JPH0826096B2 - Olefin polymerization catalyst - Google Patents

Description

TECHNICAL FIELD The present invention relates to a catalyst for olefin polymerization.

When olefins are polymerized using the catalyst of the present invention, the activity sustainability of the polymerization becomes excellent, and the molecular weight distribution of the polymer produced by this polymerization becomes easy to control.

2. Description of the Related Art In recent years, using solid components containing titanium, magnesium, and halogen as essential components, α-containing 3 or more carbon atoms
Many proposals have been made for producing highly stereoregular polymers of olefins. According to the conventional proposed method, in the actual polymerization, in addition to the above solid component and the organoaluminum compound, in order to increase the stereoregularity of the product polymer, an electron donating compound is added at the time of polymerization. Need to be used (for example, JP-A-57-63310, 57-63311, 57
-63312, 59-117509, 59-191731, 59-2
06407, 59-206408, 59-206410, etc.). The catalyst system using an electron-donating compound as the known third component has insufficient activity durability during polymerization,
On the other hand, it was difficult to control the molecular weight distribution, which is one of the polymerization factors of the product polymer. Generally, the use of electron donor compounds to increase the stereoregularity of the product polymer results in a polymer with a certain molecular weight distribution. Therefore, when a fourth component is added to control their molecular weight distribution, in many cases, due to the interaction between the third component and the fourth component or the competitive action with respect to the first component or the second component, stereoregularity is obtained. The current situation is that the molecular weight distribution is not sufficiently controlled.

SUMMARY OF THE INVENTION The present invention provides a catalyst for olefin polymerization, which comprises a combination of the following components (A), (B) and (C).

Component (A) Component (i): solid component containing tetravalent titanium, magnesium and halogen as essential components, and component (ii): general formula R ¹ R _{2 3-n} Si (OR ³ ) _n (however, , R ¹ represents a branched hydrocarbon residue, R ² represents a hydrocarbon residue which is the same as or different from R ¹ , R ³ represents a hydrocarbon residue, and n represents a number of 1 ≦ n ≦ 3. ) A silicon compound represented by the formula :), a solid catalyst component obtained by contacting the component, component (B) organoaluminum compound, component (C) alcohol and / or silanol.

EFFECTS OF THE INVENTION According to the present invention, the problems of the above-mentioned prior art can be solved. The effects of the present invention are listed below.

(A) In the present invention, it is possible to polymerize olephins, which has excellent durability of polymerization activity.

(B) In the present invention, the polymerization temperature characteristics are good and high temperature polymerization is possible.

(C) It is possible to control the molecular weight distribution of the product polymer, and particularly to narrow the molecular weight distribution.

Detailed Description of the Invention The catalyst of the present invention is characterized by combining the component (A), the component (B) and the component (C).

Component (A) As the component (i) which is a solid component containing tetravalent titanium, magnesium and halogen as essential components used in the production of the component (A) used in the present invention, known components can be used.

For example, JP-A-53-45688, JP-A-54-3894, and JP-A-54-3.
1092, 54-39483, 54-94591, 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 component (i), 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 (i).

Examples of the magnesium source used for producing the above component (i) include magnesium halide, dialkoxymagnesium, alkoxymagnesium halide, magnesium oxyhalide, dialkylmagnesium, magnesium oxide, magnesium hydroxide and magnesium carboxylate. Examples include magnesium compounds.

Further, as a titanium source, 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 represents halogen,
n represents a number of 0 ≦ n ≦ 4. ) And titanium compounds. Specific examples include TiCl ₄ , TiBr ₄ , Ti (O
_{C 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 ) B
r 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 (OC
H ₂ CH (C ₂ H ₅ ) C ₄ H ₉ ] ₄ , and so on.

Further, it may be a molecular compound obtained by reacting TiX ' ₄ (where X'represents halogen) with an electron donor. 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 ₃ H ₅ , TiCl ₄ · ClCOC ₂ H ₅ , TiCl ₄ · C ₄ H ₄ O, and the like.

