JP2541562B2 - Catalyst for stereoregular polymerization of olefins - Google Patents

Description

Description: BACKGROUND OF THE INVENTION Technical Field The present invention relates to a catalyst for stereoregular polymerization of olefins. More specifically, the present invention, when applied to the polymerization of an α-olefin having 3 or more carbon atoms by using a specific catalyst, is capable of producing a highly stereoregular polymer under stable polymerization conditions and advantageously in industrial production. Is possible.

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

However, such a catalyst using an electron-donating compound as the third component (external donor) reduces the polymerization rate due to the reaction between the organoaluminum compound and the electron-donating compound, and is intended to increase the polymerization rate. When the polymerization temperature is raised, the above reaction is promoted. Therefore, it is limited to increase the polymerization temperature to increase the polymerization amount (improve the production efficiency). There is a problem that it becomes difficult to control the performance.

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

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

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

[Outline of Invention]

SUMMARY OF THE INVENTION The present invention aims to provide a solution to the above points. That is, α having 3 or more carbon atoms according to the present invention
The olefin stereoregular polymerization catalyst is composed of the following components (A) and (B).

Component (A) A solid catalyst component obtained by contacting the following components (i) to (iv).

Component (i): Solid component containing tetravalent titanium, magnesium and halogen as essential components, Component (ii): General formula R ¹ _m X _n Si (OR ² ) _4-mn (where R ¹ is in the α-position Carbon is second or third grade and has 3 carbons
Is a branched chain hydrocarbon residue of ~ 20, R ² has 1 to 10 carbon atoms.
X is halogen, m and n are 0 <m ≦ 3 and 0 ≦ n ≦ 3, respectively, and 0 <m + n ≦ 3. ) A silicon compound represented by the following formula: Component (iii): Organoaluminum compound Component (iv): General formula (However, R ³ is a hydrocarbon residue.) A polymer silicon compound having a structure represented by: as a repeating unit, Component (B) an organoaluminum compound.

EFFECTS OF THE INVENTION The catalyst for stereoregular polymerization of α-olefins having 3 or more carbon atoms of the present invention does not use an electron-donating compound (external donor) at the time of polymerization, so that the polymerization rate does not decrease, and the boiling heptane of the produced polymer does not exist. It reduces the stereoregularity due to the extraction test, and therefore does not cause a problem even if the assembly temperature is increased, which solves the problems of known catalysts.

These characteristics are very advantageous in industrial production and are important characteristics of the catalyst. Although the reason why such a catalyst has been obtained has not been sufficiently analyzed, the silicon compound of the component (ii), the organoaluminum compound of the component (ii), and the specific poimer case of the component (iv) used in the present invention are used. It is presumed to be due to the interaction of elementary compounds.

[Specific Description of the Invention]

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

Component (A) The component (A) of the catalyst of the present invention is a solid catalyst component obtained by contacting the following components (i) to (iv). Here, "obtaining by contacting" does not mean that the target is only the ones listed (that is, (i) to (iv)), but the coexistence of the purposeful fifth component. Do not exclude

Component (i) Component (i) is a solid component containing tetravalent titanium, magnesium and halogen as essential components. Here, "containing as an essential component" means that a purposeful other element may be contained in addition to the three components indicated.
It is indicated that each of these elements may exist as any purposeful compound, and that these elements may exist as bonded to each other. The solid components themselves containing titanium, magnesium and halogen are known. For example, JP-A-53-45
688, 54-3894, 54-31092, 54-39483
No. 54, No. 54-94591, No. 54-118484, No. 54-131589
No. 55, No. 55-75411, No. 55-90510, No. 55-60511,
55-127405, 55-147507, 55-155003,
56-18609, 56-70005, 56-72001, 56-8
6905, 56-90807, 56-155206, 57-3803
No. 57-34103, No. 57-92007, No. 57-121003,
58-5309, 58-5310, 585311, 58-87
06, 58-27732, 58-32604, 58-32605
No. 58-67703, No. 58-117206, No. 58-127708
No. 58, No. 58-183708, No. 58-183709, No. 59-149905
No. 59-149906 and the like are used.

