JPH06122717A - Production of alpha-olefin polymer - Google Patents

Abstract

PURPOSE:To provide a method by which a highly stereoregular polymer can be obtained in high yield. CONSTITUTION:This production method comprises polymerizing an alpha-olefin in the presence of a catalyst comprising a combination of a solid catalyst component (A) and an organoaluminum compound and adding an organic carboxylic acid to the system before the amount of the polymer yielded exceeds 5% of the intended final polymer amount, the component (A) containing as the essential ingredients titanium, magnesium, a halogen, and an electron-donating organosilicon compound represented by the formula R<1>R<2>3-nSi(OR<3>)n (wherein R<1> is a branched or alicyclic hydrocarbon residue; R<2> is a branched, alicyclic, or linear hydrocarbon residue; R<3> is a branched or linear hydrocarbon residue; and 2<=n<=3).

Description

Detailed Description of the Invention

[Background of the Invention]

TECHNICAL FIELD The present invention relates to a method for producing an α-olefin polymer. More specifically, the present invention relates to a catalyst comprising a combination of a specific solid catalyst component and an organoaluminum compound, and when carrying out the polymerization of an α-olefin having 3 or more carbon atoms, the content of the total polymer is 0 to 5%. The present invention relates to a method for producing a polymer of α-olefin, in which a polymer having high stereoregularity is obtained in an extremely high yield by adding an organic carboxylic acid before the formation of

[0002]

2. Description of the Related Art Recently, solid components containing titanium, magnesium and halogen as essential components have been used to
Many proposals have been made to produce a highly stereoregular polymer of propylene in a high yield (see, for example, JP-A-57-57).
63310, 57-63311, 57-633.
No. 12, No. 58-138706, No. 58-13871.
No. 1, 58-138705, etc.). However, to the knowledge of the inventors, the activity of these catalyst systems has not yet reached a satisfactory level and it was thought that further improvement was needed. By the way, a method of adding an organic carboxylic acid to a polymerization catalyst system comprising a polymerization catalyst having a high stereoregularity and an organoaluminum compound has already been disclosed in JP-A-61-69821. It is intended to improve the properties of the polymer by adding an organic carboxylic acid as a catalyst deactivator at the copolymerization stage in producing the polymer.

[0003]

[Means for solving the problem]

SUMMARY OF THE INVENTION The present invention is based on the fact that a specific solid catalyst component and an organoaluminum compound component are combined with an organic carboxylic acid as a third component to obtain a catalyst system having higher activity than ever before. Is.

<Summary> That is, in the method for producing an α-olefin polymer according to the present invention, when the α-olefin is brought into contact with a catalyst formed by combining the following components (A) and (B) for polymerization, , 0 to 5% of total polymer production
The following component (C) is added before the formation of. Component (A): Solid catalyst component R ¹ R ² _3-n Si (OR ³ ) _n (1 containing titanium, magnesium, halogen, and the organosilicon type electron-donating compound represented by the formula (1) as essential components. [Wherein R ¹ is a branched or cyclic aliphatic hydrocarbon residue, R ² is a branched or cyclic aliphatic or linear hydrocarbon residue, and R ³ is a branched or linear hydrocarbon residue. Group, n is 2 ≦
n ≦ 3. ] Component (B): Organoaluminum Compound Component (C): Organic Carboxylic Acid

<Effect> According to the present invention, a highly crystalline propylene polymer can be obtained in an extremely high yield, so that the catalyst cost can be reduced and the crystallinity is higher than that of the conventional catalyst. Since polypropylene can be obtained,
It is preferably used for applications such as automobile parts, home electric appliance parts, and packaging materials for which high rigidity is required. Since it is said that the organic carboxylic acid acts as a deactivator for the Ziegler type catalyst, it is unexpected that the organic carboxylic acid acts as a catalyst activity improver in the present invention.