As the halogen source, 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 the above component (i). Examples of the electron donor include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, ethers,
Examples thereof include oxygen-containing electron donors such as acid amides and acid anhydrides, and nitrogen-containing electron donors such as ammonia, amines, nitriles and isocyanates.

More specifically, methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol,
1 to 1 carbon atoms such as isopropyl ginzyl alcohol
18 alcohols; phenols having 6 to 25 carbon atoms which may have an alkyl group, such as phenol, cresol, xylenol, ethyl phenol, propyl phenol, cumyl phenol, nonyl phenol, and naphthol;
C3-C15 ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone and benzophenone; C2-C15 ketones such as acetaldehyde, propionaldehyde, octylaldehyde, 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, penzyl benzoate, methyl toluate,
Ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxy benzoate, diethyl phthalate, dibutyl phthalate,
C2-C20 organic acid esters such as diheptyl phthalate, γ-butyrolactone, α-valerolactone, coumarin, phthalide and ethylene carbonate; silicic acid esters such as ethyl silicate, butyl silicate and phenyltriethoxysilane. Inorganic acid esters such as; acetyl chloride,
Acid halides having 2 to 15 carbon atoms such as benzoyl chloride, toluic acid chloride, anisic acid chloride, phthaloyl chloride and iso-phthaloyl chloride; methyl ether, ethyl ether, isopropyl ether, butyl ether, aluminum ether, tetrahydrofuran, anisole, diphenyl C2-C20 ethers such as ethers; acetic acid amides, benzoic acid amides, acetamides such as toluic acid amides; methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, Amines such as tetramethylethylenediamine; Nitriles such as acetonitrile, benzonitrile, tolunitrile;
And so on. Two or more of these electron donors can be used.

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.

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.

The component (i) used in the present invention is Si in addition to the above essential components.
Cl _4, CH ₃ SiCl _3, silicon compounds such as methylhydrodiene _{polysiloxane, Al (O iso C 3 H} 8) 3, AlCl 3, AlBr 3, Al
Aluminum compounds such as (OC ₂ H ₅ ) ₃ , Al (OCH ₃ ) ₂ Cl, and (OC
_{H 3) 3, B (OC} 2 H 5) 3, B (OC 6 H 5) Other components used in such boron compound ₃ such as is possible, the solid component thereof is of silicon, as a component of aluminum and boron, etc. It may remain inside.

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. The amount of the halogen source compound used may be in the range of 1 × 10 ^{−4 to} 1000 by molar ratio with respect to the amount of the magnesium compound to be used, preferably 0.01 to 100. The amount of the boron compound used is 1 × 10 ⁻³ to 10 in terms of molar ratio with respect to the amount of the magnesium compound used.
It may be in the range of 0, and preferably in the range of 0.01 to 10.

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.

As the contact component (i) used in the present invention, the solid component obtained as described above can be used as it is, or the prepolymerized component obtained by contacting this solid component with olefins in the presence of an organoaluminum compound. Can also be used as When the component (i) is preliminarily polymerized, the component (ii) is preferably brought into contact after preliminarily polymerized.

When component (i) is preliminarily polymerized, the conditions for prepolymerization of olefins for producing component (i) are not particularly limited, but generally the following conditions are preferred. The polymerization temperature is 0 to 80 ° C, preferably 10 to 60 ° C
Is. The polymerization amount is 0.001 per gram of solid component.
Preferably polymerizing ~ 50 grams of olefins,
More preferably, 0.1 to 10 grams of olefins are polymerized.

As the organoaluminum component at the time of prepolymerization, those generally known can be used.

As a specific example, Al (C ₂ H ₅ ) ₃ , Al (isoC ₄ H ₉ ) ₃ , Al (C ₅ H
₁₃ ) ₃ , Al (C ₈ H ₁₇ ) ₃ , Al (C ₁₀ H ₂₁ ) ₃ , Al (C ₂ H ₅ ) ₂ Cl, Al (iso
_{C 4 H 9) 2 Cl,} Al (C 2 H 5) 2 H, Al (isoC 4 H 9) 2 H, Al (C 2 H 5) 2 (OC 2
H ₅ ), etc.

