JPH06104688B2 - Process for producing catalyst component for α-olefin polymerization - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a catalyst component for α-olefin polymerization. More specifically, the present invention relates to a method for producing a so-called carrier-type titanium-containing solid catalyst component having a high degree of stereoregular polymerization ability and activity for producing an α-olefin polymer having stereoregularity. The carrier-type titanium-containing solid catalyst component according to the present invention is further used in combination with an organoaluminum compound as a catalyst for polymerization of α-olefin.

Prior Art Regarding titanium-supported catalyst systems, it has long been known to add various electron-donating compounds to the catalyst system for the purpose of improving the stereoregularity of the polymer (J. Poly
merScience, Polymer Letters, 3 , 855 (1965), in particular, a number of catalyst production methods have been proposed in which an electron-donating compound is contained in a titanium-supported solid catalyst component. Among electron-donating compounds such as esters, amines, ketones, and ethers, esters, particularly esters of polycarboxylic acids having a specific structure and esters of monocarboxylic acids having an alkyl group of a specific structure, are stereoregular. It has been shown to exert an excellent effect in obtaining a functional polymer (JP-A-54)
-94590, JP-A-57-63310, JP-A-57-63311,
And JP-A-58-145707.

SUMMARY OF THE INVENTION The present inventors previously disclosed in JP-A-60-130607 that an excellent solid catalyst component for α-olefin polymerization can be produced by using an electron-donating compound having a specific structure. The present inventors use the same electron-donating compound as that used in the prior application, additionally use a specific compound [component (C)], and, depending on specific production conditions, the above-mentioned known technique or prior application. The present invention has been achieved by finding that a titanium-containing solid catalyst component for α-olefin stereoregular polymerization which is superior to that obtained by the technique can be obtained.

That is, the present invention comprises: Component (A): magnesium halide-containing solid, Component (B): (Where R is a C _1-12 hydrocarbon residue or A C _2-12 organic residue having a structural site represented by, R ¹ and R ² are each a C _1-12 alkyl group, aryl group, alkyl-substituted aryl group, or aryl-substituted alkyl group), And a component (C): a halogen compound of Si or Ti, is contacted with each other in a temperature range of 50 ° C. or lower, and then this is contacted with a component (D): a halogen compound of tetravalent titanium. The present invention provides a method for producing a catalyst component for α-olefin polymerization.

Effects of the Invention It is well known to use organic carboxylic acid monoesters as electron donating compounds to be incorporated into the solid titanium catalyst component, especially in the stereoregular polymerization of α-olefins with organoaluminum compounds and Si-O-. When a Ziegler-type catalyst is formed by combining a co-catalyst composed of a silicon compound having a C bond and a solid titanium catalyst component, the organic carboxylic acid monoester contained in the solid titanium catalyst component is an aromatic carboxylic acid ester (special (Kaisho 54-94590) and It is known that (at least one of R and R'is a saturated or unsaturated branched chain hydrocarbon residue having 3 to 20 carbon atoms) (JP-A-57-63310). is there.

When the compounds defined as the component (B) of the present invention are used in place of these known electron-donating compounds, the effect thereof is higher than that of the known organic carboxylic acid monoesters. Although α-olefin stereoregular polymerization is possible (see JP-A-60-130607), in the present invention, this reaction is carried out in the reaction of contacting the components (A) and (B). ) And the reaction is carried out at a relatively low temperature of 50 ° C. or lower, it is possible to produce a titanium-containing solid catalyst component capable of significantly higher α-olefin stereoregular polymerization.

DETAILED DESCRIPTION OF THE INVENTION In the titanium-containing solid catalyst component of the present invention, component (A), component (B) and component (C) are contacted with each other in a temperature range of 50 ° C. or lower, and then contacted with component (D). Is manufactured.

[Component (A)]

Component (A) is a magnesium halide-containing solid. As the halogen, fluorine, chlorine, bromine and iodine can be used, of which chlorine is preferable.