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

Further, the tetravalent titanium compound serving as the source of tetravalent titanium is represented by the general formula Ti (OR ⁴ ) _4-n X _n (wherein R ⁴ is a hydrocarbon residue,
Preferably, it has about 1 to 10 carbon atoms, X represents halogen, and n represents a number of 0 ≦ n ≦ 4. ). As a specific example, TiCl ₄ , TiBr ₄ ,
Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₃ Cl, T
_{i (O-iC 3 H 7} ) Cl 3, Ti (O-nC 4 H 9) Cl 3, Ti (O-nC 4
_{H 9) 2 Cl 2, Ti} (OC 2 H 5) Br 3, Ti (OC 2 H 5) (OC 4 H 9) 2 C
_{l, Ti (O-nC 4} H 9) 3 Cl, Ti (O-C 6 H 5) Cl 3, Ti (O-
iC ₄ H ₉ ) ₂ Cl ₂ , Ti (OC ₅ H ₁₁ ) Cl ₃ , Ti (OC ₆ H ₁₃ ) Cl ₃ , Ti
(OC ₂ H ₅ ) ₄ , Ti (O-nC ₃ H ₇ ) ₄ , Ti (O-nC
_{4 H 9) 4, Ti (} O-iC 4 H 9) 4, Ti (O-nC 6 H 13) 4, Ti
_{(O-nC 8 H 17)} 4, Ti _{[OCH 2 CH (C 2 H 5} ) C 4 H 9 ] _4, and the like.

Further, it is also possible to use a molecular compound obtained by reacting TiX ' ₄ (here, X'represents halogen) with an electron donor described later. Specific examples include TiCl ₄ · CH ₃ COC ₂ H ₅ , TiCl
₄・ CH ₃ CO ₂ C ₂ H ₅ , TiCl ₄・ C ₆ H ₅ NO ₂ , TiCl ₄・ CH ₃ COCl, TiC
l ₄・ C ₆ H ₅ COCl, TiCl ₄・ C ₆ H ₅ CO ₂ C ₂ H ₅ , TiCl ₄・ ClCOC
₂ H ₅ , TiCl ₄ , C ₄ H ₄ O, etc. can be mentioned.

The halogen source is usually supplied from the above-mentioned halogen compound of magnesium and / or titanium, but is supplied from a known halogenating agent such as an aluminum halide, a silicon halide, or a phosphorus halide. You can also do it.

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

Solid components used in the present invention include SiCl in addition to the above essential components.
₄ , silicon compounds such as CH ₃ SiCl ₃ , methyl hydrogen polysiloxane, Al (OiC ₃ H ₇ ) ₃ , AlCl ₃ , AlBr ₃ , Al
Aluminum compounds such as (OC ₂ H ₅ ) ₃ and Al (OCH ₃ ) ₂ Cl, and boron compounds such as B (OCH ₃ ) ₃ , B (OC ₂ H ₅ ) ₃ and B (OC ₆ H ₅ ) ₃ It is possible to use other components, and it does not matter that they remain in the solid component as components such as silicon, aluminum and boron.

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

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

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

The amount of each of the above components used is arbitrary as long as the effects of the present invention are recognized, but generally the following ranges are preferred.

The titanium compound may be used in a molar ratio of 1 × 10 ^{−4 to} 1000, preferably 0.01 to 10 with respect to the amount of the magnesium compound used. When a compound therefor is used as a halogen source, the amount used is 1 × 10 6 in molar ratio with respect to the amount of magnesium used, regardless of whether the titanium compound and / or the magnesium compound contains halogen. ^It is preferably in the range of ^{-2 to} 1000, and more preferably in the range of 0.1 to 100.

The amount of silicon, aluminum and boron compound used is preferably in the range of 1 × 10 ^{−3 to} 100, preferably 0.01 to 1 in terms of molar ratio with respect to the amount of magnesium compound.
Within the range of.

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

Component (i) is produced, for example, by the following production method using the above-mentioned titanium source, magnesium source and halogen source, and optionally other components such as an electron donor.

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

(B) A method 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 halogen compound of silicon into contact with a solid component obtained by contacting a magnesium halide with titanium tetraalkoxide and a specific polymer silicon compound.