Of these, Al (C ₂ H ₅ ) ₃ and Al (isoC ₄ H ₉ ) ₃ are preferable.
Is. It is also effective to use a combination of a trialkylaluminum and an alkylaluminum halide, or a combination of a trialkylaluminum, an alkylaluminum halide and an alkylaluminum ethoxide.

As a specific example, the combination of Al (C ₂ H ₅ ) ₃ and Al (C ₂ H ₅ ) ₂ Cl
Combined use of (isoC ₄ H ₉ ) ₃ and Al (isoC ₄ H ₉ ) ₂ Cl, Al (C ₂ H ₅ ) ₃ and Al (C ₂
H ₅ ) _1.5 Cl _1.5 combined use, Al (C ₂ H ₅ ) ₃ and Al (C ₂ H ₅ ) ₂ Cl and Al (C
₂ H ₅ ) ₂ (OC ₂ H ₅ ) may be used in combination.

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

Examples of olefins used during the prepolymerization include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-pentene-1 and the like. It is also possible to make hydrogen coexist during the prepolymerization.

Thus, a prepolymerized component (i) in which a solid component containing tetravalent titanium, magnesium and halogen as essential components is brought into contact with an olefin in the presence of an organoaluminum compound is obtained.

The component (ii) to be contacted with the above component (i) for producing the contact component (A) used in the method of the present invention is represented by the general formula: R ¹ R ² _3-n Si (OR ³ ) _n (provided that , R ¹ is a branched hydrocarbon residue, R ² is a hydrocarbon residue which is the same as or different from R ^1, and R ³ is a hydrocarbon residue,
n is a silicon compound represented by 1 ≦ n ≦ 3).

Here, R ¹ is preferably branched from a carbon atom adjacent to a silicon atom. The branching group in that case is an alkyl group, a cycloalkyl group or an aryl group (for example,
A phenyl group or a methyl-substituted phenyl group). More preferable R ¹ is such that the carbon atom adjacent to the silicon atom, that is, the α-position carbon atom is a secondary or tertiary carbon atom.

In particular, those having a tertiary carbon atom bonded to a silicon atom are preferable. The carbon number of R ¹ is usually 3 to 20, preferably 4 to 10. R ² has 1 to 20 carbon atoms, preferably 1 to
It is usually a branched or linear aliphatic hydrocarbon group of 10. R ³ is usually an aliphatic hydrocarbon group, preferably a linear aliphatic hydrocarbon group having 1 to 4 carbon atoms.

 Specific examples of the silicon compound as the component (ii) are shown below.

_{(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 , etc.

The contact conditions of the above-mentioned component (i) (either prepolymerized or non-prepolymerized) and component (ii) are as follows:
It may be arbitrary as long as the effect of the present invention is recognized, but the following conditions are generally preferable. The contact temperature is about −50 to 200 ° C., preferably 0 to 100 ° C.

Examples of the contact method include a mechanical method using a rotary ball mill, a vibration mill, a jet mill, a medium stirring / pulverizing machine, and a method of bringing into contact by stirring in the presence of an inert diluent. Inert diluents used at this time include aliphatic or aromatic hydrocarbons and halohydrocarbons, polysiloxanes and the like.

The amount ratio of the component (i) and the component (ii) with or without the pre-polymerization of the component (i) is the atomic ratio of silicon of the component (ii) to the titanium component constituting the component (i) (silicon / titanium).
May be in the range of 0.01 to 1000, preferably in the range of 0.1 to 100.

Component (B) Component (B) is an organoaluminum compound. As a specific example, R ⁵ _3-n AlX _n or R ⁶ _3-m Al (OR ⁷ ) _m (where R ⁵
And R ⁶ may be the same or different and may be a hydrocarbon residue or hydrogen atom having about 1 to 20 carbon atoms, R ⁷ is a hydrocarbon residue, X is halogen, and n and m are 0 ≦ n <3 and 0 <, respectively. m <3
Is the number of. ). In particular,
(A) Trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, etc., (b) diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, ethyl Alkyl aluminum halides such as aluminum dichloride, (c) diethyl aluminum hydride, diisobutyl aluminum hydride, (d) diethyl aluminum ethoxide, and aluminum alkoxides such as diethyl aluminum phenoxide.