Here, the "magnesium halide-containing solid" means magnesium halide itself, magnesium halide modified by another electron donating compound other than the component (B), or a magnesium halide dissolving agent ( For example, a solid compound such as a solid product obtained by subjecting a hydrocarbon solution containing tetrabutyl titanate, an ether, a phosphoric acid ester) to a precipitation treatment by a known method (eg, addition of methylhydrogenpolysiloxane, titanium tetrachloride). It also includes.

[Component (B)]

The component (B) is an electron donating compound represented by the following formula.

Here, R is a hydrocarbon residue having 1 to 12 carbon atoms (C _1-12 ),
Or It is an organic residue having a structural part and having 2 to 12 carbon atoms (C _2-12 ). Further, R is preferably a relatively short-chain unbranched hydrocarbon residue having 1 to 4 carbon atoms, and The carbons of are preferably unbranched carbon atoms. And, as this compound, a compound having no polar atom such as O, S and N in a portion other than the above-mentioned specific structure is generally used. R ¹ and R ² are each 1 to 12 carbon atoms
Is an alkyl group, an aryl group, an alkyl-substituted aryl group, or an aryl-substituted alkyl group. Among the compounds represented by the formula (B), particularly preferred are ethylene oxide or propylene oxide of a lower aliphatic monocarboxylic acid (R ¹ has about 1 to 12 carbon atoms) or benzoic acid (R ¹ is a phenyl group). Ethers of adducts (1 mol), especially lower (C ₁ -C ₁₂ ) alkyl or phenyl or tolyl ethers.

Specific examples of such an electron donating compound include, for example, 2-methoxyethyl acetate (CH ₃ CO ₂ CH ₂ CH ₂
OCH ₃ ), 2-ethoxyethyl acetate (CH ₃ CO ₂ CH ₂ C
H ₂ OC ₂ H ₅ ), 2-butoxyethyl acetate (CH ₃ CO ₂ C
H ₂ CH ₂ OC ₄ H ₉ ), 3-methoxybutyl acetate (CH ₃ C
O ₂ (CH ₂ ) ₂ CH (OCH ₃ ) CH ₃ ), 2- (2-ethoxyethoxy) ethyl acetate (CH ₃ CO ₂ CH ₂ CH ₂ OCH ₂ CH ₂ OC
₂ H ₅ ), 2-p-triloxyethyl acetate (CH ₃ CO
₂ CH ₂ CH ₂ OC ₆ H ₄ (CH ₃ )), ethoxymethyl acetate (CH ₃ CO ₂ CH ₂ OC ₂ H ₅ ), 3-ethoxypropyl acetate (CH ₃ CO ₂ CH ₂ CH ₂ CH ₂ OC) ₂ H ₅ ), 4-ethoxybutyl acetate (CH ₃ CO ₂ CH ₂ CH ₂ CH ₂ CH ₂ OC ₂ H ₅ ), n-butylcarbitol acetate (CH ₃ CO ₂ (CH ₂ CH ₂ O) ₂ C ₄ H ₉ ), 2
- butoxyethyl = propionate _{(CH 3 CH 2 CO 2 CH} 2 CH 2 O
C ₄ H ₉ ), 2-isobutoxyethyl propionate (CH
₃ CH ₂ CO ₂ CH ₂ CH ₂ OCH ₂ CH (CH ₃ ) ₂ ), 2-ethoxyethyl =
n- butyrate _{(C 4 H 9 CO 2 CH} 2 CH 2 OC 2 H 5), 2- ethoxyethyl = isobutyrate _{((CH 3) 2 CHCO 2} CH 2 CH 2 OC
₂ H ₅ ), 2-ethoxyethyl benzoate (C ₆ H ₅ CO ₂ CH
_{2 CH 2 OC 2 H 5)} , 2- isopropoxyethyl = benzoate _{(C 6 H 5 CO 2 CH} 2 CH 2 OCH (CH 3) 2), p- methoxybenzyl = acetate (CH ₃ CO ₂ CH ₂ -C ₆ H ₄ OCH ₃ ), 4′-ethoxyphenyl = 4-n-butylbenzoate (CH ₃ (CH ₂ ) ₃ C
_{6 H 4 CO 2 C 6 H} 4 OC 2 H 4), tetrahydrofurfuryl = n-butyrate _{(CH 3 (CH 2) 2} CO 2 CH 2 (C 4 H 7 O)) and the like. Among these, 2-ethoxyethyl acetate and 2
-Methoxyethyl acetate is preferred.

