JPH0723407B2 - Catalyst component for propylene polymerization - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Technical Field The present invention relates to a catalyst component which provides a polymer having high activity and good polymer properties.

Conventionally, when a magnesium compound such as magnesium halide, magnesium oxyhalide, dialkylmagnesium, alkylmagnesium halide, magnesium alkoxide, or a complex of dialkylmagnesium and organoaluminum is used as a carrier for a transition metal compound such as a titanium compound, it becomes a highly active catalyst. , And many inventions have been proposed.

In these prior arts, the catalytic activity is high to some extent, but the polymer properties of the polymer produced are not sufficient, and improvement is desired. Polymer properties are extremely important in slurry polymerization, gas phase polymerization and the like. This is because if the polymer properties are poor, polymer adhesion in the polymerization tank and other problems may occur.

In such a method, it is common to use a large amount of a titanium halogen compound (particularly titanium tetrachloride) as a transition metal compound such as titanium so that the titanium compound is contained in the catalyst component. The basic unit is bad. This is extremely inconvenient for producing a catalyst. Many titanium halogen compounds that were not included as catalyst components need to be removed from the catalyst components, which necessitates a large amount of solvents, etc., leading to an increase in catalyst production costs, and unnecessary titanium. The halogen compound needs to be decomposed, but in that case, halogen gas, hydrogen halide, etc. are often generated, which is extremely bad in terms of environmental hygiene. Therefore, it is desired to improve the basic unit of titanium halogen compound.

By the way, as a prior art similar to the present invention (detailed later), there is one described in JP-A-55-104303.
According to this known technique, by using a phosphorus compound, the stereoregularity does not change even when the molecular weight (MFR) of the produced polymer changes. However, as far as the present inventors know, this known technique seems to have the following two problems.

(B) The stereoregularity of the produced polymer is insufficient and the isotacticity is only about 94%.

(B) A large amount of titanium halide (TiC
l ₄ ) is used.

[Outline of Invention]

SUMMARY OF THE INVENTION The present invention aims to provide a solution to the above-mentioned problems, and it is an object of the present invention to achieve the above-mentioned objects by a catalyst component composed of a specific component.

That is, the propylene polymerization catalyst component according to the present invention,
It is characterized by comprising a contact product of the following components (A) and (B).

Component (A) is of the formula Ti (OR ² ) _4- nXn (wherein R ² represents a hydrocarbon residue having 1 to 10 carbon atoms, X represents halogen, and n represents a number of 0 ≦ n ≦ 3). Represented titanium compound, formula Mg (OR)
_2- mXm (where R is a hydrocarbon residue having 1 to 10 carbon atoms,
(X represents halogen, m represents a number of 0 ≦ m ≦ 2, respectively)
A Ziegler-type catalyst solid component prepared by using as an essential component an electron-donating compound selected from a magnesium compound represented by and a phthalic acid ester and a phthalic acid halide.

Component (B) Phosphorus halogen compound.

Effects When the solid catalyst component according to the present invention is used as a transition metal component of a Ziegler catalyst to polymerize an olefin, a polymer polymer having high activity and good stereoregularity can be obtained.

Also, unexpectedly, a polymer with higher stereoregularity is obtained than when using a titanium halide compound such as titanium tetrachloride. The reason why such a polymer with high stereoregularity is obtained is not yet clear. Polymers with high stereoregularity are important for widening the application of polymer polymers.

And in order not to use the titanium halide compound,
It is not necessary to treat the titanium halide compound during the catalyst production, and the production cost can be greatly reduced, which is extremely advantageous in industrial production.

[Specific Description of the Invention]

Catalyst component and production thereof The catalyst component of the present invention is produced by contacting the components (A) to (B).

Ingredient (A) Ingredient (A) of the present invention is (i) the formula Ti (OR ² ) _4- nXn (wherein R ² is a hydrocarbon residue having 1 to 10 carbon atoms, X is halogen, and n is 0). And a titanium compound represented by the formula (b) formula Mg (OR) ₂₋ mXm (where:
R is a hydrocarbon residue having 1 to 10 carbon atoms, X is halogen, and m is a number of 0 ≦ m ≦ 2), and a magnesium compound represented by (c) phthalic acid ester and phthalic acid halide is selected. Any compound can be used as long as it is prepared by using the electron donating compound as an essential component and can be used as the solid component of the Ziegler type catalyst by satisfying these conditions.