In addition to these (a) to (d) organoaluminum compounds, other organometallic compounds such as R ⁸ _3-a Al (OR ⁹ ) _a (where 1
≦ a <3, R ⁸ and R ⁹ are the same or different hydrocarbon residue having about 1 to 20 carbon atoms. It is also possible to use an alkylaluminum alkoxide represented by the formula (1). For example, a combination of triethylaluminum and diethylaluminum ethoxide, a combination of diethylaluminum monochloride and diethylaluminum ethoxide, a combination of ethylaluminum dichloride and ethylaluminum diethoxy, a combination of triethylaluminum and diethylaluminum ethoxide and diethylaluminum chloride. It can be used in combination.

Component (C) The component (C) used in the present invention is alcohol and / or
Or silanol. Aliphatic alcohols and aromatic alcohols are used as alcohols.

As the aliphatic alcohol, monohydric or polyhydric alcohol can be used, and usually has about 1 to 20 carbon atoms, preferably 1 carbon atom.
Those having a hydrocarbon residue of about 10 are used.

Specific examples include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, se.
c-butyl alcohol, t-butyl alcohol, isoamyl alcohol, n-amyl alcohol, n-hexyl alcohol, cyclohexyl alcohol, n-octyl alcohol, 2-ethylhexyl alcohol, stearyl alcohol, benzyl alcohol, ethylene glycol, propylene glycol, glycerin, Etc.

As the aromatic alcohol, phenol and naphthol having up to about 20 carbon atoms which may be substituted with an alkyl group, an alkoxy group and / or a halogen atom are used.

Specific examples include phenol, m-cresol, o-
Cresol, p-cresol, p-methoxyphenol, 2,6-dimethylphenol, β-naphthol, α-
Examples thereof include naphthol, naphthoresorcin, resorcin, 2,6-xylenol, 3,5-xylenol, carvacrol and catechol.

Silanol is represented by the general formula R ¹⁰ ySi (OH) _4-y (wherein R ¹⁰ is a hydrocarbon residue having about 1 to 20 carbon atoms, and y is 1 ≦ y <4). ). Specific examples include (CH ₃ ) ₃ SiOH, (C ₂ H ₅ ) ₃ SiOH, (CH ₃ ) ₂ Si (OH) ₂ , and (C ₂ H ₅ ).
_{2 Si (OH) 2, (} C 6 H 5) 2 Si (OH) 2, and the like.

Two or more kinds of the above alcohols and / or silanols may be used in combination.

Among the above alcohols, preferably 1 to 10 carbon atoms
It is a fatty alcohol to a degree, for example CH ₃ OH, C ₂ H ₅ O
_{H, n-C 4 H 9} OH, (2-C 2 H 5) C 6 H 12 OH, n-C 6 H 13 OH , and the like. Further, preferable examples of the phenols include phenol, o-cresol, m-cresol, p-cresol and the like. Further, as preferable examples of silanols, (CH ₃ ) ₃ SiOH, (C ₂ H ₅ ) ₃ SiOH, (C ₆ H ₅ ) ₂ Si
(OH) ₂ etc.

The amounts of the component (A), the component (B) and the component (C) used may be arbitrary as long as the effects of the present invention are recognized, but generally, the following ranges are preferable. The amount of component (B) used is in the range of 1 to 1000, preferably 10 to 300, in terms of Al / Ti (molar ratio) with respect to the titanium component constituting component (A). The amount of component (C) used is in the range of 0.001 to 100, preferably 0.01 to 10, in terms of component (C) / component (B) (molar ratio) relative to the amount of component (B) used. Is.

(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, hexane,
Saturated aliphatic or aromatic hydrocarbons such as heptane, pentane, cyclohexane, benzene and toluene may be used alone or as a mixture.

The polymerization temperature is from room temperature to about 200 ° C, preferably 50 to 150.
The temperature is 0 ° C., and hydrogen can be supplementarily used as a molecular weight regulator at that time.