[Component (C)]

The component (C) is a halogen compound of Si or Ti. Specific examples of such compounds include, for example, SiX ₄ , CH
₃ SiX ₃ , (C ₆ H ₅ ) ₂ SiX ₂ , (C ₆ H ₅ ) ₃ SiX, HSiX ₃ , TiX ₄ , TiX
₃ (OBu), TiX ₂ (OBu) ₂ , TiX ₂ (OBu) ₃ , (X = halogen, Bu
= Butyl group) and the like. Among halogens, C1 is particularly preferable.

These compounds may be used alone or in combination of two or more kinds, or may be compounds having the same component (C) and component (D) such as a halogen compound of titanium.

[Component (D)]

The component (D) is a halogen compound of tetravalent titanium.
Chlorine is preferred as the halogen. Preferred titanium halogen compounds are those represented by the general formula Ti (OR ') _n Cl _4-n (R' is a hydrocarbon residue of C _{1 to} C ₆ ) with n = 0 or 1. Specific examples thereof include titanium tetrachloride and titanium trichlorobutoxy.

[Quantity ratio]

The component ratio of each of the components (A) to (D) is arbitrary and not critical as long as the effects of the present invention are observed.

Generally, the component (B) has a molar ratio [component (B) / Mg] of the electron-donating compound component (B) to the magnesium halogen compound present in the component (A) of 0.01 to 6, preferably 0.03. Used in a ratio of ~ 1.

Further, the component (C) has a molar ratio [component (C) / Mg] with respect to the magnesium halogen compound present in the component (A).
It is used in a proportion of 0.01 to 5, preferably 0.05 to 3.

However, the preferred quantitative ratio relationship between the components (A), (B) and (C) is also related to the mutual contact temperature of these three components, and in general, [component (B) / component (A)] is the same. In this case, the higher the mutual contact temperature and the larger the amount of the component (C) used, the larger the amount of the component (B) contained in the mutual contact treatment product. Therefore, the amount of the component (B) in the contact-treated product is determined by the correlation between the component (A) / component (B) / component (C) ratio and the treatment temperature. These preferable conditions are that the molar ratio of the content of the component (B) in the contact-treated product to the Mg in the product [component (B) / M
The amount ratio between the components and the mutual contact treatment temperature are determined so that the value g] is 0.001 to 0.3.

Component (D) can be used in a wide range of proportions, but in general, the amount of titanium atoms contained in the titanium-containing solid catalyst component produced by various methods is 0.5 to 15% by weight, preferably 0.5 to 10% by weight. It is preferable to adjust so that

[Mutual contact treatment]

In the present invention, the mutual contact treatment is carried out at 50 ° C. or lower, generally 0 to 50 ° C., preferably 5 to 40 ° C. This processing time is not particularly limited, but is usually 30 minutes to
It takes about 5 hours.

The mutual contact method between the components (A) to (C) can be carried out in the following various modes.

A) The components (A), (B) and (C) are introduced and contacted simultaneously.

(B) The component (C) is introduced dropwise into the coexisting system of the components (A) and (B).

C) The component (B) is introduced dropwise into the coexisting system of the components (A) and (C). And so on.