As the polymer silicon compound, those represented by the following formula are suitable.

(Here, R is a hydrocarbon residue having about 1 to 10 carbon atoms, and n is the degree of polymerization such that the viscosity of the polymer silicon compound is about 1 to 100 centistokes.) Specifically, methylhydrogen Polysiloxane,
Examples include ethyl hydrogen polysiloxane, phenyl hydrogen polysiloxane, cyclohexyl hydrogen polysiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane. it can.

(D) A method in which a magnesium compound is dissolved with titanium tetraalkoxide and an electron donor, and a titanium compound is brought into contact with a solid component precipitated by a halogenating agent or a titanium halogen compound.

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

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

As the catalyst component (i) used in the present invention, the solid component obtained as described above can be used as it is, or the solid component is brought into contact with olefins in the presence of an organoaluminum compound to carry out prepolymerization. It may be obtained from

When the component (i) is prepolymerized, the conditions for prepolymerizing the olefins for producing the component (i) are not particularly limited, but the following conditions are generally preferred. The polymerization temperature is 0 to 80 ° C, preferably 10 to 16 ° C
Is. The polymerization amount is 0.001 per gram of solid component.
It is preferred to polymerize ~ 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 (iC 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 (iC ₄ H ₉ ) Cl, Al (C ₂ H ₅ ) ₂ H, Al (iC ₄ H ₉ ) ₂
H, Al (C ₂ H ₅ ) ₂ (OC ₂ H ₅ ) and the like.

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

Specific examples are: Al (C ₂ H ₅ ) ₃ and Al (C ₂ H ₅ ) ₂ Cl combined, Al (iC ₄ H ₉ ) ₃ and Al (iC ₄ H ₉ ) ₂ Cl combined, Al (C
₂ H ₅ ) ₃ and Al (C ₂ H ₅ ) _1.5 Cl _1.5 combined, Al (C ₂ H ₅ ) ₃ and A
One example is the combined use of l (C ₂ H ₅ ) ₂ Cl and Al (C ₂ H ₅ ) ₂ (OC ₂ H ₅ ).

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 the 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, the prepolymerized component (i) is obtained.

Ingredient (ii) Ingredient (ii) used to produce ingredient (A) is
Formula ^{_{R 1 m X n Si (OR}} 2) 4-mn ( provided that, R ¹ is branched chain hydrocarbon residue having 3 to 20 carbon atoms in the secondary or tertiary carbon in position alpha, R ² Is a hydrocarbon residue having 1 to 10 carbon atoms, X
Is halogen, and m and n are silicon compounds represented by 0 <m ≦ 3 and 0 ≦ n ≦ 3, respectively, and 0 <m + n ≦ 3.

As a specific example, _{(CH 3) 3 CSi (CH} 3) (OCH 3) 2, (CH 3) 3 CSi (HC (C
_{H 3) 2) (OCH 3} ) 2, (CH 3) 3 CSI (CH 3) (OC
₂ H ₅ ) ₂ , (C ₂ H ₅ ) ₃ CSi (CH ₃ ) (OCH ₃ ) ₂ , (CH ₃ ) (C
_{2 H 5) CH-Si (} CH 3) (OCH 3) 2, C 2 H 5 C (CH 3) 2 Si (C
H ₃ ) (OCH ₃ ) ₂ , C ₂ H ₅ C (CH ₃ ) ₂ Si (CH ₃ ) (OC
₂ H ₅ ) ₂ , (CH ₃ ) ₃ CSi (OCH ₃ ) ₃ , (CH ₃ ) ₃ CSi (OC
_{2 H 5) 3, (C} 2 H 5) 3 CSi (OC 2 H 5) 3, (CH 3) (C 2 H 5) C
HSi (OCH ₃ ) _{3 and the} like can be mentioned.

Among these, preferred are silicon compounds having a tertiary carbon atom at the α-position of R ¹ and having a branched chain hydrocarbon residue having 4 to 10 carbon atoms.