Here, the preparation using (a) to (c) as essential components means that the components (a) to (c) are used as manufacturing raw materials.
It does not mean only to be prepared using only. Therefore, the component (A) of the present invention includes the components (a) to
In addition to these, other components such as silicon, aluminum, and boron can be used as long as they are prepared by using (C), and these can remain in the component (A). is there.

The component (A) can be produced by any purposeful method. Specific examples of suitable production methods are as follows.

(1) Manufacturing method (i) A method of bringing magnesium halide, a titanium compound containing an OR ² group, and an electron donating compound into contact with each other.

(Ii) A method of contacting an alkoxy-containing magnesium compound, an OR ² group-containing titanium compound, an electron-donating compound and a halogen source compound when the above compounds do not have halogen.

(Iii) A method of bringing an electron donor and a halogen compound of silicon into contact with a solid component obtained by contacting magnesium halide, titanium tetraalkoxide and a specific polymer silicon compound.

(Iv) A method in which a magnesium compound (preferably a halogen compound) is dissolved in titanium tetraalkoxide and an electron donor and then deposited.

These production methods are well known for producing Ziegler-type solid catalyst components. The following documents can be cited as disclosures of these manufacturing methods. JP-B-52-36913, JP-A-54-40293, JP-A-58-32605,
58-183709, 59-149905, etc.

Of these, preferred are (i) and (iv).

(2) Raw Material (a) As an example of the titanium compound used for producing the component (A), a compound represented by the following formula can be given.

Ti (OR ² ) _4- nXn (wherein R ² is a hydrocarbon residue having 1 to 10 carbon atoms, X represents halogen, and n represents a number of 0n3).

Specific _{examples, Ti (OC 2 H 5)} 4, Ti (O-iC 3 H 7) 4, Ti (O-nC 4 H 9) 4, Ti (O-nC 6 H 13) 4, Ti (O _{-nC 3 H 7) 4, Ti} (O-iC 4 H 9) 4, Ti (O-nC 8 H 17) 4, Ti _{[OCH 2 CH (C 2 H 5} ) C 4 H 9 ] _4, Ti ( _{OC 2 H 5) 3 Cl,} Ti (OC 2 H 5) 2 Cl 2, Ti (O-nC 4 H 9) 3 Cl, Ti (O-nC 4 H 9) 2 Cl 2, Ti (OC 2 H 5 _{) 3 Br, Ti (OC 6} H 13) Cl 3, Ti (O-nC 8 H 17) 2 Cl 2, and the like.

Further, the titanium compound for the component (A) may be a condensate of the above compounds. For example, a compound represented by the following formula can be given.

(Here, R ^{3 to} R ⁶ may be the same or different and have from 1 to 1 carbon atoms.
It is a hydrocarbon residue of about 10 and n represents a number of about 2 to 10.) Specific examples of such a condensate include n = 2, n = 4, and n = 10 of isopropoxide. Examples of the polymer include normal butoxide n = 2, n = 4, n = 7, and n = 10.

(B) The magnesium compound used for producing the component (A) has the formula Mg (OR) ₂₋ mXm (wherein R is a hydrocarbon residue having 1 to 10 carbon atoms, X is halogen,
m is a magnesium compound represented by 0 ≦ m ≦ 2). Specific examples include magnesium halide, dialkoxy magnesium, and alkoxy magnesium halide.

Chlorine is a suitable halogen for the "halide" in these compounds. R in the above formula is phenyl having 1 to 10 carbon atoms or phenyl. Particularly preferred among these are magnesium halides, especially magnesium chloride.

(C) The electron donor that can be used for producing the solid component (A) is selected from phthalic acid esters and phthalic acid halides. Specific examples thereof include diethyl phthalate, dibutyl phthalate, diheptyl phthalate, and phthaloyl chloride. Two or more kinds of these electron donors can be used.

