JPH0819176B2 - Olefin polymerization catalyst - Google Patents

Description

Description: BACKGROUND OF THE INVENTION Technical Field The present invention relates to a catalyst for olefin polymerization. More specifically, the present invention provides the use of olefins, particularly α-olefins having 3 or more carbon atoms, by using a specific catalyst,
When applied to the above-mentioned polymerization, the highly stereoregular polymer can be advantageously produced in industrial production under stable polymerization conditions.

Conventionally proposed catalysts for olefin polymerization consisting of organoaluminum and solid catalyst components containing titanium, magnesium and halogen as essential components have extremely high activity, but when the stereoregularity of the product polymer is a problem, It was necessary to use an electron donating compound during the polymerization.

However, such a catalyst that uses an electron-donating compound as the third component (external donor) reduces the polymerization rate due to the reaction between the organoaluminum compound and the electron-donating compound, and the polymerization rate is increased to increase the polymerization rate. Since increasing the temperature accelerates the above reaction, it is limited to increase the polymerization temperature to increase the polymerization amount (improve the production efficiency) .Therefore, control the molecular weight of the product polymer and the product polymer performance. Is difficult to control.

Therefore, it is desired to develop a catalyst system which can solve the above problems and can produce a highly stereoregular polymer with a high catalyst yield without using an electron donating compound as a third component (external donor).

Prior art JP-A-58-138715 discloses a titanium complex (1) containing tetravalent titanium, magnesium, halogen and an electron donor as essential components, which does not use an external donor, and Si.
Obtained by reacting with an organosilicon compound (2) having a —O—C bond in the presence of an organoaluminum compound, or by treating the titanium complex with an organoaluminum compound and then reacting with the organosilicon compound. Disclosed is a method of polymerizing with the solid component obtained and a catalyst system formed from organoaluminum.

However, although the above problems are being solved by this proposal, there is a limit in the performance of the product polymer obtained, and further deterioration of the catalyst over time, the amount ratio of the titanium component and the organoaluminum compound used during the polymerization. There are still many points to be improved, such as restrictions on.

[Outline of Invention]

SUMMARY OF THE INVENTION The present invention aims to provide a solution to the above points. That is, the catalyst for olefin polymerization according to the present invention comprises the following component (A) and component (B).

Component (A) Component (i): Solid component containing tetravalent titanium, magnesium and halogen as essential components, Component (ii): General formula R ¹ _m X _n Si (OR ² ) _4-mn (where R ¹ and R ² are hydrocarbon residues, X is halogen, m and n are 0 ≦ m ≦ 3 and 0, respectively.
≦ n ≦ 3 and 0 ≦ m + n ≦ 3. A solid compound component obtained by contacting a silicon compound represented by the formula (4), component (iii): organozinc compound.

Component (B) Organoaluminum compound.

Effect of the Invention The catalyst for olefin polymerization of the present invention does not use an electron-donating compound (external donor) at the time of polymerization, so that the polymerization rate does not decrease, and therefore no problem occurs even if the polymerization temperature is raised. It solves the problem.

These characteristics are extremely advantageous in industrial production and are important points as the characteristics of the catalyst. The reason why such a catalyst is obtained has not been fully analyzed yet, but it is considered that it is due to the interaction between the silicon compound of the component (ii) and the organozinc compound of the component (iii) used in the present invention.

[Specific Description of the Invention]

[Catalyst] The catalyst of the present invention comprises a specific component (A) and a specific component (B).
It consists of Here, “consisting of” does not mean that the ingredients are only those listed (ie, A and B) and does not exclude the coexistence of a purposeful third ingredient.

Component (A) The component (A) of the catalyst of the present invention is a solid catalyst component obtained by bringing the above-mentioned components (i) to (iii) into contact with each other. Here, "obtaining by contacting" does not mean that the target is only the ones listed (that is, (i) to (iii)), but the coexistence of the purposeful fourth component. Do not exclude

Component (i) The solid component containing tetravalent titanium, magnesium and halogen used as the component (i) as essential components is a known solid component. That is, JP-A-53-45688 and JP-A-54-3
894, 54-31092, 54-39483, 54-94591,
54-118484, 54-131589, 55-75411, 55-9
0510, 55-90511, 55-127405, 55-147507
No. 55, No. 55-155003, No. 56-18609, No. 56-70005, No. 5
6-72001, 56-86905, 56-90807, 56-155206
57-3803, 57-34103, 57-92007, 57-
121003, 58-5309, 58-5310, 58-5311,
58-8706, 58-27732, 58-32604, 58-3260
No. 5, No. 58-67703, No. 58-117206, No. 58-127708,
58-183708, 58-183709, 59-149905, 59-
The materials described in each publication of No. 149906 are used.

