to 1000, preferably 10 to 500.

Olefins used to polymerize the catalyst system (olefin) present invention have the general formula R-CH = CH ₂ (wherein R is a hydrocarbon residue of the hydrogen atoms or 1 to 10 carbon atoms, branched It may have a group). Specifically, there are olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1. Ethylene and propylene are preferred.

In the case of these polymerizations, it is possible to carry out up to 50% by weight, preferably 20% by weight, of said olefins with ethylene, and with propylene up to 30% by weight of said olefins, especially ethylene. Can be copolymerized with. Copolymerization with other copolymerizable monomers (for example, vinyl acetate, diolefin) can also be performed.

Experimental Example Example A-1 [Production of Component (A)] A fully dried, nitrogen-substituted 0.4 liter ball mill was filled with 40 12 mmφ stainless steel balls, and MgCl 2 was used.
20 g of ₂ and 15.5 ml of diheptyl phthalate were introduced, and the mixture was pulverized with a rotary ball mill for 48 hours. After the pulverization was completed, the mixed pulverized composition was taken out of the mill in the dry box. Subsequently, 8.8 g of the ground composition was introduced into a flask which had been sufficiently replaced with nitrogen, 25 ml of n-heptane and 25 ml of TiCl ₄ were further introduced, and the mixture was reacted at 100 ° C. for 3 hours. After completion of the reaction, it was thoroughly washed with n-heptane. When a part of the obtained solid component was taken out and the composition was analyzed, the Ti content was 3.01 weight percent (component (a)).

50 ml of sufficiently purified n-heptane was introduced into a flask sufficiently replaced with nitrogen, then 5 g of the component (a) obtained above was introduced, and then as component (c). 2.3 ml of was introduced and contacted at 70 ° C. for 2 hours.
After completion of contact, washing with n-heptane, then component (b)
As a carrier, 4.5 ml of phenyltriethoxysilane was introduced and contacted at 30 ° C. for 2 hours. After the contact was completed, it was washed with n-heptane to obtain the component (A).

[Polymerization of propylene]

In a stainless steel autoclave with an internal volume of 1.5 liter equipped with a stirring and temperature control device, 500 ml of sufficiently dehydrated and deoxygenated n-heptane, 125 mg of triethylaluminum (component (B)), and the catalyst component synthesized above 15 mg of (Component (A)) was introduced. Then, 60 ml of H ₂ was introduced, the temperature was raised and the pressure was increased, polymerization pressure = 5 kg / cm ² G, polymerization temperature = 75 ° C., polymerization time =
Polymerization was carried out for 2 hours.

After the polymerization was completed, the obtained polymer slurry was separated by filtration and the polymer was dried. As a result, 83.6 g of polymer was obtained. 0.92 grams of polymer were obtained from one perfusate. From the boiling heptane extraction test, all products II
(Hereinafter abbreviated as T-II) was 95.3 weight percent. The MFR of this polymer was 8.7 g / 10 minutes, and the bulk density of the polymer was 0.38 g / cc.

Example A-2 [Production of Component (A)] n was dehydrated and deoxygenated in a flask that had been sufficiently replaced with nitrogen.
- introducing from heptane 100 ml then MgCl ₂ 0.
1 mol, 0.2 mol of Ti (O-nC ₄ H ₉ ) ₄ was introduced, and 2 at 95 ℃
Reacted for hours. After completion of the reaction, the temperature was lowered to 40 ° C., and then 12 ml of methylhydropolysiloxane (having 20 centistokes) was introduced and reacted for 3 hours. The solid component produced was washed with n-heptane.

Then, the flask was thoroughly purged with nitrogen and purified in the same manner as above. 50 ml of n-heptane was introduced, and 0.03 mol of the solid component synthesized above in terms of Mg atom was introduced. Then, 25 ml of n-heptane was mixed with 0.05 mol of SiCl ₄ and introduced into the flask at 30 ° C. for 30 minutes and reacted at 70 ° C. for 1 hour. After completion of the reaction, it was washed with n-heptane. Next, 25 ml of n-heptane and 0.
Mix 003 moles and introduce into flask at 70 ° C for 30 minutes.
The reaction was carried out at 5 ° C for 1 hour. After completion of the reaction, it was washed with n-heptane. Then, 5 ml of TiCl ₄ was introduced and 100
The reaction was carried out at 0 ° C for 6 hours. After completion of the reaction, it was thoroughly washed with n-heptane. The titanium content was 2.45 weight percent. It was used as the component (a) for producing the solid component (A).

A flask purified in the same manner as in Example A-1 was added with n-heptane.
50 ml was introduced, then 5 g of the component (a) obtained above was introduced, and then 1.8 ml of methylhydrogenpolysiloxane was introduced as the component (c), and the mixture was mixed at 60 ° C. for 2 hours.
Contacted for a time. After completion of contact, wash with n-heptane,
Next, diphenyldimethoxysilane was added as the component (b).
4.7 ml was introduced and the mixture was contacted at 25 ° C for 2 hours. After the contact was completed, it was washed with n-heptane to obtain a component (A).