[Detailed Description of the Invention] α- in the present invention
In the method for producing an olefin polymer, 0 to 5% of the production amount of the entire polymer is produced when an α-olefin is polymerized in the presence of a catalyst formed by combining the component (A) and the component (B). Up to the point of time, component (C) is added.

[Catalyst] The catalyst used in the present invention is a combination of specific components (A), (B) and (C). Here, "combined" does not mean that the components are only those listed (that is, A, B, and C), and other components within a range that does not impair the effects of the present invention. It is to be understood that this does not exclude the coexistence of.

<Component (A)> The component (A) is a solid catalyst component R ¹ R ² containing titanium, magnesium, halogen and an organosilicon type electron-donating compound represented by the formula (1) as essential components. _3-n Si (OR ³ ) _n (1) [wherein R ¹ is a branched or cyclic aliphatic hydrocarbon residue, R ² is a branched, cyclic aliphatic or linear hydrocarbon residue, R ³ is a branched or linear hydrocarbon residue, and n is 2 ≦
n ≦ 3. ] Here, "containing as an essential component" means that other than the four listed components may contain other purposeful elements, and each of these elements exists as a purposeful arbitrary compound. And that these elements may exist as bonded to each other.

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 and magnesium carboxylate. can give.
Of these, magnesium halide is preferable. The titanium compound serving as the titanium source is, for example, a compound represented by the general formula T
i (OR ¹ ) _4-n X _n (wherein R ¹ is a hydrocarbon residue, preferably having about 1 to 10 carbon atoms,
X represents halogen, and n represents a number of 0 ≦ n ≦ 4. ).

Specific examples of such titanium compounds include, for example, TiCl ₄ , TiBr ₄ , Ti (OC _{2
H 5) Cl 3, Ti (} OC 2 H 5) 2 Cl 2, Ti (O
_{C 2 H 5) 3 Cl,} Ti (O-iC 3 H 7) Cl 3, T
_{i (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) (O-nC 4 H} 9) 2 Cl, Ti (O-nC
_{4 H 9) 3 Cl, Ti} (O-nC 6 H 5) Cl 3, Ti
_{(O-iC 4 H 9)} 2 Cl 2, Ti (O-nC
₅ H ₁₁ ) Cl ₃ , Ti (O-nC ₆ H ₁₃ ) Cl ₃ ,
_{Ti (OC 2 H 5) 4} , Ti (O-nC 3 H 7) 4, T
_{i (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} and _{Ti [O-CH 2 CH (} C 2 H 5)
C ₄ H ₉ ] _{4 and the} like.

As the titanium compound, a complex compound of TiX ' ₄ (here, X'represents halogen) and an electron donating compound (detailed later) can also be used. Specific examples of such complex compounds include, for example, 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 CO
Cl, 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
And such as TiCl ₄ · _{C 4 H 4} O and the like. Among these titanium compounds, TiCl ₄ and Ti (O-nC ₄ H ₉ ) ₄ are preferable.

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

The halogen contained in the constituents may be fluorine, chlorine, bromine, iodine or a mixture thereof, with chlorine being particularly preferred. It is essential that the electron-donating compound is an organosilicon compound represented by the formula (1). R ¹ R ² _3-n Si (OR ³ ) _n (1) Here, R ¹ is a branched or cyclic aliphatic hydrocarbon residue, preferably having 3 to 8 carbon atoms, and having a secondary α carbon. A tertiary branched or cyclic aliphatic hydrocarbon residue, particularly preferably a branched hydrocarbon residue having 4 to 6 carbon atoms and having a secondary or tertiary α carbon, R ² is R ¹ A branched or cyclic aliphatic or straight chain hydrocarbon residue which is the same as or different from
R ³ is a branched or linear hydrocarbon residue having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, and n is 2 ≦ n ≦ 3.