Ingredient (iii) Ingredient (iii) used to produce ingredient (A)
Is an organoaluminum compound. Component (i) above
The same kind or different kind of organoaluminum compound used in the prepolymerization of can be used, but specific examples include Al (C ₂ H ₅ ) ₃ , Al (iC ₄ H ₉ ) ₃ , Al (nC 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)
Cl, Al (iC ₄ H ₉ ) ₂ Cl, Al (C ₂ H ₅ ) ₂ H, Al (iC ₄ H ₉ ) ₂ H, A
l (C ₂ H ₅ ) ₂ (OC ₂ H ₅ ), and the like.

Ingredient (iv) Ingredient (iv) used to produce ingredient (A) is of the formula Is a polymeric silicon compound having a manufacture represented by:

That is, the polymeric silicon compound has the structure represented by the formula as a repeating unit, that is, in the main chain.

In this formula, R ³ has about 1 to 10 carbon atoms, especially about 1 to 6 carbon atoms,
Is a hydrocarbon residue of. The polymerization degree of the polymer silicon compound is preferably such that the viscosity is about 1 to 100 centistokes.

Specific examples of the polymer silicon compound having such a structural unit include methylhydropolysiloxane, ethylhydropolysiloxane, phenylhydropolysiloxane, cyclohexylhydropolysiloxane, 1,1,3,3-
Examples thereof include tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane and 1,3,5,7-9-pentamethylcyclopentasiloxane.

Manufacture of Component (A) The contact conditions for the above-mentioned components (i) to (iv) may be arbitrary as long as the effects of the present invention are observed, but generally the following conditions are preferred. Contact temperature is -50 to-
The temperature is about 200 ° C, preferably 0 to 100 ° C. Examples of the contact method include a mechanical method using a rotary ball mill, a vibration mill, a jet mill, a medium stirring pulverizer, etc., and a method of contacting by stirring in the presence of an inert diluent. Examples of the inert diluent used at this time include aliphatic or aromatic hydrocarbons and halohydrocarbons.

Component (i) for producing component (A) of the present invention
The contact order of (iv) is arbitrary as long as the effect of the present invention is recognized.

The following are specific examples of such contact modes.

(A) Component (i) → Component (ii) → Component (iv) → Component (iii) (b) Component (i) → Component (iii) → Component (ii) → Component (iv) Component (i) ) → component (iv) → component (ii) → component (iii) (d) component (i) → {component (ii) + component (iv) + component (iii)} (e) component (i) → component (i) ii) → {(component (iii) +
Component (iv)} → component (ii) (f) component (i) → {component (ii) + component (iv)} → component (iii) → {component (ii) + component (iv)} (g) component (I) → {component (ii) + component (iii) + component (iv)} → {component (ii) + component (iii) + component (i
v)} The amount ratio of components (i) to (iv) may be arbitrary as long as the effects of the present invention are recognized, but generally, the following range is preferable.

The ratio of the amounts of the component (i) and the component (ii) is preferably 0.01 to 1000 in terms of the atomic ratio of silicon of the component (ii) to the titanium component constituting the component (i) (silicon / titanium), and preferably It is within the range of 0.1 to 100.

The amount of component (iii) used is preferably in the range of 0.01 to 100, preferably 0.1 to 30 in terms of atomic ratio (aluminum / titanium) of aluminum of component (iii) to titanium component constituting component (i). It is within.

The amount of component (iv) used is 0.1 to 1000, preferably 1 to 100, in the atomic ratio (silicon / titanium) of silicon of component (iv) to the titanium component constituting component (i). Is.

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

In addition to these organoaluminum compounds of (a) to (c), 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) It may also be an alkylaluminum alkoxide represented by a hydrocarbon residue having about 1 to 20 carbon atoms.). For example, combined use of triethyl aluminum and diethyl aluminum ethoxide, combined use of diethyl aluminum monochloride and diethyl aluminum ethoxide, combined use of ethyl aluminum dichloride and ethyl aluminum diethoxide, triethyl aluminum and diethyl aluminum ethoxide and diethyl aluminum chloride Can be used in combination.