[Preparation of titanium-containing solid catalyst component]

The titanium-containing solid catalyst component of the present invention comprises the constituent component (A),
It is obtained by contacting the mutual contact treatment product consisting of (B) and (C) with the component (D) collectively or stepwise or once or plural times, and can be obtained by various preparation methods. . Some of the specific preparation methods are shown below.

i) MgX ₂ (magnesium halide) is mixed and contacted with the components (B) and (C), and the obtained contact-treated product is contacted with the component (D) in a liquid phase.

ii) A pulverized product (component (A)) obtained by mixing and pulverizing MgX ₂ and an electron-donating compound other than component (B) (a known internal donor such as ethyl α-phenylbutyrate) is used as component (B). ) And component (C) are contacted simultaneously or sequentially in the liquid phase, and the contact-treated product is contacted with component (D) in the liquid phase.

iii) MgX ₂ and alcohol, ether, using a dissolving agent such as alkoxide of titanium hydrocarbon solution was prepared containing MgX _2, to this solution and is contacted with a halogenating agent, such as a halide of titanium or silicon solid Precipitate (Component (A)
Of the component (B) and component (C).
Are contacted simultaneously or sequentially in the liquid phase, and the contact-treated product is contacted with the component (D) in the liquid phase.

iv) MgX ₂ is dissolved in a hydrocarbon solvent using butyl titanate, reacted with methylhydrogenpolysiloxane to precipitate a solid (formation of component (A)), and the precipitated solid and the components (B) and ( C) is contacted simultaneously or sequentially in the liquid phase, and the contact-treated product is contacted with component (D) in the liquid phase.

The feature of the present invention is that an electron-donating compound (component (B)) having a specific molecular structure is used, and the component (A) to
(C) is in contact with a specific temperature condition,
If these characteristics are provided, the effect will be exhibited in other various titanium-containing solid catalyst component preparation methods. Therefore, the method for producing the titanium-containing solid catalyst component of the present invention is not limited to the method exemplified above.

[Polymerization of α-olefin] The titanium-containing solid catalyst component of the present invention can be used for the polymerization of α-olefin by combining it with an organoaluminum compound.

The organoaluminum compound has the general formula AlR _n X _3-n (however,
R is a hydrocarbon residue having 1 to 12 carbon atoms, X is a halogen, and n is 0 <n ≦ 3).

Specific examples of such an organoaluminum compound include tolylethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, triisohexylaluminum, trioctyl. Aluminum, diethyl aluminum hydride, diisobutyl aluminum hydride, diethyl aluminum monochloride, ethyl aluminum sesquichloride, etc. are available. Of course, these aluminum compounds
It is also possible to use together more than one species.

When carrying out a polymerization reaction of α-olefin having 3 or more carbon atoms, a catalyst system comprising a titanium-containing solid catalyst component and an organoaluminum compound according to the present invention is used for the purpose of improving stereoregularity of a produced polymer. Up to this, many compounds which have been proposed for use in Ziegler polymerization catalysts and which have an effect on stereoregularity can be further added. Examples of the compound used for such a purpose include aromatic monocarboxylic acid esters, Examples thereof include an organosilicon compound having a bond and a nitrogen or oxygen heterocyclic compound having an alkyl substituent. Specifically, for example, ethyl benzoate, ethyl p-toluate, ethyl p-anisate, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, t-
Butylmethyldimethoxysilane, tetraethylsilicate, 2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetramethylpyran and the like.

The use ratio of the titanium-containing solid catalyst component and the organoaluminum compound can be varied over a wide range, but in general, it is 1 to 1000, preferably 10 to 500 (molar ratio) per titanium atom contained in the solid catalyst component. Organoaluminum compounds can be used.

The amount of the above-mentioned stereoregulation improver used for the purpose of improving the stereoregularity of the α-olefin polymer can be achieved even when the titanium-containing solid catalyst component of the present invention is used in a very small amount. However, it is usually used in a proportion of 0.001 to 1 mol, preferably 0.01 to 0.5 mol, per 1 mol of the organoaluminum compound.

The contact or mixing order and number of times of the titanium-containing solid catalyst component, the organoaluminum compound and the steric regulation improving agent are arbitrary.