Specific examples of the silicon compound include the following substances. (CH ₃ ) ₃ CSi (CH ₃ ) (OCH ₃ ) ₂ , (CH
₃ ) ₃ CSi (CH (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 , (C
H ₃ ) (C ₂ H ₅ ) CHSi (CH ₃ ) (OC
_{H 3) 2, ((CH} 3) 2 CHCH 2) 2 Si (OCH
₃ ) ₂ , (CH ₃ ) ₃ CSi (OCH ₃ ) ₃ , (C
_{H 3) 3 CSi (OC 2} H 5) 3, (C 2 H 5) 3 CS
_{i (OCH 3) 3, (} CH 3) (C 2 H 5) CHSi
(OCH ₃ ) ₃ , (C ₂ H ₅ ) (CH ₃ ) ₂ CSi (O
C ₂ H _{5) 3,}

[Chemical 1]

The electron-donating compound is preferably used in combination with the following (a) organic acid ester or (b) organic acid halide, and the organic acid ester and the formula (1) are particularly preferable. It is a combination of various organic silicon compounds. These can be used at the same time as the catalyst preparation or in separate processing steps. As the organic acid ester, an aliphatic carboxylic acid ester, for example,
Ethyl acetate, phenyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, methyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate,
Methyl methacrylate and ethyl crotonate, ethyl cyclohexylcarboxylate and the like, and aromatic carboxylic acid esters such as methyl benzoate and ethyl benzoate.
Propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate,
Examples thereof include amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, diethyl phthalate and diheptyl phthalate.

Examples of the organic acid halide include aliphatic carboxylic acid halides such as acetyl chloride, and aromatic carboxylic acid halides such as benzoyl chloride, toluic acid chloride, anisic acid chloride, phthaloyl chloride and isophthaloyl chloride. be able to.

The amounts of the above-mentioned components used may be arbitrary as long as the effects of the present invention can be recognized, but generally the following ranges are preferable. The titanium compound is used in a molar ratio of 1 × 10 ⁻⁴ to the amount of the magnesium compound used.
The range of 100 is preferable, and the range of 0.01 to 10 is more preferable. When a compound therefor is used as a halogen source, the amount used is 1 × in molar ratio with respect to the amount of the magnesium compound used, regardless of whether the titanium compound and / or the magnesium compound does not contain halogen. The range of 10 ^{−4 to} 1000 is preferable,
The range of 0.1 to 100 is more preferable. The amount of silicon and aluminum compound used is preferably in the range of 1 × 10 ⁻³ to 10 and more preferably in the range of 0.01 to 1 with respect to the amount of the magnesium compound used. The amount of the electron-donating compound used is preferably in the range of 1 × 10 ⁻³ to 10 and more preferably in the range of 0.01 to 5 with respect to the amount of the magnesium compound used.

The component (A) is produced by using the above-mentioned components by the following production method, for example. (A) A method in which a magnesium halide is optionally contacted with an electron donating compound and a titanium compound. (B) A method of treating alumina or magnesia with a phosphorus halide compound and contacting it with a magnesium halide, an electron donating compound, or a titanium halogen-containing compound. (C) A method in which a titanium halogen compound and / or a halogen compound of silicon are brought into contact with a solid component obtained by bringing magnesium halide, titanium tetraalkoxide and a specific polymer silicon compound into contact with each other. As the polymer silicon compound, those represented by the following formula are suitable.

[Chemical 2] (Here, R is a hydrocarbon residue having about 1 to 10 carbon atoms, n
Indicates a degree of polymerization such that the viscosity of the polymer silicon compound is about 1 to 100 centistokes.) Specific examples of such polymer silicon compound include methyl hydrogen polysiloxane, ethyl hydrogen polysiloxane, and phenyl. Hydrogen polysiloxane, cyclohexyl hydrogen polysiloxane,
1,3,5,7-Tetramethylcyclotetrasiloxane and 1,3,5,7,9-pentamethylcyclopentasiloxane are preferred. (D) A method in which a magnesium compound is dissolved in titanium tetraalkoxide and an electron-donating compound, and the 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 donating compound and a titanium compound are brought into contact therewith as necessary. (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-donating compound. Among the methods for producing the above component (A), (a) or (c)
Is preferred.