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

[Use of catalyst / polymerization]

The catalyst of the present invention is, of course, applied to ordinary slurry polymerization, but is also applied to liquid phase solventless polymerization, solution polymerization, or gas phase polymerization method which uses substantially no solvent.
Further, it is also applied to a system in which continuous polymerization, batch polymerization or preliminary polymerization is carried out. The polymerization solvent in the case of slurry polymerization, hexane, heptane, pentane, cyclohexane,
Saturated aliphatic or aromatic hydrocarbons such as 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 ° C., and hydrogen can be supplementarily used as a molecular weight regulator at that time. In the slurry polymerization, the amount of component (A) used is 0.00
It is preferably within the range of 1 to 0.1 gram component (A) / liter solvent.

The olefins polymerized with the catalyst system of the present invention have the general formula R
—CH═CH ₂ (wherein R is a hydrocarbon residue having 1 to 10 carbon atoms and may have a branching group). Specifically, propylene, butene-1, pentene-
There are olefins such as 1, hexene-1, and 4-methylpentene-1. Preferred is propylene. In the case of these polymerizations, it is possible to carry out a copolymerization with olefins of up to 30% by weight with respect to propylene, or ethylene. Copolymerization with other copolymerizable monomers (for example, diolefin) can also be performed.

[Experimental example]

Example 1 [Production of component (A)] 200 ml of dehydrated and deoxygenated n-heptane was introduced into a flask which had been sufficiently replaced with nitrogen, and then MgCl ₂ was added.
0.4 _{mole, Ti (O-nC 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., and then 48 ml of methylhydropolysiloxane (20 centistokes) was introduced and the reaction was carried out for 3 hours.
The resulting solid component was washed with n-heptane.

Then, 50 ml of n-heptane purified in the same manner as above was introduced into a flask which had been sufficiently replaced with nitrogen, and 0.24 mol of the solid component synthesized above in terms of Mg atom was introduced. Then, 25 ml of n-heptane was mixed with 0.4 mol of SiCl _{4 and} introduced into the flask at 30 ° C. for 30 minutes and reacted at 70 ° C. for 3 hours. After the completion of the reaction, the resultant was washed with n-heptane. Next, 25 ml of n-heptane was added with phthalic acid chloride.
024 mol was mixed and introduced into the flask at 70 ° 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 SiCl ₄
16 ml was introduced and the reaction was carried out at 80 ° C. for 6 hours.
After completion of the reaction, it was thoroughly washed with n-heptane. The titanium content of this product was 1.86 weight percent.

Then the internal volume 1.5 with stirring and temperature control device
Into a liter stainless steel stirring tank, 500 ml of sufficiently dehydrated and deoxygenated n-heptane, 3.2 g of triethylaluminum, and 20 g of the solid component obtained above were introduced. The temperature in the stirring tank was adjusted to 20 ° C., 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. A portion was taken out and the amount of propylene polymerized was examined.
It was component (i) in grams.

50 ml of sufficiently purified n-heptane was introduced into a flask which had been sufficiently replaced with nitrogen, then 5 g of the component (i) obtained above was introduced, and then (CH ₃ ) ₃ CSi was used as a silicon compound of the component (ii). 0.16 ml of (CH ₃ ) (CCH ₃ ) ₂ was introduced, then 0.8 g of triethylaluminum and 0.75 g of methylhydrogenpolysiloxane (20 cm Stokes) were introduced, and the mixture was heated at 30 ° C.
For 2 hours. After the contact was completed, it was thoroughly washed with n-heptane. Then the same amount of component (ii) to component (iv)
Was used under the same conditions as above. After contact is over,
It was thoroughly washed with n-heptane to obtain a component (A).

The silicon compound content of the resulting component (A) was measured and found to be 7.1 weight percent.

[Polymerization of propylene]

In a stainless steel autoclave with an internal volume of 1.5 liter equipped with a stirring and temperature control device, 500 ml of sufficiently dehydrated and deoxygenated n-heptane, 125 mg of triethylaluminum as component (B) and the component (A) prepared above 15 mg was introduced as a component excluding the prepolymerized polymer.