[Polymerization of propylene]

Example A-1 except that the amount of triethylaluminum used was 250 mg in the polymerization conditions of Example A-1.
Polymerization of propylene was carried out in the same manner as in -1. As a result, 12
3 grams of polymer are obtained, MFR of this polymer = 6.5 g
/ 10 minutes, T-II = 96.0 weight percent, polymer bulk specific gravity = 0.46 g / cc.

Example A-3 [Production of Component (A)] In the synthesis of the component (a) of Example A-2, the reaction time of SiCl ₄ was 90 ° C. for 4 hours, and 0.003 phthalic acid chloride was used instead of diheptyl phthalate. Use 1 mol at 95 ° C
The component (a) was synthesized in the same manner as in Example A-2 except that the reaction was carried out for a time.

The component (a) obtained above was introduced into a flask in the same manner as in Example A-1, and then 2.0 ml of methylhydrogen polysiloxane was introduced as the component (c), and the mixture was heated at 50 ° C. for 2 hours.
Contacted for a time. After the contact, it was washed with n-heptane, then as component (b) 3.2 ml was introduced and contacted at 30 ° C. for 4 hours.
After the contact was completed, it was washed with n-heptane to obtain the component (A).

[Polymerization of propylene]

Polymerization of propylene was carried out in the same manner as in Example A-1 except that the component (A) obtained above was used. As a result, 148 g of a polymer was obtained, and the MFR of this polymer was 5.8 g / 10
Min, T-II = 97.5 weight percent, polymer bulk specific gravity =
It was 0.46 g / cc.

Example A-4 [Production of Component (A)] n was dehydrated and deoxygenated in a flask that had been sufficiently replaced with nitrogen.
- introducing from heptane 100 ml then MgCl ₂ 0.
1 mol, 0.2 mol of Ti (O-nC ₄ H ₉ ) ₄ was introduced, and 2 at 95 ℃
Reacted for hours. After the reaction was completed, the temperature was lowered to 35 ° C and 1,3,
15 ml of 5,7-tetramethylcyclotetrasiloxane was introduced and the reaction was carried out for 5 hours. The generated solid component is n
-Washed with heptane. Then, 50 ml of n-heptane was introduced into a flask that had been sufficiently replaced with nitrogen, and 0.03 mol of the solid component synthesized above was introduced in terms of Mg atom. Incidentally
0.06 mol of SiCl ₄ was introduced at 20 ° C. for 30 minutes and reacted at 50 ° C. for 3 hours. After completion of the reaction, it was washed with n-heptane to obtain a solid component (a) for producing the component (A). The titanium content in this solid component was 4.52 weight percent.

The component (a) obtained above was introduced into a flask in the same manner as in Example A-1, and then 4.6 ml (component (b)) and 2.7 ml methylhydrogenpolysiloxane (component (c))
Was introduced and the mixture was contacted at 20 ° C. for 2 hours. After contact, n
-Washed with heptane to give component (A).

[Polymerization of propylene]

Polymerization of propylene was carried out in the same manner as in Example A-1 except that the component (A) obtained above was used and the amount of triethylaluminum used was 50 mg. As a result, 92 g of a polymer was obtained, and the MFR of this polymer was 10.8 g / 10 minutes,
T-II = 93.8 weight percent, polymer bulk specific gravity = 0.46 g
It was / cc.

Examples A-5 to 5 In the production of the component (A) of Example A-2, the component (c)
A catalyst was produced in the same manner as in Example A-2 except that the compounds shown in Table A-1 were used, and propylene was also polymerized in the same manner as in Example A-2. The results are shown in Table A-1.

Examples A-8 to 10 In the production of the component (A) of Example A-2, the component (b)
A catalyst was produced in the same manner as in Example A-3 except that the compounds shown in Table A-2 were used, and propylene was also polymerized in the same manner as in Example A-3. The results are shown in Table A-2.

Examples A-11 to 13 In the polymerization of propylene of Example A-3, the component (B)
Polymerization of propylene was carried out in the same manner as in Example A-3, except that the compound shown in Table A-3 was used as the organoaluminum compound. The results are shown in Table A-3.

Example B-1 [Production of component (A)] 50 ml of sufficiently purified n-heptane was introduced into a flask sufficiently replaced with nitrogen, and then obtained in the production of the catalyst component (A) of Example A-1. The same component (a) as in 5
Gram introduced, then as component (c) 1.9 ml of was introduced and contacted at 50 ° C. for 2 hours.
After completion of contact, washing with n-heptane, then component (b)
As the component (d), 4.6 ml of diphenyldimethoxysilane as the component and 0.2 g of AlCl ₃ as the component (d) were introduced and contacted at 35 ° C. for 3 hours. After the contact was completed, it was washed with n-heptane to obtain a component (A).

[Polymerization of propylene]

Polymerization of propylene was carried out in the same manner as in Example A-1 except that 15 mg of the component (A) obtained above was used.

As a result, 85.8 g of a polymer was obtained. One liquor gave 0.77 grams of polymer. From the boiling heptane extraction test, all products II (hereinafter abbreviated as T-II) were 9
It was 6.1 weight percent. Also, the MFR of this polymer =
The polymer bulk specific gravity was 8.1 g / 10 minutes = 0.37 g / cc.