Examples of the magnesium compound used as the magnesium source in the present invention include magnesium halide, dialkoxy magnesium, alkoxy magnesium halide, magnesium oxyhalide, dialkyl magnesium, magnesium oxide, magnesium hydroxide, magnesium carboxylate and the like.

In addition, the tetravalent titanium compound serving as the titanium source has a general formula
Ti (OR ⁴ ) _4-n X _n (wherein R ⁴ is a hydrocarbon residue, preferably having about 1 to 10 carbon atoms, X is halogen, and n is 0 ≦ n ≦ 4 The compound represented by the number is shown. Specific examples include 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, Ti (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 Cl, Ti (O-nC ₄ H ₉ ) ₃ Cl, Ti (OC 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 is also possible to use a molecular compound obtained by reacting TiX ' ₄ (here, X'represents halogen) with an electron donor described later. Specific examples include TiCl ₄ CH ₃ COC ₂ H ₅ , 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 COCl, 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.

The halogen source is usually supplied from the above-mentioned magnesium and / or titanium halogen compounds, but from known halogenating agents such as aluminum halides, silicon halides, and phosphorus halides. You can also

The halogen contained in the catalyst component may be fluorine, chlorine, bromine, iodine or a mixture thereof, with chlorine being particularly preferred.

Solid components used in the present invention include SiCl in addition to the above essential components.
₄ , CH ₃ SiCl ₃ , silicon compounds such as methyl hydrogen polysiloxane, Al (OiC ₃ H ₈ ) ₃ , AlCl ₃ , AlBr ₃ , Al (OC ₂ H ₅ ) ₃ , Al (OCH ₃ ) ₂ Cl, etc. Aluminum compound and B (OCH ₃ ) ₃ , B (O
Other components such as boron compounds such as C ₂ H ₅ ) ₃ and B (OC ₆ H ₅ ) ₃ can be used, and it is possible that these remain in the solid component as components such as silicon, aluminum and boron. Absent.

Furthermore, when producing this solid component, it can also be produced using an electron donor as an internal donor.

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

More specifically, (i) methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropylbenzyl alcohol, etc.
To 18 alcohols, (b) phenol, cresol, xylenol, ethylphenol, propylphenol, cumylphenol, nonylphenol, phenols having 6 to 25 carbon atoms and optionally having an alkyl group such as naphthol, (c) acetone , Methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc., having 3 to 15 carbon atoms, (d) acetaldehyde, propionaldehyde, octyl aldehyde, benzaldehyde, tolualdehyde, naphthaldehyde, etc., having 2 to 15 carbon atoms, (E) Methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, ethyl stearate, chloroacetic acid Chill, dichloroacetic ethyl acetate, methyl methacrylate, ethyl crotonate, 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, diheptyl phthalate, γ-butyrolactone, α-valerolactone, coumarin, phthalide, ethylene carbonate, etc. C2 to C20 organic acid esters, (f) ethyl silicate, butyl silicate, inorganic acid esters such as silicates such as phenyltriethoxysilane, (to) acetyl chloride,
Benzoyl chloride, toluic acid chloride, anisic acid chloride, phthaloyl chloride, isochlorophthaloyl and other acid halides having 2 to 15 carbon atoms, (thi) methyl ether, ethyl ether isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether Such as C2-C20 ethers, (li) acetic acid amide, benzoic acid amide, acetic acid amides such as toluic acid amide, (nu) methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline , Amines such as pyridine, picoline, and tetramethylethylenediamine,
(L) Acetonitrile, benzonitrile, nitriles such as tolunitrile, and the like. Two or more of these electron donors can be used. Among these, organic acid esters and acid halides are preferable, and fudaric acid esters and phthalic acid halides are particularly preferable.

The amount of each component used may be arbitrary as long as the effects of the present invention are recognized, but generally, the following ranges are preferable.