Then, introduce 60 ml of hydrogen, raise the temperature and pressure,
Polymerization was carried out under the conditions of polymerization pressure = 5 kg / cmG, polymerization temperature = 75 ° C., and polymerization time = 2 hours. After the polymerization was completed, the obtained polymer slurry was separated by filtration and the polymer was dried. As a result, 201.6 grams of polymer was obtained. One filtrate yielded 0.56 grams of polymer. From the boiling heptane extraction test, all products II (hereinafter abbreviated as T-II) were 99.3.
It was weight percent. The MFR was 1.1 g / 10 minutes, and the bulk density of the polymer was 0.49 g / CC.

Example 2 [Production of component (A)] In the production of component (A) of Example 1, diheptyl phthalate was used in place of phthalic acid chloride, and SiCl ₄ 16
A solid component was prepared in the same manner as in Example 1 except that 15 ml of TiCl ₄ was used instead of ml. The titanium content of the obtained solid component was 2.41 weight percent.

Preliminary polymerization was performed in the same manner as in Example 1 except that the amount of triethylaluminum used was 4.3 g using the solid component produced above. The polymerization amount of propylene at this time was 0.9 g per 1 g of the above solid component [component (1)].

50 ml of sufficiently purified n-heptane was introduced into a flask which had been sufficiently replaced with nitrogen, then 5 g of the component (i) obtained above was introduced, and then (CH ₃ ) ₃ CSi was used as a silicon compound of the component (ii). 0.34 ml of (CH ₃ ) (OCH ₃ ) ₂ was introduced, and 0.6 ml of 1,1,3,3-tetramethyldisiloxane was further introduced, and the mixture was contacted at 50 ° C. for 1 hour. After the contact was completed, it was thoroughly washed with n-heptane. Then, 0.19 g of triethylaluminum was introduced and contact was carried out at 50 ° C. for 1 hour. After the contact was completed, it was thoroughly washed with n-heptane. Then, as the silicon compound of component (ii),
0.3 ml of (CH ₃ ) ₃ CSi (CH ₃ ) (OCH ₃ ) ₂ was introduced and contacted at 50 ° C. for 1 hour. After the contact was completed, it was thoroughly washed with n-heptane to obtain a component (A). A portion was taken out and the silicon compound content was measured and found to be 6.8 weight percent.

[Polymerization of propylene]

Polymerization of propylene was carried out in the same manner as in Example 1 except that the above component (A) was used and the amount of triethylaluminum used as the component (B) was 250 mg. As a result, 224.7 grams of polymer was obtained. T-II = 99.0
% By weight, MFR = 1.75 g / 10 min, polymer bulk specific gravity = 0.49 g / CC.

Example 3 [Production of Component (A)] A fully dried and nitrogen-substituted 0.4 liter ball mill was filled with 40 12 mmφ stainless steel balls, and 20 g of MgCl ₂ and 12.4 ml of diethyl phthalate were introduced into this. Then, it was crushed by a rotary ball mill for 48 hours. After the pulverization was completed, the mixed pulverized composition was taken out of the mill in the dry box. Then, 8.1 g of the ground composition was introduced into a flask thoroughly replaced with nitrogen, 25 ml of n-heptane and 25 ml of TiCl ₄ were introduced, and the mixture was mixed at 100 ° C. for 3 hours.
Allowed to react for hours. After completion of the reaction, it was thoroughly washed with n-heptane. When a part of the obtained solid component [component (i)] was taken out and the composition was analyzed, the Ti content was 3.43 wt%.

Next, 50 ml of sufficiently purified n-heptane was introduced into a flask thoroughly replaced with nitrogen, 5 g of the component (i) obtained above was introduced, and then 2.4 ml of diphenyldimethoxysilane was introduced as the component (ii). And then 30
The reaction was carried out at 0 ° C for 1 hour. After completion of the reaction, it was thoroughly washed with n-heptane. Then tri-n-hexyl aluminum
1.7 grams and methyl hydrogen polysiloxane
1.1 gram was introduced and contacted at 25 ° C for 60 minutes. After the contact was completed, it was thoroughly washed with n-heptane. Then, 2.4 ml of diphenyldimethoxysilane and 1.1 ml of methylhydrogenpolysiloxane were introduced and contacted at 40 ° C. for 1 hour. After the contact was completed, it was thoroughly washed with n-heptane to obtain a component (A). When a portion was taken out and the silicon compound content was measured, it was 10.7 weight percent.