Further, the titanium-containing solid catalyst component according to the present invention can be subjected to a preliminary contact treatment (so-called preliminary polymerization treatment) with a small amount of olefin in the presence of an organoaluminum compound prior to the polymerization of α-olefin. The olefins that can be used in the prepolymerization treatment are α-
It may be olefin or may be different α-olefin.

The olefins used for the polymerization include ethylene, propylene, 1-butene, 1-hexene, 4-methylpentene-
1, etc., and not only homopolymerization but also random copolymerization and block copolymerization of these can be performed. Regarding copolymerization, polyunsaturated compounds such as conjugated dienes and non-conjugated dienes can also be used as the copolymerization olefin.

As the polymerization method, a so-called slurry polymerization method in which an inert hydrocarbon such as hexane or heptane is used as a solvent, a liquid phase polymerization method in which a liquefied monomer is used as a solvent, or a gas phase polymerization method in which a monomer is present as a gas phase can be used. .

The polymerization temperature is generally about 20 to 150 ° C, preferably 40 to 100 ° C.
The polymerization pressure is about atmospheric pressure to about 100 atmospheres, preferably about atmospheric pressure to about 50 atmospheres. The molecular weight of the polymer is controlled mainly by a method using hydrogen.

Experimental Example Example 1 (Production of Titanium-Containing Solid Catalyst Component) 50 ml of dehydrated and deoxygenated heptane was introduced into a 300 ml flask that had been sufficiently replaced with nitrogen, and then 0.1 mol of MgCl ₂ (magnesium chloride) and Ti (OBu) ₄ ( After introducing 0.2 mol of tetrabutoxytitanium), the mixture is reacted at 90 ° C. for 2 hours to obtain MgC
A hydrocarbon solution of l ₂ was prepared. Next, add 12 ml of methylhydrogen polysiloxane (20 cps) and add 4 at 40 ℃.
After reacting for a time, about 40 g of an off-white solid was deposited. The precipitated solid was thoroughly washed with heptane and analyzed, and it was found that the precipitated solid contained 14.3% by weight of MgCl ₂ .

20 g (MgCl ₂ = 30 mM) was sampled from this precipitated solid to prepare a slurry of component (A) containing 50 ml of heptane,
0.51 ml of 2-ethoxyethyl acetate (CH ₃ CO ₂ CH ₂ CH ₂ OC ₂ H ₅ /Mg=0.125) into the heptane slurry of this component (A)
(Molar ratio), and then triphenylchlorosilane 0.
44g ((C ₆ H ₅ ) ₃ SiCl / Mg = 0.05 molar ratio) and dibutoxydichlorotitanium 10 mM (Ti (OBu) ₂ Cl ₂ /Mg=0.33 molar ratio) were added all at once, and at 20 ° C for 2 hours. After the contact, the supernatant was removed and washed to obtain a mutual contact treated product between the components (A) to (C). 25 ml of a heptane solution containing 1.5 ml of TiCl ₄ (titanium tetrachloride) was added dropwise to this treated product, and the product was contacted at 50 ° C for 1.5 hours.
25 ml of I ₄ was added and the mixture was treated at 80 ° C. for 2 hours. And
The treatment under the same conditions with 25 ml of TiCl ₄ was repeated twice, and the solid was washed by decantation (heptane).
(5 times with 200 ml) to obtain a target titanium-containing solid catalyst component slurry. When a part of this slurry was sampled and heptane was evaporated to dryness and analyzed, 2.
It contained 85% by weight of titanium.

Reference Example 1 (Polymerization of Propylene) In an autoclave equipped with a stirrer having an internal volume of 1 liter, 500 ml of dried and degassed heptane, 107 mg of diphenyldimethoxysilane, 250 mg of triethylaluminum.
(Si / Al = 0.2 molar ratio) and 0.5 mg in terms of Ti atom from the above solid contact component slurry were introduced in this order under a propylene atmosphere, and 100 ml of hydrogen was added to initiate polymerization. Polymerization was carried out under conditions of propylene pressure of 7 kg / cm ² G, 70 ° C. and 3 hours. After the completion of the polymerization, residual monomers were purged, the polymer slurry was separated, and the amount of each polymer produced was determined by drying the powder polymer and concentrating the liquid.