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 a compound for that purpose is used as a halogen source, the amount used is 1 × 10 6 in molar ratio with respect to the amount of magnesium used, regardless of whether the titanium compound and / or the magnesium compound contains halogen. ^It is preferably in the range of ^{-2 to} 1000, and more preferably in the range of 0.1 to 100. The amount of silicon, aluminum, and boron compounds used is 1 × 10 6 in molar ratio with respect to the amount of magnesium compound used above.
^It is preferably in the range of ^{-3 to} 100, and more preferably in the range of 0.01 to 1.

The amount of the electron-donating compound used is preferably in the range of 1 × 10 ⁻³ to 10 with respect to the amount of the above-mentioned magnesium compound used, and more preferably in the range of 0.01 to 5.

Component (i) 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.

(A) A method of bringing a magnesium halide, an electron donor and a titanium-containing compound into contact with each other.

(B) A method of treating alumina or magnesia with a phosphorus halide compound, and bringing it into contact with a magnesium halide, an electron donor, and a titanium halogen-containing compound.

(C) A method of contacting a titanium halide and / or a silicon halide 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.) Specifically, methylhydrogen Polysiloxane,
Examples include ethyl hydrogen polysiloxane, phenyl hydrogen polysiloxane, cyclohexyl hydrogen polysiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane. it can.

(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 in which an organomagnesium compound such as a Grignard reagent is allowed to act with a halogenating agent, a reducing agent, etc., and then an electron donor and a titanium compound are brought into contact therewith.

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

Ingredient (ii) Ingredient (ii) used to produce ingredient (A) is
General formula R ¹ _m X _n Si (OR ² ) _4-mn (wherein R ¹ and R ² are hydrocarbon residues, X is halogen, and m and n are 0 ≦ m ≦ 3 and 0 ≦, respectively). n ≦ 3 and 0
≦ m + n ≦ 3). R ¹ and R ² are each about 1 to 20, preferably 1
It is preferably a hydrocarbon residue of -10. X is preferably chlorine, at least in terms of economy.

Specific examples include (CH ₃ ) Si (OCH ₃ ) ₃ , (CH ₃ ) Si (OC ₂ H ₅ ) ₃ , (C ₂ H ₅ ) ₂ Si (OCH ₃ ) ₂ , (nC ₆ H ₁₁ ) Si. _{(OCH 3) 3, (C} 2 H 5) Si (OC 2 H 5) 3, (nC 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, Si (OC 2 H 5) 3 Cl, (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, Si (OCH 3) 2 Cl 2, (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, (nC 3 H 7) Si (OC 2 H 5) 3, _{(CH 3) Si (OC 3} H 7) 3, (C 6 H 5) (CH 2) Si (OC 2 H 5) 3, _{(CH 3) 3 CSi (CH} 3) (OCH 3) 2, (CH 3) 3 CSi (HC (CH 3) 2) (OCH 3) 2, (CH 3) 3 CSi (CH 3) (OC 2 H ₅ ) ₂ , (C ₂ H ₅ ) ₃ CSi (CH ₃ ) (OCH ₃ ) ₂ , (CH ₃ ) (C ₂ H ₅ ) CH Si (CH ₃ ) (OCH ₃ ) ₂ , ((CH ₃ ) ₂ CHCH ₂ ) Si (OCH ₃ ) ₂ , C ₂ H ₅ C (CH ₃ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂ , C ₂ H ₅ C (CH ₃ ) ₂ Si (CH ₃ ) (OC ₂ H _{5) 2, (CH 3)} 3 CSi (OCH 3) 3, (CH 3) 3 CSi (OC 2 H 5) 3, (C 2 H 5) 3 CSi (OC 2 H 5) 3, (CH ₃ ) (C ₂ H ₅ ) CHSi (OCH ₃ ) _{3 and the} like.

Of these, preferred is a branched chain hydrocarbon residue having a secondary or tertiary carbon atom at the α-position of R ¹ and a carbon number of 3 to 20, particularly R ¹
Is a silicon compound having a branched-chain hydrocarbon residue having 4 to 10 carbon atoms in the α-position is tertiary.

Ingredient (iii) Ingredient (iii) used to produce ingredient (A)
Is an organozinc compound.