[Polymerization of propylene]

Polymerization of propylene was carried out under the same conditions as in Example 1. 101.4 grams of polymer were obtained, T-II = 97.9
Weight percent, MFR = 5.3 g / 10 min, polymer bulk specific gravity = 0.
It was 41 g / CC.

Example 4 [Production of Component (A)] n was dehydrated and deoxidized in a flask which had been sufficiently replaced with nitrogen.
- introducing from heptane 100 ml then MgCl ₂ 0.
1 mol, 0.2 mol of Ti (O-nC ₄ H ₉ ) ₄ was introduced, and 2 at 95 ℃
Allowed to react for hours. After the reaction was completed, the temperature was lowered to 35 ° C and 1,3,
15 ml of 5,7-tetramethylcyclotetrasiloxane was introduced and the reaction was carried out for 5 hours. The generated solid component is n
-Washed with heptane. Then, 50 ml of n-heptane was introduced into a flask that had been sufficiently replaced with nitrogen, and 0.03 mol of the solid component synthesized above was introduced in terms of Mg atom. Incidentally
0.06 mol of SiCl ₄ was introduced at 20 ° C. for 30 minutes and reacted at 50 ° C. for 3 hours. After completion of the reaction, it was washed with n-heptane to obtain a solid component (i) for producing the component (A). The titanium content in this solid component was 4.52 weight percent.

Using this component (i), the (CH ₃ ) ₃ CSi (C
Contact was performed under the same conditions as in Example 2 except that the amount of H ₃ ) (OCH ₃ ) ₂ used was 2.9 ml. After the completion of the contact, the resultant was sufficiently washed with n-heptane to obtain Component (A). The silicon compound content of component (A) was measured and found to be 6.4 weight percent.

[Polymerization of propylene]

Under the polymerization conditions of Example 2, propylene was polymerized in the same manner as in Example 2 except that the amount of triethylaluminum used was 63 mg and the polymerization temperature was 70 ° C. As a result, 113 grams of polymer were obtained, MFR = 5.8g / 10
Min, T-II = 97.2 weight percent, polymer bulk specific gravity =
It was 0.48 g / CC.

Example 5 Component (A) was produced under the same conditions as in Example 1 except that ethyl benzoate was used in place of phthaloyl chloride in the production of component (A) of Example 1. Polymerization of propylene was also carried out in the same manner as in Example 1. As a result, 7
3.6 grams of polymer were obtained, MFR = 5.5 g / 10 min, T-
II = 95.1 weight percent, polymer bulk specific gravity = 0.44 g / CC
Met.

Examples 6 to 10 The production of the component (A) of Example 1 was carried out in exactly the same manner, except that the amounts and types of the silicon compounds used as the component (ii) and the component (iv) were changed to the compounds shown in Table 1. Then, propylene was polymerized in exactly the same manner. The results are shown in Table-1.

Example 11 [Production of component (A)] Component (i) was produced in the same manner as in Example 1.

50 ml of sufficiently purified n-heptane was introduced into a flask which had been sufficiently replaced with nitrogen, then 5 g of the component (i) obtained above was introduced, and then (CH ₃ ) ₃ CSi was used as a silicon compound of the component (ii). 0.08 ml of (CH ₃ ) (OCH ₃ ) ₂ was introduced, and they were contacted at 30 ° C. for 1 hour. Then, 1.5 g of the component (iv), methylhydrogenpolysiloxane, was introduced and the mixture was contacted at 30 ° C. for 2 hours. Then, 0.5 g of component (iii), triethylaluminum, was introduced and contacted at 40 ° C. for 2 hours. After the contact was completed, it was thoroughly washed with n-heptane to obtain a component (A).

[Polymerization of propylene]

Polymerization was carried out under exactly the same conditions as in Example 1. 210.4
Grams of polymer were obtained, T-II = 98.9 weight percent, MFR = 1.7 g / 10 min, polymer bulk specific gravity = 0.49 g / CC.

Example 12 The component (A) prepared in Example 1 was used for polymerization for 6 hours.