The component (A) used in the present invention may be the solid component obtained as described above as it is, or the solid component may be brought into contact with olefins in the presence of an organoaluminum compound for prepolymerization. May be obtained by performing.

When the component (A) is preliminarily polymerized, the conditions for prepolymerizing the olefins for producing the component (A) are not particularly limited, but the following conditions are generally used. preferable. The polymerization temperature is preferably 0 to 80 ° C, more preferably 10 to 60 ° C. As the polymerization amount, 0.001 to 50 g of olefins is preferably polymerized per 1 g of the solid component, and 0.1 to 10 g of olefins is more preferably polymerized.

As the organoaluminum compound component which may be used in the prepolymerization, those generally known as Ziegler type organoaluminum compounds can be used. As a specific example, the compound shown in the section of the description of the component (B) described later, that is, an organoaluminum compound can be used.

The amount of the organoaluminum component used during the prepolymerization is Al / T relative to the Ti component in the solid component (A).
The i (molar ratio) is preferably from 1 to 20, more preferably from 2 to 10.

Examples of olefins used in the prepolymerization include ethylene, propylene, 1-butene, 1-hexene and 3-methyl-1-butene.

<Component (B)> The component (B) is an organoaluminum compound. Specific examples of organoaluminum compounds suitable for use as component (B) 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 each is a hydrocarbon residue or hydrogen atom having about 1 to 20 carbon atoms, R
⁷ is a hydrocarbon residue, X is a halogen, and n and m are 0 ≦ n <3 and 0 <m <3, respectively). Specifically, (a) trialkylaluminum, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum and tridecylaluminum, etc., (b) alkylaluminum halide, for example, diethylaluminum monochloride, (C) Dialkyl aluminum hydrides such as diisobutyl aluminum monochloride, ethyl aluminum sesquichloride and ethyl aluminum dichloride, such as diethyl aluminum hydride and dibutyl aluminum hydride,
(D) Aluminum alkoxides such as diethyl aluminum ethoxide and diethyl aluminum phenoxide.

In addition to these organoaluminum compounds (a) to (d), other organometallic compounds such as R ⁸ _3-a Al
(OR ⁹ ) _a (where 1 ≦ a ≦ 3, R ⁸ and R ⁹ are
A hydrocarbon residue having about 1 to 20 carbon atoms, which may be the same or different. ) Can be used in combination with the alkylaluminum alkoxide. For example, combined use of triethyl aluminum and diethyl aluminum alkoxide, combined use of diethyl aluminum monochloride and diethyl aluminum ethoxide, combined use of ethyl aluminum dichloride and diethyl aluminum ethoxide, combined use of triethyl aluminum and diethyl aluminum ethoxide and diethyl aluminum monochloride, etc. Can be given.

<Component (C)> The component (C) is an organic carboxylic acid. As such a component (C), a monovalent or polyvalent organic carboxylic acid having about 1 to 15 carbon atoms is preferable. Specifically, (a) an aliphatic monocarboxylic acid having about 1 to 15 carbon atoms including the carbon number of the carboxyl group,
For example, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caprylic acid, pivalic acid, acrylic acid, methacrylic acid, crotonic acid, monochloroacetic acid, etc. Dicarboxylic acids, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, etc.
A cycloaliphatic carboxylic acid, such as cyclohexane monocarboxylic acid, cyclohexene monocarboxylic acid and cis-1,2-cyclohexanedicarboxylic acid, (d)
Similarly, an aromatic monocarboxylic acid having about 7 to 15 carbon atoms, for example, benzoic acid, toluic acid, anisic acid, cinnamic acid, etc. (e) Similarly, an aromatic dicarboxylic acid having about 8 to 15 carbon atoms, for example, Mention may be made of phthalic acid, isophthalic acid and terephthalic acid.