(D) Optional component It is also possible to contain other components as an optional component, if necessary. Examples of compounds used for such purpose include silicon halides such as SiCl ₄ , silicon compounds such as lower alkylhalosilanes such as CH ₃ SiCl ₄ and alkylhydrogenpolysiloxane, aluminum halides such as AlCl ₃ and lower alkoxyaluminum. Halides such as Al (OC ₂ H ₅ ) ₂ Cl, lower alkoxy aluminum such as Al (OC ₂ H ₅ ) ₃ , Al (OiC ₃ H ₈ ).
₃ , such as aluminum compounds, lower alkoxyboron such as B (OCH ₃ ) ₃ , B (OC ₂ H ₅ ) ₃ , B (OnC ₄ H ₉ ) ₃
And the like, such as boron compounds.

Of these, preferred are silicon compounds, particularly alkylhydrogenpolysiloxanes having the structural unit represented by the formula below.

Here, R ⁷ is a hydrocarbon residue having about 1 to 10 carbon atoms, particularly about 1 to 6 carbon atoms. The polymer silicon compound preferably has a viscosity of about 0.1 to 100 centistokes.

Specific examples of the polymer silicon compound having such a structural unit include methylhydrogenpolysiloxane,
Examples thereof include ethylhydrogenpolysiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane.

(3) Amount Ratio The amount of each component constituting the component (A) may be any amount as long as the effects of the present invention can be recognized, but generally, the following range is preferable. The amount of the titanium compound used is in the range of 1 × 10 ^{−3 to} 1000, preferably 0.01 to 10 in terms of molar ratio with respect to the magnesium compound, and the amount of the electron-donating compound used is in the molar amount relative to the magnesium compound. 1 in ratio
It is in the range of x10 ^{-3 to} 100, preferably in the range of 0.01 to 10. The amount of halogen used is in the range of 1 to 100, preferably in the range of 2 to 50, based on magnesium, in the component (A). The amount of the optional component used is arbitrary as long as the effects of the present invention are not impaired and the effects of use thereof are recognized, but in the case of a typical methylhydrogenpolysiloxane, the molar ratio to the above-mentioned magnesium compound is a molar ratio. It is in the range of 1 × 10 ^{−2 to} 100, preferably in the range of 0.1 to 10, and more preferably in the range of 1 to 5.

Component (B) Component (B) is a phosphorus-halogen compound. Generally, a compound represented by the following formula is used.

PXa ▲ R ⁸ _b ▼ (OR ⁹ ) c or POXd ▲ R ¹⁰ _e ▼ (OR ¹¹ ) f where X is a halogen, and R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ each have about 1 to 10 carbon atoms. Represents a hydrocarbon residue, a + b + c = 3 or 5, 0 <a ≦ 5, 0 ≦ b <5,0
≦ c <5, d + e + f = 3, 0 <d ≦ 3, 0 ≦ e <3,
0 ≦ f <3.

Specific examples of the compounds represented by the formula of the former, _{(b) PCl 3, PCl 5, PBr} 3, PBr 5, phosphorus halides and the like, _{(ii) P (C 2 H 5)} 2 Cl, P (CH ₃ ) Cl ₂ , P (C ₆ H ₅ ) ₂ Cl, P (n-C ₄ H ₉ ) Br ₂ , alkyl phosphorus halides such as (C) P (OCH ₃ ) Cl ₂ , P (OC ₂ H ₅ ) Alkoxyhalogenated phosphorus such as Cl ₂ , P (OCH ₃ ) ₂ Cl, P (O-nC ₄ H ₉ ) Cl ₂ and P (OC ₆ H ₅ ) Cl ₂ are available, which are represented by the latter formula. Specific examples of the compound to be used include (d) oxyhalogenated phosphorus such as POCl ₃ and POBr ₃ , and (e) oxyalkyl halogenated phosphorus such as PO (C ₂ H ₅ ) Cl ₂ and PO (CH ₃ ) Cl _2. ,
(F) Oxyalkoxy halides such as PO (OCH ₃ ) Cl ₂ and PO (OC ₂ H ₅ ) Cl ₂ are available. Among these, preferred are PCl ₃ , PCl ₅ , POCl ₃ , PBr ₃ , P (OCH ₃ ) Cl ₂ , P (C ₂ H ₅ ) Cl ₂ and the like, and more preferred are PCl ₃ , P
Cl ₅ and POCl ₃ .