In a stainless steel autoclave with an internal volume of 1.5 liter equipped with a stirring and temperature control device, 500 ml of sufficiently dehydrated and deoxygenated n-heptane, 100 mg of triethylaluminum as component (B),
Then, 10 mg of the catalyst component (A) synthesized above was introduced as a component excluding the prepolymerized polymer. Next, 80 ml of H ₂ was introduced, the temperature was raised and the polymerization pressure was increased.
Polymerization was carried out under the conditions of 5 kg / cmG, polymerization temperature of 75 ° C. and polymerization time of 6 hours. After the weight was finished, the obtained polymer slurry was separated by filtration and the polymer was dried. The results are shown in Table-2.

Example 13 The component (A) prepared in Example 1 was used to carry out polymerization at 85 ° C. The results are shown in Table-2.

Comparative Example 1 [Production of Component (A)] In the production of the component (A) of Example 1, the component (iii)
And the contact was performed under exactly the same conditions except that the component (iv) was not used. The silicon compound content of component (A) is 3.
It was 6 weight percent.

[Polymerization of propylene]

Polymerization of propylene was carried out under the same conditions as in Example 1. 199.5 grams of polymer are obtained, T-II = 98.6
Weight percent, MFR = 2.3 g / 10 min, polymer bulk specific gravity = 0.
It was 46 g / CC.

Comparative Examples 2 and 3 Using the component (A) of Comparative Example 1 for 6 hours polymerization and 85
C. Weighed. The results are shown in Table-2.

Comparative Example 4 [Production of Component (A)] In the production of the component (A) of Example 1, the components were contacted under the same conditions as in Example 1 except that the component (ii) was not used. Almost no silicon compound content of component (A) was detected.

[Polymerization of propylene]

Polymerization of propylene was carried out under the same conditions as in Example 1 except that the component (A) obtained above was used. 99.4 grams of polymer were obtained, T-II = 70.6 weight percent, MFR = 5.6 g / 10 min, polymer bulk specific gravity = 0.37 g / cc.

Comparative Example 5 [Production of Component (A)] In the production of the component (A) of Example 1, the components were contacted under the same conditions as in Example 1 except that the component (iv) was not used. The silicon compound content of component (A) was 6.7 weight percent.

[Polymerization of propylene]

Polymerization of propylene was carried out under the same conditions as in Example 1 except that the component (A) obtained above was used. 200.7 grams of polymer was obtained, T-II = 98.8 weight percent, MFR = 1.2 g / 10 min, polymer bulk specific gravity = 0.48 g / cc.

Comparative Example 6 [Production of Component (A)] In the production of the component (A) of Example 1, as the component (ii), instead of (CH ₃ ) ₃ CSi (CH ₃ ) (OCH ₃ ) ₂ , (C
Production was performed in exactly the same manner except that H ₃ ) ₂ Si (OC ₂ H ₅ ) ₂ was used.

The silicon compound content of the obtained component (A) was measured and found to be 2.1% by weight.

[Polymerization of propylene]

Polymerization of propylene was carried out under the same conditions as in Example 1. As a result, 120.8 g of polymer was obtained. T-II = 83.4% by weight of this polymer, MFR = 5.7 g / 1
At 0 minutes, the bulk density of the polymer was 0.41 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)

(57) [Claims] 1. A catalyst for stereoregular polymerization of an α-olefin having 3 or more carbon atoms, which comprises the following components (A) and (B). Component (A) A solid catalyst component obtained by contacting the following components (i) to (iv). Component (i): Solid component containing tetravalent titanium, magnesium and halogen as essential components, Component (ii): General formula R ¹ _m X _n Si (OR ² ) _4-mn (provided that R ¹
Is a branched chain hydrocarbon residue having a secondary or tertiary α-carbon and a carbon number of 3 to 20, R ² is a hydrocarbon residue of a carbon number of 1 to 10, X is a halogen, m and n are 0 <m ≦ 3 and 0 ≦ n, respectively
≦ 3, and 0 <m + n ≦ 3. ) A silicon compound represented by the following formula: Component (iii): Organoaluminum compound Component (iv): (However, R ³ is a hydrocarbon residue.) A polymer silicon compound having a structure represented by: as a repeating unit, Component (B) an organoaluminum compound.