Of these, carboxylic acids having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, are preferred, and 1 to 1 carbon atoms are preferred.
A carboxylic acid of 5 is particularly preferred. Among the carboxylic acids, monocarboxylic acids are preferable, and aliphatic monocarboxylic acids are more preferable. These compounds may contain a functional group other than the carboxyl group as long as the effects of the present invention are not impaired.

The ratio of the component (C) used can be selected within a wide range, but the molar ratio to the organoaluminum component is usually 0.01 to 0.8, preferably 0.05 to.
The range is 0.5.

<Preparation of Olefin Polymerization Catalyst> The catalyst used in the present invention is a combination of the component (A), the component (B) and the component (C) (the meaning of "combined" means the component (A ) And component (B) as described above), the present invention has a feature in this combination. That is, in the method for producing an olefin polymer of the present invention, 0 to 5% of all polymers are produced when the α-olefin is polymerized in the presence of the catalyst composed of the solid catalyst component and the organoaluminum compound component. It is important to add the organic carboxylic acid component up to the point. Further, as a method of forming the present catalyst system, an organoaluminum compound component and an organic carboxylic acid component may be contacted in advance and used.

[Catalyst Use / Polymerization] <Polymerization> The catalyst system of the present invention is, of course, applied to ordinary slurry polymerization, but it is substantially solvent-free liquid phase solventless polymerization or solution polymerization. , Or the gas phase polymerization method. As the polymerization solvent in the case of slurry polymerization, saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene and toluene can be used alone or as a mixture. The polymerization temperature is preferably room temperature to 200 ° C., more preferably 50 to
The temperature is 150 ° C, particularly preferably 60 to 100 ° C. Hydrogen can also be used supplementarily as a molecular weight regulator at that time.

<Α-Olefin> The α-olefin used for the polymerization in the catalyst system of the present invention has the general formula RC
H = CH ₂ (wherein R is a hydrogen atom, or may have a branched group, and has 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms,
Is a hydrocarbon residue of). Specifically, there are α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene and 3-methyl-1-butene. Among them, the catalyst of the present invention is particularly suitable for the polymerization of propylene, but it is also suitably used when copolymerizing ethylene or 1-butene with propylene in a random or block manner.

[0032]

EXAMPLES Example 1 [Production of Component (A)] 200 ml of dehydrated and deoxygenated n-heptane was introduced into a flask sufficiently replaced with nitrogen, 0.4 mol of MgCl ₂ and Ti (O-n) were added.
C ₄ H _{9) 4} was 0.8 mol introduced and reacted for 2 hours while maintaining the 95 ° C.. After completion of the reaction, lower the temperature to 40 ° C,
Then, 48 ml of methyl hydrogen polysiloxane (from 20 centistokes) was introduced and reacted for 3 hours. The solid component produced was washed with n-heptane. Then, 50 ml of purified n-heptane was introduced into a flask that had been sufficiently replaced with nitrogen, and 0.24 mol of the solid component synthesized above was introduced in terms of Mg atom. Then, 25 ml of n-heptane was added to SiCl ₄₀ .
While mixing 4 mol and keeping at 30 ° C., the mixture was introduced into the flask over 60 minutes and reacted at 90 ° C. for 3 hours. to this,
Further, by mixing 0.016 mol of phthalic acid chloride with 25 ml of n-heptane, while maintaining the temperature at 90 ° C, 3
The mixture was introduced into the flask over 0 minutes and reacted at 90 ° C. for 1 hour. After completion of the reaction, it was washed with n-heptane. Then, 0.24 mmol of SiCl ₄ was introduced into this, and 100 ° C.
And reacted for 3 hours. After the reaction was completed, it was thoroughly washed with n-heptane. 50 ml of sufficiently purified n-heptane was introduced into a flask which had been sufficiently replaced with nitrogen, and then 5 g of the solid component obtained above was introduced, and further (CH ₃ ) ₃
0.81 ml of CSi (CH ₃ ) (OCH ₃ ) ₂ was introduced and contacted at 30 ° C. for 2 hours. After contact is completed n-
It was thoroughly washed with heptane.