The organozinc compound is represented by the general formula R ³ _2-a Z _n X _a (wherein R ³ is a hydrocarbon residue, X is a halogen or alkoxide group, and a represents a number of 0 ≦ a <2).
Those represented by are suitable. R ³ has 1 carbon atom
The thing of about 10 is preferable. The alkyl portion of the alkoxide group preferably has about 1 to 6 carbon atoms. Halogen is preferably chlorine, at least in terms of economy.

Specific examples include (CH ₃ ) ₂ Zn, (C ₂ H ₅ ) ₂ Zn, (iC ₄ H ₉ ) ₂ Zn, (nC ₈ H ₁₇ ) ₂ Zn, (C ₂ H ₅ ) ZnCl, (nC ₄ H ₉ ) ZnCl, (CH ₃ ) Zn (OC ₂ H ₅ ), (C ₂ H ₅ ) Zn (OCH ₃ ), and the like.

Production of Component (A) The contact conditions of the above-mentioned components (i) to (iii) may be arbitrary as long as the effect of the present invention is recognized,
Generally, the following conditions are preferred. Contact temperature is -50 to
The temperature is about 200 ° C, preferably 0 to 100 ° C. Examples of the contacting method include a mechanical method using a rotary ball mill, a vibration mill, a jet mill, a medium stirring pulverizer, 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 and halohydrocarbons, polysiloxanes (for example, the above-mentioned polymeric silicon compounds), and the like.

The amount ratio of component (i) to component (iii) 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 (i) and the component (ii) is such that the component (i) with respect to the titanium component constituting the component (i) is
i) The atomic ratio of silicon (silicon / titanium) is 0.01 to 1000
Is preferably in the range of 0.1 to 100, and more preferably in the range of 0.1 to 100.
The amount of the component (iii) used is preferably in the range of 0.01 to 100, preferably 0.1 to 30 in terms of atomic ratio of zinc of the component (iii) to the titanium component constituting the component (i) (zinc / titanium). It is within.

Component (B) Component (B) is an organoaluminum compound.

Specific examples include R ⁵ _3-n AlX _n or R ⁶ _3-m Al (OR ⁷ ) _m (wherein R ⁵ and R ⁶ may be the same or different and have 1 to 20 carbon atoms).
A hydrocarbon residue or a hydrogen atom, R ⁷ is a hydrocarbon residue, X is a halogen, n and m are each 0 ≦ n <3,
It is a number of 0 <m <3. ). Specifically, (a) trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, and tridecyl aluminum,
(B) Diethyl aluminum monochloride, diisobutyl aluminum monochloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride,
And aluminum alkoxides such as (c) diethylaluminum hydride, diisobutylaluminum hydride, (d) diethylaluminum ethoxide, and diethylaluminum phenoxide.

These (a) other organometallic compounds with an organoaluminum compound to (c), for example _{^{R 8 3-a Al (OR}} 9) a ( wherein,
1 ≦ a ≦ 3, R ⁸ and R ⁹ are the same or different hydrocarbon residues having about 1 to 20 carbon atoms. It is also possible to use an alkylaluminum alkoxide represented by the formula (1). 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.

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

[Use of catalyst / polymerization]

The catalyst 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 which uses substantially no solvent.
Further, it is also applied to a system in which continuous polymerization, batch polymerization or preliminary polymerization is carried out. In the case of slurry polymerization, as a solvent, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, or toluene is used alone or as a mixture. Polymerization temperature is from room temperature to 20
The temperature is about 0 ° C., preferably 50 to 150 ° C., and hydrogen can be supplementarily used as a molecular weight regulator at that time.

The olefins polymerized with the catalyst system of the present invention have the general formula R
—CH═CH ₂ (where R is a hydrogen atom, or 1 to 10 carbon atoms)
Hydrocarbon residue of, and may have a branching group. ). Specifically, there are olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, and 4-methylpentene-1. Ethylene and propylene are preferred. In these polymerizations, up to 50% by weight, preferably up to 20% by weight, of the olefins can be copolymerized with ethylene, and up to 30% by weight of the olefins, especially ethylene, with respect to propylene. , Can be copolymerized. Copolymerization with other copolymerizable monomers (for example, vinyl acetate, diolefin, etc.) can also be performed.