Example B-2 [Production of component (A)] 50 ml of sufficiently purified n-heptane was introduced into a flask sufficiently replaced with nitrogen to obtain the catalyst component (A) of Example A-2. 5 g of the same component (a) as described above was introduced, 0.2 g of AlCl ₃ (component (d)) and 2.0 ml of methylhydrogenpolysiloxane were introduced, and the mixture was contacted at 70 ° C. for 2 hours. After the contact was completed, it was washed with n-heptane. Then phenyltriethoxysilane 4.8
After introducing milliliter, the mixture was contacted at 30 ° C. for 2 hours. After the contact was completed, it was washed with n-heptane to obtain the component (A).

[Polymerization of propylene]

Polymerization of propylene was carried out in the same manner as in Example B-1 except that the component (A) obtained above was used and the amount of triethylaluminum (component (B)) used was 250 mg.

As a result, 131 grams of polymer was obtained, MFR of this polymer = 5.8 g / 10 min, T-II = 97.0 weight percent,
The bulk density of the polymer was 0.44 g / cc.

Example B-3 [Production of component (A)] In the synthesis of the component (a) of Example B-2, the reaction time of SiCl ₄ was 90 ° C. for 4 hours, and 0.003 phthalic acid chloride was used instead of diheptyl phthalate. Use 1 mol at 95 ° C
The component (a) was synthesized in the same manner as in Example B-2 except that the reaction was performed for a time.

Component (a) obtained above is introduced into a flask as in Example B-1, then 2.0 ml of methylhydrogenpolysiloxane as component (c) and 0.2 g of AlCl ₃ as component (d) are introduced. And contacted at 70 ° C. for 2 hours. After the contacting is finished, it is washed with n-heptane, and then, as the component (b), 3.2 ml was introduced and contacted at 30 ° C. for 3 hours.
After the contact was completed, it was washed with n-heptane to obtain the component (A).

[Polymerization of propylene]

Polymerization of propylene was carried out in the same manner as in Example B-1 except that the component (A) obtained above was used.

The result was 155 grams of polymer, MFR = 5.5 g / 10 min, T-II = 97.8 weight percent of this polymer,
The bulk density of the polymer was 0.46 g / cc.

Example B-4 [Production of component (A)] 5 g of the same component (a) as obtained in the production of the component (A) of Example A-4 was introduced into a flask sufficiently replaced with nitrogen, To this, 0.35 g of AlBr ₃ was added as the component (d) and reacted at 50 ° C. for 1 hour. Then Introduce 5.7 ml (component (b)) and 2.2 ml of methylhydrogenpolysiloxane to give 20
Contact was carried out at 0 ° C. for 2 hours. After the contact was completed, it was washed with n-heptane to obtain the component (A).

[Polymerization of propylene]

Polymerization of propylene was carried out in the same manner as in Example B-1 except that the amount of triethylaluminum used was 50 mg using the component (A) obtained above. As a result, 95 g of a polymer was obtained, and the MFR of this polymer was 9.6 g / 10 min.
-II = 94.5 weight percent, polymer bulk specific gravity = 0.46 g / c
It was c.

Examples B-5 to 5 In the production of the component (A) of Example B-2, the component (c)
The catalyst components were produced in the same manner as in Example B-2 except that the compounds shown in Table B-1 were used, and propylene was also polymerized in the same manner as in Example B-2. The results are shown in Table B-1.
Shown in.

Examples B-8 to 10 In the production of the component (A) of Example B-3, the component (b)
Was produced in the same manner as in Example B-3 except that the compounds shown in Table B-2 were used, and propylene was also polymerized in the same manner as in Example B-3. The results are shown in Table B-2.

Examples B-11 to 13 In the polymerization of propylene of Example B-3, the component (B) was used.
Polymerization of propylene was carried out in the same manner as in Example A-3, except that the compounds shown in Table B-3 were used as the organoaluminum compound of. The results are shown in Table B-3.

Examples B-14 to 16 In the production of the component (A) of Example B-3, the component (d)
Except that the amount of AlCl ₃ used in
Production was carried out in the same manner as in Example B-3, and propylene was polymerized in the same manner as in Example B-3. The results are shown in Table B-4.

[Brief description of drawings]

FIG. 1 is intended to help the understanding of the technical content of the present invention regarding the Ziegler catalyst.

Claims (1)

[Claims] 1. An olefin polymerization catalyst comprising the following components (A) and (B) in combination. Component (A): Catalyst component obtained by contacting the following component (a), component (b) and component (c), component (a): magnesium dihalide and general formula Ti
(OR ¹ ) _4- nXn (provided that R ¹ is a hydrocarbon residue having 1 to 10 carbon atoms, X is halogen, and n is a number of 0 ≦ n ≦ 4) is an essential component. A solid component obtained by bringing them into contact with each other, component (b): a silicon compound having a Si-O-C bond, component (c): a silicon compound having a Si-H bond, component (B): an organoaluminum compound .