Contact of Component (A) with Component (B) The catalyst component for olefin polymerization according to the present invention is a contact product of the above components (A) and (B).

The contact conditions of the component (A) and the component (B) may be arbitrary as long as the effect of the present invention is recognized, but generally, the following conditions are preferable. Contact temperature is -50 ℃ to 200 ℃
The degree is preferably 0 ° C 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, and the like, 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, and polysiloxanes. The atmosphere at the time of contact is preferably made of an inert gas.

The amount ratio of the component (A) and the component (B) is in the range of 1 × 10 ^{−3 to} 100 in terms of the atomic ratio of phosphorus of the component (B) to the titanium component constituting the component (A) (phosphorus / titanium). , Preferably 0.1
Within the range of 10 to 10.

Olefin Polymerization Catalyst Formation The catalyst components of the present invention can be used in the polymerization of olefins in combination with an organometallic compound that is a cocatalyst. Any of the organometallic compounds of metals of Groups I to IV of the Periodic Table known as cocatalysts can be used. In particular, organic aluminum compounds are preferable.

Specific examples of the organoaluminum compound include those represented by the following formula.

▲ R ¹² _3-n ▼ AlXn or ▲ R ¹² _3-m ▼ Al (OR ¹⁴ ) m (wherein R ¹² and R ¹³ may be the same or different and are a hydrocarbon residue having about 1 to 20 carbon atoms or Hydrogen, R ¹⁴ is a hydrocarbon residue having about 1 to 20 carbon atoms, X is halogen, n and m are 0n <2 and 0m, respectively.
The number is 1. ) Specific examples include (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,
Alkyl aluminum halides such as (c) Diethyl aluminum hydride, Dialkyl aluminum hydrides such as diisobutyl aluminum hydride,
(D) Alkyl aluminum alkoxides such as diethyl aluminum ethoxide, diethyl aluminum butoxide, diethyl aluminum phenoxide, and the like.

These organoaluminum compounds (a) to (c) are replaced with other organometallic compounds such as ▲ R ¹⁵ _3-a ▼ A l (OR ¹⁶ ) a (1a3, R ¹⁵ and
R ¹⁶ is a hydrocarbon residue which may be the same or different and has about 1 to 20 carbon atoms. It is also possible to use an alkylaluminum alkoxide represented by the formula (1). For example, combination of triethylaluminum and diethylaluminum ethoxide, combination of diethylaluminum monochloride and diethylaluminum ethoxide, combination of ethylaluminum dichloride and ethylaluminum diethoxide, triethylaluminum, diethylaluminum ethoxide and diethylaluminum chloride. It can be used in combination with.

The amount of these organometallic compounds used is not particularly limited,
The weight ratio with respect to the solid catalyst component of the present invention is preferably within the range of 0.5 to 1000.

In order to improve the stereoregularity of an olefin polymer having 3 or more carbon atoms, it is effective to add and coexist an electron donating compound such as an ether, an ester, an amine or a silane compound during the polymerization. The amount of the electron-donating compound used for such a purpose is 0.
It is 001 to 2 mol, preferably 0.01 to 1 mol.

Among the electron-donating compounds used as the so-called “external donor”, preferred are piperidine, C—OR group-containing compounds and Si—OR group-containing compounds. Specifically, 2, 2, 6,
6, tetramethylpiperidine, Etc.

Polymerization The catalyst system of the present invention is applicable to homopolymerization of propylene or copolymerization of propylene with olefins such as ethylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1. In the case of copolymerization, it is possible to carry out copolymerization with up to 30% by weight with respect to propylene of said olefins, in particular ethylene. Copolymerization with other copolymerizable monomers (for example, diolefin) can also be performed.

The catalyst system of the present invention is applied not only to ordinary slurry polymerization, but also 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. 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 ° C. to 150 ° C., and hydrogen can be supplementarily used as a molecular weight regulator at that time.