[Experimental example]

Example 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 20 g of MgCl ₂ and 15.5 ml of diheptyl phthalate were introduced into this. Then, it was crushed by 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 that 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 [component (i)] was taken out and the composition was analyzed, the Ti content was 3.01% by weight.

Next, 50 ml of sufficiently purified n-heptane was introduced into a flask thoroughly replaced with nitrogen, and 5 g of the component (i) obtained above was added to the flask as component (ii) (C
_{H 3) 3 CSi (CH 3} ) (OCH 3) 2 and 1.2 ml and component (ii
i) the reduction of Zn (C ₂ H _{5) 2} was introduced 0.4 g, 2 at 30 ° C.
Contacted for a time. After the contact was completed, it was thoroughly washed with n-peptane to obtain a 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 as component (B),
And 15 mg of the catalyst component (A) synthesized above was introduced. Then, 60 ml of H ₂ was introduced, the temperature was raised and the pressure was increased, the polymerization pressure = 5 kg / cmG, the polymerization temperature 75 ° C., the polymerization time =
Polymerization was carried out under the condition of 2 hours. After completion of the polymerization, the obtained polymer slurry was separated by filtration and the polymer was dried.

As a result, 88.7 grams of polymer was obtained. on the other hand,
The effluent yielded 0.58 grams of polymer. From the boiling heptane extraction test, all products II (hereinafter abbreviated as TI.I)
It was 97.2 weight percent. The MFR was 3.9 g / 10 minutes, and the bulk density of the polymer was 0.41 g / cc.

Example 2 [Production of Component (A)] 200 ml of dehydrated and deoxygenated n-heptane was introduced into a flask sufficiently replaced with nitrogen, and then MgCl ₂ was added.
0.1 mol and 0.2 mol of Ti (O-nC ₄ H ₉ ) ₄ were introduced and reacted at 95 ° C. for 2 hours. After completion of the reaction, the temperature was lowered to 40 ° C., 12 ml of methylhydropolysiloxane (20 centistokes) was then introduced, and the reaction was carried out for 3 hours. The resulting solid component was washed with n-heptane. Then, 50 ml of n-heptane purified in the same manner as above was introduced into a flask which had been sufficiently replaced with nitrogen, and 0.03 mol of the solid component synthesized above was introduced in terms of Mg atom. Then, 25 ml of n-heptane was mixed with 0.05 mol of SiCl ₄ and the mixture was mixed at 30 ° C. for 30
The mixture was introduced into the flask for 1 minute and reacted at 70 ° C. for 3 hours. After the completion of the reaction, the resultant was washed with n-heptane. Then, 25 ml of n-heptane was mixed with 0.003 mol of phthalic acid chloride, and the mixture was introduced into the flask at 70 ° C for 30 minutes and reacted at 95 ° C for 1 hour. After the completion of the reaction, the resultant was washed with n-heptane.
Then, 5 ml of TiCl ₄ was introduced and the reaction was carried out at 100 ° 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 (i) for producing the solid component (A).

Using this component (i), (CH ₃ ) ₃ CSi (CH ₃ ) of component (ii)
Contact was performed under the same conditions as in Example 1 except that the amount of (OCH ₃ ) ₂ used was changed to 1.6 ml. After contact, n
-Washed thoroughly with heptane to give component (A).

[Polymerization of propylene]

Use 150 parts of component (B) triethylaluminum
Polymerization of propylene was carried out under the same conditions as the polymerization of propylene of Example 1 except that milligram was used.

The result was 172 grams of polymer, MFR = 2.8g
/ 10 minutes, TI.I = 98.5 weight percent, polymer bulk specific gravity =
It was 0.48 g / cc.

Examples 3 to 6 In the production of the solid component (A) of Example 2, the component (i
Polymerization of propylene was carried out in the same manner as in Example 2 except that the compounds shown in Table 1 were used in place of (CH ₃ ) ₃ CSi (CH ₃ ) (OCH ₃ ) ₂ as the silicon compound of i). Example 2
It carried out similarly to. The results are shown in Table-1.

Examples 7 to 9 Polymerization was performed in the same manner as in Example 3 except that the organoaluminum compound shown in Table 2 was used in place of the organoaluminum as the component (B) in the propylene polymerization in Example 3. The results are shown in Table-2.