Stereoregularity of this powder polymer (hereinafter referred to as product II)
Was determined by a boiling n-heptane extraction test. Also, all
II (ratio of the amount of boiling n-heptane insoluble polymer to the total amount of polymer produced) was determined by the following formula.

The results obtained are shown below.

Activity: 40.6 × 10 ⁴ (gpp / gTi): 11,700 (gpp / g solid catalyst) Attack production rate ^* : 0.58% Product II: 98.7% Total II: 98.2% BD (bulk density): 0.46 (g / cc) MFR : 2.2 (g / 10 min) * Attack production rate = (liquid-concentrated polymer / all-produced polymer) × 100 Example 2 (production of titanium-containing solid catalyst component) 20 g of precipitated solid obtained by the method of Example 1 (MgCl ₂ (= 30 mM)
Into a precipitated solid slurry of 100 ml of heptane.
Ethoxyethyl acetate 0.45 ml (CH ₃ CO ₂ C ₂ H ₄ OC ₂ H ₅ / Mg
(0.11 molar ratio), and then TiCl2 as the component (C).
₄ 3.0 ml was added and mutual contact treatment between components (A) to (C) was carried out at 25 ° C. for 1 hour. After washing the contact-treated product with heptane, 10 ml of TiCl ₄ was first added as a washing (D) to 50
After treatment at ℃ for 1 hour and removing the supernatant, Ti
The operation of adding 20 ml of Cl ₄ and performing contact treatment at 90 ° C. for 2 hours was repeated twice. After this treatment, the solid was washed by decantation to obtain the target titanium-containing solid catalyst component slurry. (Ti content = 3.52 wt%) Reference Example 2 (Polymerization of Propylene) Polymerization of propylene was carried out in the same manner as in Reference Example 1 except that the catalyst component of the present invention produced in Example 2 was used.

The obtained results are shown in Table 1.

Example 3 (Production of solid catalyst component containing titanium) 20 g of precipitated solid obtained by the method of Example 1 (MgCl ₂ = 30 mM)
Using, heptane 50ml to precipitate solids slurry in 2-ethoxyethyl acetate _{0.45ml (CH 3 CO 2 CH 2} CH 2 OC 2 H 5 / Mg
= 0.11 molar ratio), and then 5 ml (2 M / l solution of Ti (OBu) ₂ Cl ₂ (10
mM) for 30 minutes at 25 ° C, and then 1 ml of TiCl ₄
Mutual contact treatment between the components (A) to (C) was performed by additionally adding and continuing contact for 30 minutes. After washing this contact-treated product with heptane, first, as component (D), (TiCl ₄ 1.7 ml / heptane 25 ml) solution was added and treated at 50 ° C. for 1 hour, and then the supernatant was removed, and then TiCl ₄ 20 ml was added again. In addition, the operation of performing the contact treatment at 80 ° C. for 2 hours was repeated twice. After this treatment, the solid was washed by decantation to obtain the target titanium-containing solid catalyst component slurry.
(Ti content = 3.19 wt%) Reference Example 3 (Polymerization of Propylene) Polymerization of propylene was carried out in the same manner as in Reference Example 1 except that the catalyst component of the present invention obtained in Example 3 was used.

The obtained results are shown in Table 1.