(Olefin) Olefin used for polymerizing with the catalyst system of the present invention has the general formula R-CH = CH ₂ (wherein R is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and a branched group May be present). Specifically, ethylene,
Propylene, butene-1, pentene-1, hexene-
There are olefins such as 1,4-methylpentene-1. Ethylene and propylene are preferred.

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

Examples 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 Mg was used.
Cl ₂ (30 g) and diheptyl phthalate (23.3 milliliter) were introduced, and the mixture was pulverized with a rotary ball mill for 48 hours. After the completion of the pulverization, the mixed pulverized composition was taken out of the mill in a dry box. Then, 26.4 g of the ground composition was introduced into a flask which had been sufficiently replaced with nitrogen, and 25 milliliters of n-heptane and 75 milliliters of TiCl ₄ were introduced and reacted at 100 ° C. for 3 hours. After completion of the reaction, it was thoroughly washed with n-heptane.
A part of the obtained solid component was taken out and the composition was analyzed. As a result, it was a solid component containing Ti, magnesium, and halogen as essential components having a Ti content of 3.12% by weight.

Then an internal volume of 1.5 with stirring and temperature control
500 ml of sufficiently dehydrated and deoxygenated n-heptane, 4.2 g of triethylaluminum, and 20 g of the solid component obtained above were introduced into a liter stainless steel stirring tank. Set the temperature in the stirring tank to 20 ℃,
Propylene was introduced at a constant rate, and propylene was polymerized for 30 minutes. After the completion of the polymerization, it was thoroughly washed with n-heptane. When a part of the solid component was taken out and the amount of propylene polymerized was examined, 0.97 g of propylene per 1 g of the solid component was the component (i).

50 milliliters of sufficiently purified n-heptane was introduced into a flask thoroughly replaced with nitrogen, then 5 g of the component (i) obtained above was introduced, and then as a silicon compound of the component (ii). Was introduced at 0.68 milliliter and contacted at 30 ° C. for 2 hours.
After the contact was completed, it was thoroughly washed with n-heptane to obtain a 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 milliliters of fully dehydrated and deoxygenated n-heptane, 125 milligrams of triethylaluminum as component (B),
As the component (C), 7.0 mg of methyl alcohol and 15 mg of the component (A) prepared above except the polymer prepolymerized were introduced.

Then, introduce 60 milliliters of hydrogen, raise the temperature and pressure,
Polymerization pressure = 5 kg / cm ² G, polymerization temperature = 75 ° C., polymerization time = 2
Polymerization was carried out under the condition of time. After the polymerization was completed, the obtained polymer slurry was separated by filtration and the polymer was dried. As a result, 102 grams of polymer was obtained. From one filtrate 0.8 g of polymer was obtained. From the boiling heptane extraction test, all products II (hereinafter abbreviated as T-II) were 9
It was 7.2 weight percent. The MFR was 2.3 / 10 minutes and the bulk density of the polymer was 0.40 g / cc. When the Q value, which is a measure of the molecular weight distribution of the product polymer, was examined, it was Q = 5.3.

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.
0.4 mol and 0.8 mol of Ti (O-nC ₄ H ₉ ) ₄ were introduced and reacted at 95 ° C for 2 hours. After the completion of the reaction, the temperature was lowered to 40 ° C., and then 48 milliliters of methylhydropolysiloxane (of 20 centistokes) were introduced, followed by a reaction for 3 hours. The resulting solid component was washed with n-heptane.

Next, 50 milliliters of n-heptane purified in the same manner as in Example 1 was introduced into a flask sufficiently replaced with nitrogen, and 0.24 mol of the solid component synthesized above was introduced in terms of Mg atom.
Then, 25 milliliters of n-heptane was mixed with 0.4 mol of SiCl ₄ and the mixture was introduced into the flask at 30 ° C for 60 minutes and reacted at 90 ° C for 3 hours.

To this, 25 milliliters of n-heptane was mixed with 0.016 mol of phthalic acid chloride, and the mixture was introduced into the flask at 90 ° C for 30 minutes and reacted at 90 ° C for 1 hour.