Experimental Example Example-1 Production of Component (A) A fully dried and nitrogen-substituted ball mill having a volume of 0.4 liter was filled with 40 12 mmφ stainless steel balls,
20 g of MgCl ₂ , 6.5 ml of diheptyl phthalate and 5.0 g of Ti (OBu) ₂ Cl ₂ were introduced, and the mixture was pulverized with a rotary ball mill for 48 hours. After the pulverization was completed, the mixed pulverized product was taken out from the mill in a dry box and used as a component (A).

Contact of component (A) and component (B) 50 ml of sufficiently produced n-heptane was introduced into a flask sufficiently replaced with nitrogen, and 5 g of the component (A) produced above was used as the component (B). 1 gram of PCl ₅ was introduced and contacted at 100 ° C. for 6 hours. After the contact was completed, it was washed with n-heptane to obtain a catalyst component. When a part of it was taken out and analyzed, the titanium content of the catalyst component was 1.43 weight percent.

Polymerization of Propylene 500 ml of fully dehydrated and deoxygenated n-heptane, 125 mg of triethylaluminum, 53.6 mg of diphenyldimethoxysilane, and the above synthesized, were placed in a stainless steel autoclave with an internal volume of 1.5 liter equipped with a stirring and temperature control device. The catalyst component
Introduced 15 mg. Then, 60 ml of H ₂ was introduced, the temperature was raised and the polymerization pressure was 5 kg / cmG, and the polymerization temperature was 75.
Polymerization was performed under the conditions of ° C and polymerization time = 2 hours. After the polymerization was completed, the obtained polymer slurry was put on a filter to separate the polymer, and the polymer was dried.

79.4 grams of polymer were obtained. On the other hand, from the excess fluid,
86 grams of polymer were obtained. From the boiling heptane extraction test, the total product II (hereinafter abbreviated as T-II) was 94.3% by weight. The MFR was 7.6 (g / 10 min) and the bulk density of the polymer was 0.41 (g / cc).

Example-2 Synthesis of Component (A) n was dehydrated and deoxygenated in a flask that had been sufficiently replaced with nitrogen.
- introducing heptane 200 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 40 ° C., and then 12 ml of methylhydropolysiloxane (20 centistokes) was added and the reaction was carried out for 3 hours. The produced 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 introduced into the flask at 30 ° C. for 30 minutes, and reacted at 70 ° C. for 3 hours. After completion of the reaction, it 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 completion of the reaction, it was washed with n-heptane (synthesis of component A). Then, 0.5 gram of PCl ₅ was introduced and reacted at 100 ° C. for 6 hours. After completion of the reaction, it was washed with n-heptane. The titanium content in the obtained catalyst component was 0.99 weight percent.

Polymerization of Propylene Polymerization was carried out under the same conditions as in Example 1 except that the amount of diphenyldimethoxysilane used was 26.8 mg. 226 grams of polymer were obtained, MFR = 4.3 (g / 10 min), T-II = 99.0 weight percent, polymer bulk specific gravity = 0.47 (g / cc).

Example-3 Production of Component (A) A ball mill purified in the same manner as in Example-1 was filled with balls in the same manner as in Example-1, and 12 g of Mg (OC ₂ H ₅ ) Cl was added.
Phthalyl chloride 3.1 ml, Ti (OBu) Cl ₃
3.7 g of each was introduced and crushed by a rotary ball mill for 80 hours. After the pulverization was completed, the mixed pulverized product was taken out from the mill in a dry box to obtain a component (A).

Contact of component (A) and component (B) 50 ml of sufficiently purified n-heptane was introduced into a flask that had been sufficiently replaced with nitrogen, and 5 g of the component (A) produced above and PCl as the component (B). 1 gram of ₃ was introduced and contact was performed at 100 ° C. for 3 hours. After the contact was completed, it was washed with n-heptane to obtain a catalyst component. The titanium content of the catalyst component was 1.68 weight percent.

Polymerization of Propylene Polymerization was carried out in the same manner as in Example 1 except that 52 mg of phenyltriethoxysilane was used instead of diphenyldimethoxysilane.

68.5 grams of polymer were obtained, MFR = 4.6 (g / 10 min),
T-II = 95.8 weight percent, MFR = 7.8 (g / 10 minutes),
The bulk density of the polymer was 0.37 (g / cc).