Examples 4-5, Comparative Examples 1-2 (Production of Titanium-Containing Solid Catalyst Component) 20 g of precipitated solid (MgCl ₂ = 30 mM) obtained by the method of Example 1.
Using, heptane 50ml to precipitate solids slurry in 2-ethoxyethyl acetate _{4.09ml (CH 3 CO 2 CH 2} CH 2 OC 2 H 5 / Mg
(1.0 mol ratio = 1.0) and then as component (C) (TiCl ₄ 0.55
ml / heptane 25 ml) solution (Ti = 5 mM) was added dropwise over 2 hours at the mutual contact treatment temperature shown in Table 2, and after aging at the same temperature for 30 minutes, the components were washed (A) to (). C)
An inter-contact treated product between the two was obtained. To this product slurry was added each (TiCl ₄ 1.0 ml / heptane 25 ml) solution to give 20
After contacting at ℃ for 1 hour, the supernatant was removed, washed and washed again (TiCl
₄ 3.0 ml / heptane 25 ml) solution was added and after contacting at 50 ° C for 1 hour, the supernatant was removed and washed, and 20 ml of TiCl ₄ was added to add 8 ml.
The operation of performing the contact treatment at 0 ° C. for 2 hours was repeated 3 times.
After this treatment, the solid is washed by decantation to obtain the titanium-containing solid catalyst component slurry of the present invention (Examples 4 to 5).
And comparative catalyst component slurries (Comparative Examples 1 and 2) were obtained.

Reference Examples 4 to 7 (Polymerization of Propylene) Polymerization of propylene was carried out in the same manner as in Reference Example 1 except that the titanium-containing solid catalyst components obtained in Examples 4 to 5 and Comparative Examples 1 and 2 were used.

The obtained results are shown in Table 2.

Examples 6 to 8 (Production of catalyst component) 0.55 ml of TiCl ₄ used as the component (C) in Example 4
Instead of TiCl ₄ 0.22 ml (Ti = 2 mM) and SiCl ₄ 0.23 ml (S
A titanium-containing solid catalyst component slurry was obtained under the same conditions and methods as in Example 4, except that i = 2 mM) was also used in combination.

Reference Examples 8-10 (Polymerization of Propylene) Using the titanium-containing solid catalyst components obtained in Examples 6-8,
The diphenyldimethoxysilane used in Reference Example 1 was used as a polymerization-added Si compound shown in Table 3, and Si / Al (molar ratio) was set to the value shown in Table 3 (the amount of triethylaluminum used is 250 mg of a fixed amount). ) Polymerization of propylene was carried out in the same manner as in Reference Example 1 except for the above.

The results obtained are shown in Table 3.

Example 9 (Production of Titanium-Containing Solid Catalyst Component and Preliminary Polymerization Treatment Catalyst Thereof) A titanium-containing solid catalyst component was produced by the method and conditions of Example 2 and prepolymerization treatment was carried out. In the prepolymerization process, a heptane slurry was prepared using 3 g of titanium-containing solid catalyst component (Ti content: 3.42 wt%) (30 g solid catalyst / l slurry).
After adding 0.48 g of triethylaluminum (Al / Ti (molar ratio) = 2) at a temperature of 0 ° C., 6 g of propylene was introduced and contacted for 20 minutes to carry out.

Reference Example 11 (Polymerization of Propylene) Using the prepolymerization treatment catalyst of the present invention produced in Example 9,
Polymerization of propylene was carried out in the same manner as in Reference Example 1 by introducing each catalyst component under the temperature condition of 70 ° C.

The results obtained are shown below.

Activity: 27.8 × 10 ⁴ (gpp / gTi) 9500 (gpp / g solid catalyst) Attack production rate: 0.52% Product II: 98.4% Total II: 97.9% BD: 0.47 (g / cc) MFR: 2.5 (g / 10 Minutes)

[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. Component (A): magnesium halide-containing solid, component (B): (Where R is a C _1-12 hydrocarbon residue or A C _2-12 organic residue having a structural site represented by, R ¹ and R ² are each a C _1-12 alkyl group, aryl group, alkyl-substituted aryl group, or aryl-substituted alkyl group), And a component (C): a halogen compound of Si or Ti, is contacted with each other in a temperature range of 50 ° C. or lower, and then this is contacted with a component (D): a halogen compound of tetravalent titanium. A method for producing a catalyst component for α-olefin polymerization.