[Polymerization of propylene] 1.5 liters of sufficiently purified n-heptane, 500 milligrams of triethylaluminum, 53 milligrams of acetic acid, a solid produced as described above in a stainless steel autoclave with an internal volume of 3 liters equipped with a stirrer. After introducing 30 mg of each catalyst component (A), 500 ml of hydrogen was introduced. Then, the autoclave was heated to a temperature of 75 ° C., and propylene was pressure-supplied until a pressure of 5 kg / cm ² was reached to start the polymerization of propylene. The pressure was maintained for 3 hours to continue the polymerization. Then, the introduction of the monomers was stopped, unreacted monomers were purged, the produced polymer was separated from heptane, and dried. As a result, 6
62.3 g of powdered polypropylene was obtained. When n-heptane was removed from the filtrate by heating, 0.66 g of a polymer was obtained. Therefore, the catalyst yield of this catalyst system is 22100 g-polypropylene / g-solid catalyst (g
-PP / g-CAT). The melt flow rate (MFR) was 6.8 g / 10 minutes, and the bulk density of the produced polymer was 0.51. The Olsen flexural modulus is ASTM
As a result of measurement by the method of D-747-70, it was 14900. Polypropylene powder 5 thus obtained
After dissolving g in 300 ml of boiling xylene,
The polymer was gradually cooled to 23 ° C. and left at 23 ° C. for 10 hours to separate the precipitated polymer by filtration. The polymer component obtained by concentrating and drying the filtrate was vacuum dried at 90 ° C. to obtain a percentage of 23 ° C. xylene-soluble component (hereinafter abbreviated as CXS). As a result, CXS
Was 0.14% by weight.

Comparative Example 1 Polymerization of propylene was carried out in the same manner as in Example 1 except that acetic acid was not added. The obtained results are as shown in Table 1.

Examples 2 to 6 Polymerization of propylene was carried out in the same manner as in Example 1 except that the compound shown in Table 1 was added as the component (C) instead of acetic acid. The obtained results are as shown in Table 1.

Example 7 Polymerization of propylene was carried out in the same manner as in Example 1 except that the addition amount of acetic acid was changed as shown in Table 1. The obtained results are as shown in Table 1.

Example 8 [Production of component (A)] 200 ml of dehydrated and deoxygenated n-heptane was introduced into a flask sufficiently replaced with nitrogen, and then 0.4 mol of MgCl ₂ and Ti (O-n) were added.
C ₄ H _{9) 4} was 0.8 mol introduced and reacted for 2 hours at 95 ° C.. After completion of the reaction, the temperature was lowered to 40 ° C., 48 ml of methylhydrogenpolysiloxane (20 centistokes) was then introduced, and the reaction was carried out for 3 hours. The solid component produced was washed with n-heptane. Then, 50 ml of purified n-heptane was introduced into a flask that had been sufficiently replaced with nitrogen, and 0.24 mol of the solid component synthesized above was introduced in terms of Mg atom. Then, n-
25 ml of heptane was mixed with 0.4 mol of SiCl ₄ and the mixture was introduced into the flask over 60 minutes while maintaining the temperature at 30 ° C, and reacted at 90 ° C for 3 hours. Further, 25 ml of n-heptane was mixed with 0.016 mol of phthalic acid chloride, and the mixture was introduced into the flask over 30 minutes while maintaining the temperature at 90 ° C, and reacted at 90 ° C for 1 hour. After completion of the reaction, it was washed with n-heptane. Then add SiCl ₄
0.24 mmol was introduced and reacted at 100 ° C. for 3 hours. After the reaction was completed, it was thoroughly washed with n-heptane. 50 ml of sufficiently purified n-heptane was introduced into a flask thoroughly replaced with nitrogen, 5 g of the solid component obtained above was introduced, and 2.32 ml of dicyclopentyldimethoxysilane was introduced, and the mixture was introduced at 30 ° C. for 2 hours. Contacted. After the contact was completed, it was thoroughly washed with n-heptane.