Example-4 In the production of the component (A) of Example-2, except that diethyl phthalate was used instead of phthaloyl chloride,
We manufacture under exactly the same conditions and use POCl as component (B)
_The catalyst was prepared in exactly the same manner except that ₃ 0.7 grams were used.

Polymerization of propylene was also carried out under exactly the same conditions as in Example-2. 132 grams of polymer were obtained, MFR = 7.1 (g / 10
Min), T-II = 98.6 weight percent, and polymer bulk specific gravity = 0.45 (g / cc).

Comparative Example-1 In the preparation of the catalyst component of Example-2, the catalyst component was prepared in exactly the same manner except that 0.004 mol of ethyl benzoate was used instead of phthaloyl chloride. In the polymerization of propylene of Example-2, phenyltrimethoxysilane 2 was used instead of diphenyldimethoxysilane.
Polymerization was carried out under exactly the same conditions except that 1.7 mg was used. 81.4 grams of polymer were obtained, MFR =
7.8 (g / 10 min), T-II = 95.1 weight percent, and polymer bulk specific gravity = 0.42 (g / cc).

Examples-5 to 7 In the production of the catalyst component of Example-2, PC of the component (B)
The catalyst components were prepared in exactly the same manner except that the amount of l ₅ used was as shown in Table 1. Further, propylene was polymerized in exactly the same manner. The results are shown in Table-1.

Examples-8 to 9 In the production of the catalyst component of Example-2, the catalyst component was produced in exactly the same manner except that the phosphorus compound shown in Table 2 was used instead of PCl ₅ , and the polymerization of propylene was also conducted in exactly the same manner. I went to.

The obtained results were as shown in Table-2.

Comparative Examples-2 to 4 In the production of the component (A) of Example-1, the production was carried out in the same manner except that the compounds shown in Table 3 were used instead of diheptyl phthalate and Ti (OBu) ₂ Cl _2. The propylene was polymerized in exactly the same manner. The results are shown in Table-3.

Example 10 Production of Component (A) A fully deaerated flask was thoroughly degassed and purified with n-
100 ml of heptane was added, then 0.05 mol of MgCl ₂ , 0.1 mol of Ti (O-nC ₄ H ₉ ) ₄ and n-C ₄ H ₉ OH were added.
When 0.2 mol of each was introduced and stirred at 90 ° C. for 2 hours, it was completely dissolved and a uniform solution was obtained. The temperature was lowered to 70 ° C., 0.3 mol of SiCl ₄ was introduced, and the mixture was stirred for 2 hours. A solid component was deposited, and the solid component was thoroughly washed with heptane. Then, 0.006 mol of phthalic acid chloride was introduced at 70 ° C. and reacted for 2 hours. After completion of the reaction, it was thoroughly washed with n-heptane to obtain a component (A).

Contact between the component (A) and the component (B) A purified nitrogen-heptane was placed in a flask which had been sufficiently replaced with nitrogen.
Introducing 50 ml, the component (A) produced above
4g and PCl ₅ 0.6g respectively, 100 ℃
For 6 hours. After the contact was completed, it was washed with n-heptane to obtain a catalyst component. The titanium content of the catalyst component is 1.71.
It was weight percent.

Polymerization of Propylene Polymerization of propylene was carried out under the same conditions as in Example-1. 138 grams of polymer were obtained, T-II = 97.1 weight percent, MFR = 5.3 (g / 10 min), polymer bulk specific gravity = 0.39 (g / cc).

[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 component for propylene polymerization, which comprises a contact product of the following components (A) and (B). Component (A) is of the formula Ti (OR ² ) _4- nXn (wherein R ² represents a hydrocarbon residue having 1 to 10 carbon atoms, X represents halogen, and n represents a number of 0 ≦ n ≦ 3). Represented titanium compound, formula Mg (OR)
_2- mXm (where R is a hydrocarbon residue having 1 to 10 carbon atoms,
(X represents halogen, m represents a number of 0 ≦ m ≦ 2, respectively)
A Ziegler-type catalyst solid component prepared by using as an essential component an electron-donating compound selected from a magnesium compound represented by and a phthalic acid ester and a phthalic acid halide. Component (B) Phosphorus halogen compound.