Example 10 [Production of Component (A)] 100 ml of dehydrated and deoxygenated n-heptane was introduced into a flask sufficiently replaced with nitrogen, and then MgCl ₂ was added.
0.1 mol and 0.2 mol of Ti (O-nC ₄ H ₉ ) ₄ were introduced and reacted at 95 ° C. for 2 hours. After the reaction was completed, the temperature was lowered to 35 ° C and 1,3,5,7
-Introducing 15 ml of tetramethylcyclotetrasiloxane and reacting 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. Then, 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 (i) for producing the component (A). The titanium content in the solid component was 4.52 weight percent.

Next, 50 ml of sufficiently purified n-heptane was introduced into a flask which had been sufficiently replaced with nitrogen, and 5 g of the component (i) obtained above was added to the flask, followed by Zn as the component (iii).
1.5 g of (iC ₄ H ₉ ) ₄ was introduced, and the mixture was contacted at 30 ° C. for 1 hour, and after completion of the contact, it was thoroughly washed with n-heptane. Then, 4.7 ml of (CH ₃ ) CSi (CH ₃ ) (OCH ₃ ) ₂ was introduced as the component (ii) and contacted at 40 ° C. for 1 hour. After the contact was completed, it was thoroughly washed with n-heptane to obtain a component (A).

[Polymerization of propylene]

Under the polymerization conditions of Example 2, propylene was polymerized in the same manner as in Example 2 except that the amount of the component (B) triethylaluminum used was 63 mg and the polymerization temperature was 70 ° C. 109 grams of polymer are obtained, MFR = 8.6g
/ 10 minutes, TI.I = 96.2 weight percent, polymer bulk specific gravity =
It was 0.46 g / cc.

Example 11 Component (A) was produced under the same conditions as in Example 2 except that ethyl benzoate was used instead of phthaloyl chloride in the production of component (A) of Example 2. Polymerization of propylene was also carried out in the same manner as in Example 2. as a result,
77.8 grams of polymer were obtained, MFR = 6.3 g / 10 min, TI.
I = 93.3 weight percent, polymer bulk specific gravity = 0.41 g / cc.

Example 12 In the production of the component (A) of Example 1, 1.8 ml of (CH ₃ ) ₃ CSi (CH ₃ ) (OCH ₃ ) ₂ was used as the component (ii) and Zn (C ₂ H ₅ was used as the component (iii). ) The same production was carried out except that 0.47 g of Cl was introduced and contact was carried out at 50 ° C. for 1 hour, and propylene was polymerized in exactly the same manner. 80.4 grams of polymer were obtained, TI.I = 96.6 weight percent, MFR = 4.3g
/ 10 minutes, the polymer bulk specific gravity was 0.42 g / cc.

Examples 13 to 16 In the production of the component (A) of the example 2, a catalyst was produced in the same manner as in the example 2 except that the compounds shown in Table 3 were used as the silicon compound of the component (ii). Polymerization was performed in the same manner as in Example 2. The results are shown in Table-3.

Comparative Examples 1-2 In the production of the component (A) of Examples 1-2, the component (ii
Component (A) was prepared in exactly the same manner, except that Zn (C ₂ H ₅ ) ₂ was not used as i), and propylene was polymerized in exactly the same manner. The results are shown in Table-4.

Comparative Example 3 In the production of the component (A) of Example 2, the component (A) was produced without using the component (ii) and the component (iii), and propylene was polymerized in exactly the same manner. 118 grams of polymer were obtained, MFR = 30.6 g / 10 min, polymer bulk specific gravity = 0.32 g / cc, TI.I = 68.9 weight percent.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is for assisting the understanding of the technical contents of the present invention relating to the Ziegler catalyst.

Claims (1)

[Claims] 1. An olefin polymerization catalyst comprising the following components (A) and (B). Component (A) Component (i): Solid component containing tetravalent titanium, magnesium and halogen as essential components, Component (ii): General formula R ¹ _m X _n Si (OR ² ) _4-mn (where R is ¹ and R ² are hydrocarbon residues, X is halogen, m
And n are 0 ≦ m ≦ 3 and 0 ≦ n ≦ 3, respectively, and 0 ≦ m + n ≦ 3. A solid compound component obtained by contacting a silicon compound represented by the formula (4), component (iii): organozinc compound. Component (B) Organoaluminum compound.