[Propylene Polymerization] Propylene was polymerized in the same manner as in Example 1. The obtained results are as shown in Table 1.

Comparative Example 2 Propylene was polymerized in the same manner as in Example 8 except that acetic acid was not added. The obtained results are as shown in Table 1.

Example 9 [Production of component (A)] 200 ml of dehydrated and deoxygenated n-heptane was introduced into a flask sufficiently replaced with nitrogen, and then 0.4 mol of MgCl ₂ and Ti (O-n) were added.
C ₄ H _{9) 4} was 0.8 mol introduced and reacted for 2 hours at 95 ° C.. After completion of the reaction, the temperature was lowered to 40 ° C., 48 ml of methylhydrogenpolysiloxane (20 centistokes) was then introduced, and the reaction was carried out for 3 hours. The solid component produced was washed with n-heptane. Then, 50 ml of purified n-heptane was introduced into a flask that had been sufficiently replaced with nitrogen, and 0.24 mol of the solid component synthesized above was introduced in terms of Mg atom. Then, n-
25 ml of heptane was mixed with 0.4 mol of SiCl ₄ and the mixture was introduced into the flask over 60 minutes while maintaining the temperature at 30 ° C. and reacted at 90 ° C. for 2 hours. After completion of the reaction, it was thoroughly washed with n-heptane. 50 ml of sufficiently purified n-heptane was introduced into a flask thoroughly replaced with nitrogen, then 5 g of the solid component obtained above was introduced, and 1 (CH ₃ ) ₃ CSi (CH ₃ ) (OCH ₃ ) ₂ was added. ．
62 ml of the solution was introduced and contacted for 2 hours while maintaining the temperature at 30 ° C. After the contact was completed, it was thoroughly washed with n-heptane.

[Polymerization of propylene] Polymerization of propylene was carried out in the same manner as in Example 1 except that the component (A) was changed to the solid component obtained above. The obtained results are as shown in Table 1.

Comparative Example 3 Propylene was polymerized in the same manner as in Example 9 except that acetic acid was not added. The obtained results are as shown in Table 1.

Example 10 Polymerization of propylene was carried out in the same manner as in Example 9 except that benzoic acid was added instead of acetic acid. The obtained results are as shown in Table 1.

[Table 1]

[Production of Propylene Block Copolymer] Example 11 A stirring autoclave having an internal volume of 200 liters was sufficiently replaced with propylene, and then 45 liters of purified n-heptane were introduced to carry out 10.5 g of triethylaluminum. 6.5 g of the solid catalyst component prepared in Example 1, 1.0 g of acetic acid
Was maintained at 70 ° C. and was introduced under a propylene atmosphere.
In the first-stage polymerization, after heating the autoclave to 75 ° C., propylene was added to 9. while maintaining the hydrogen concentration at 7.0% by volume.
It was started by introducing at a feed rate of 0 kg / hour. After 231 minutes, the introduction of propylene was stopped. The pressure in the autoclave at this time was 6.0 kg / cm ² G. Further, the polymerization was continued at 65 ° C. for 90 minutes. Then, the propylene in the gas phase was purged to 0.2 kg / cm ² G. Next, after lowering the temperature of the autoclave to 65 ° C., post-stage polymerization was introduced at a feed rate of 3.78 kg / hour of propylene and 2.52 kg / hour of ethylene for 31 minutes, and then the polymerization was continued for 30 minutes. The obtained slurry was filtered and dried to obtain 32.5 kg of a powdery block copolymer. Details of the results are shown in Table 2. In the table, the weight ratio of the first-stage polymerization and the second-stage polymerization and the weight ratio of propylene and ethylene in the second-stage polymerization are calculated values on a feed basis.