After the completion of the reaction, the resultant was washed with n-heptane. Then to this
0.24 mmol of SiCl ₄ was introduced and reacted at 100 ° C. for 3 hours. After completion of the reaction, it was thoroughly washed with n-heptane. This was used as a solid component for producing the component (i).

Component (i) was produced under the same conditions as in Example 1 except that this solid component was used. The amount of propylene prepolymerized as the component (i) thus obtained was 1.02 g per 1 g of the above solid component.

Then, the component (i) and the component (ii) were contacted. The contact was carried out in the same manner as in Example 1 except that the amount of the silicon compound as the component (ii) used in Example 1 was changed to 0.81 milliliter.
I went as well. After the completion of the contact, the resultant was sufficiently washed with n-heptane to obtain Component (A).

[Propylene polymerization]

Polymerization of propylene was carried out in the same manner as in Example 1 except that 10 mg of ethyl alcohol was used as the component (C) in the polymerization of Example 1. As a result, 176 g of a polymer was obtained, T-II = 98.9 weight percent, MFR = 2.1 g / 10 minutes, polymer bulk specific gravity = 0.47 g / cc, Q =
It was 5.0.

Example 3 [Production of Component (A)] 200 ml of dehydrated and deoxygenated n-heptane was introduced into a flask thoroughly 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
15 milliliters of 3,5,7-tetramethylcyclotetrasiloxane was introduced and reacted for 5 hours. The resulting solid component was washed with n-heptane.

Then, n-heptane was added to a flask that had been sufficiently replaced with nitrogen.
After introducing 100 milliliters, the solid component synthesized above was converted into Mg.
0.03 mol was introduced in terms of atoms. Then add 0.06 mol of SiCl ₄ to 2
The mixture was introduced at 0 ° 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 component (i).

Using this component (i) as the silicon compound of component (ii) The components (i) and (ii) were contacted in the same manner as in Example 1 except that the amount was 1.9 milliliter. After contact, n
-Washed thoroughly with heptane to give component (A).

[Polymerization of propylene]

In the polymerization conditions of Example 1, the polymerization temperature was 70 ° C.,
Polymerization of propylene was carried out under the same conditions as in Example 1 except that 20.6 mg of phenol was used as the component (C). The result was 82.4 grams of polymer, T
-II = 97.4 weight percent, MFR = 3.7 g / 10 min, polymer bulk specific gravity = 0.46 g / cc, Q = 5.2.

Examples 4 to 7 In the propylene polymerization of Example 2, propylene was polymerized in the same manner as in Example 2 except that the compounds shown in Table 1 were used as the component (C). The results are shown in Table-1.

Examples 8 to 11 Propylene was polymerized in the same manner as in Example 3 except that the silicon compound shown in Table 2 was used as the component (ii) in the production of the component (A) in Example 3. The results are shown in Table-2.

Examples 12 to 15 In the same manner as in Example 2 except that the amount of the component (C) ethyl alcohol used in the polymerization of propylene was changed in the amounts shown in Table 3 in Example 2, the component (A) was used.
Was produced and propylene was polymerized. The results are shown in Table-3.

In the polymerization of propylene of Example 16 Example _{1, n-C 6 H 13} OH12.0 milligrams and (CH ₃₎ as component (C) ₃ SiOH9.8
The reaction was performed in the same manner as in Example 1 except that milligram was used. As a result, 93 g of the polymer was obtained, and T-
II = 97.3 weight percent, MFR = 2.1 g / 10 min, polymer bulk specific gravity = 0.40 g / cc, Q = 5.2.

[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. A catalyst for olefin polymerization, which comprises a combination of the following components (A), (B) and (C). Component (A) Component (i): solid component containing tetravalent titanium, magnesium and halogen as essential components, and component (ii): general formula (However, R ¹ is a branched chain hydrocarbon residue, R ² is the same or different hydrocarbon residue as R ¹ , R ³ is a hydrocarbon residue,
n represents a number of 1≤n≤3), a solid catalyst component obtained by contacting with a silicon compound, component (B) organoaluminum compound, component (C) alcohol and / or silanol.