Comparative Example 4 The procedure of Example 11 was repeated except that 8.7 g of the solid catalyst component prepared in Example 1 was used in preparing the block copolymer, and that acetic acid was not added before the first-stage polymerization. I went. As a result, the pressure inside the autoclave at the end of the propylene feed in the first-stage polymerization was 6.0 kg / cm ² G, and 32.2 kg of a powdery block copolymer was obtained.
The details of the obtained results are as shown in Table 2.

[Table 2]

<Practical physical property measurement method> The powder block copolymers obtained in Example 11 and Comparative Example 4 were blended with the following additives, pelletized by an extruder under the same conditions, and thickened by an injection molding machine. A sheet having a size of 4 mm was prepared and the physical properties were evaluated. Additives 2,6-tert butylphenol - Le 0.10 wt% RA1010 (Ciba Geigy) 0.05 wt% calcium stearate 0.10 wt% PTBBA-A1 (manufactured by Shell Chemical) 0.10 wt% Measurement of Physical Properties Various The physical properties were measured by the following methods. (A) Flexural modulus: ASTM-D790 (b) Izod impact strength (0 ° C): ASTM-D25
6 (with notch)

Example 12 After thoroughly replacing the stirring autoclave having an internal volume of 200 liters with propylene, 60 liters of purified n-heptane were introduced, 15.0 g of triethylaluminum, and the solid catalyst component prepared in Example 1. 0 g, acetic acid 0.05
g at 60 ° C. under a propylene atmosphere. further,
Propylene 10.8 kg / hour and ethylene 0.2 at a temperature of 65 ° C. while maintaining the gas phase hydrogen concentration at 6.5% by volume.
1-butene was polymerized at a feed rate of 1.2 kg / hour for 4 hours. The pressure in the autoclave at this time was 4.0 kg / cm ² G. Then, the polymerization was continued for 1 hour. Then, the product was filtered and dried to obtain 36.7 kg of powdery propylene / random copolymer. The MFR of this copolymer was 5.2 g / 10 minutes,
The ethylene content was 2.2% by weight and the 1-butene content was 8.4% by weight. The solvent-soluble product was 1.1.
It was 6 kg.

Comparative Example 5 In preparing a random copolymer, 4.1 g of the solid catalyst component prepared in Example 1 was used, the hydrogen concentration in the gas phase was kept at 4.5% by volume, and before polymerization. The same operation as in Example 12 was performed except that acetic acid was not added to. As a result, the pressure in the autoclave at the end of the monomer feed was 3.9 kg / cm ² G, and 356 kg of a propylene / random copolymer was obtained. MFR of this copolymer
Is 5.2 g / 10 minutes, the ethylene content is 2.1% by weight,
The content of 1-butene was 8.7% by weight. The solvent-soluble product was 2.21 kg.

[0049]

According to the production method of the present invention, an α-olefin polymer having high stereoregularity can be obtained in a high yield.
It has been described above in the section of [Summary of Invention].

[Brief description of drawings]

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

Claims (1)

[Claims] 1. When a .alpha.-olefin is brought into contact with a catalyst composed of a combination of the following components (A) and (B) to polymerize, 0 to 5% of the total amount of the polymer is produced. The method for producing an α-olefin polymer, characterized in that the following component (C) is added at the time of. Component (A): Solid catalyst component R ¹ R ² _3-n Si (OR ³ ) _n (1 containing titanium, magnesium, halogen, and the organosilicon type electron-donating compound represented by the formula (1) as essential components. [Wherein R ¹ is a branched or cyclic aliphatic hydrocarbon residue, R ² is a branched or cyclic aliphatic or linear hydrocarbon residue, and R ³ is a branched or linear hydrocarbon residue. Residue, n is 2
≦ n ≦ 3. ] Component (B): Organoaluminum Compound Component (C): Organic Carboxylic Acid