JP2806983B2 - Method for producing olefin polymer - Google Patents

Description

Description: BACKGROUND OF THE INVENTION <Technical Field> The present invention relates to a method for producing an olefin polymer. More specifically, the present invention relates to a method for producing a polymer of olefins, particularly an α-olefin having 3 or more carbon atoms, using a specific catalyst to produce a highly stereoregular polymer.
It relates to a method of producing at a temperature of 150 ° C. or more.

Conventionally, using a catalyst comprising a solid catalyst component containing titanium, magnesium and halogen (and an electron donor as required) and a catalyst comprising an organoaluminum compound (and an electron donor as necessary), It is known that polymers can be produced. However, conventional catalyst systems have a polymerization temperature of 90 ° C or less, preferably 80 ° C or less,
In the case of, often exhibits the performance as a catalyst, for example, a catalyst capable of producing a highly stereoregular polymer at a high temperature of 150 ° C. or higher has not been proposed to the knowledge of the present inventors. .

[Summary of the Invention]

<Summary> The present invention aims to provide a solution to the above points.

That is, the production of the olefin polymer according to the present invention,
It is characterized in that an olefin is brought into contact with a catalyst obtained by bringing the following components (A) and (B) into contact with each other at a temperature of 150 ° C. or higher to carry out polymerization.

Component (A) A catalyst product of the following components (i), (ii) and (iii): Component (i) A solid component for a Ziegler-type catalyst containing titanium, magnesium and halogen as essential components, Component (ii) General formula R ¹ _m X _n Si (OR ² ) _4-mn (where R ¹ and R ² are hydrocarbon residues, X is halogen, m and n are 0 ≦ m ≦ 3 and 0, respectively)
≦ n ≦ 3, and 0 ≦ m + n ≦ 3. The silicon compound represented by), component (iii) an organoaluminum compound, component (B) an organoaluminum compound represented by the following general formula, the general formula _{^{R 3 3-a H a Al}} ( provided that, R ³ is 6 carbon atoms 20 hydrocarbon residues, a is a number satisfying 0 ≦ a ≦ 1) <Effect> In the present invention, it is impossible to produce a highly stereoregular polymer with a conventional catalyst. Under the above high temperature conditions, it is possible to produce an olefin polymer having high activity and high stereoregularity at the same level as low-temperature polymerization at 80 ° C. or lower. Further, the polymer obtained by the present invention has a feature that the molecular weight distribution is wider than that of a polymer obtained by conventional so-called low-temperature polymerization at 80 ° C. or lower.

[Specific description of the invention]

[I] Catalyst The catalyst of the present invention comprises specific components (A) and (B)
. Here, “consisting of a combination” does not mean that the components are only those listed (ie, A and B), and does not exclude the coexistence of other components in a purposeful manner.

<Component (A)> Component (A) of the catalyst of the present invention is a solid catalyst component obtained by contacting the following components (i) to (iii). Here, "obtained by contact" does not mean that the object is only the indicated one (i.e., (i) to (iii)), but the coexistence of other components as appropriate. Do not eliminate.

Component (i) Component (i) is a solid component for a Ziegler-type catalyst containing titanium, magnesium and halogen as essential components. Here, "containing as an essential component" means that in addition to the three components listed, other purposeful elements may be included, and each of these elements exists as a purposeful arbitrary compound. And that these elements may be present as bonded to each other. The solid components themselves containing titanium, magnesium and halogen are known. For example,
JP-A-53-45688, JP-A-54-3894, JP-A-54-31092 and JP-A-54-31092
54-39483, 54-94591, 54-118484, 54-
131589, 55-75411, 55-90510, 55-9051
No. 1, 55-127405, 55-147507, 55-155003
No. 56-18609, No. 56-70005, No. 56-72001,
56-86905, 56-90807, 56-155206, 57
-3803, 57-34103, 57-92007, 57-1210
No. 03, No. 58-5309, No. 58-5310, No. 58-5331, No.
58-8706, 58-27732, 58-32604, 58-32
No. 605, No. 58-67703, No. 58-117206, No. 58-127708
Nos. 58-183708, 58-183709, 59-149905
And those described in JP-A-59-149906 and the like.

Examples of the magnesium compound serving as a magnesium source used in the present invention include magnesium halide, dialkoxymagnesium, alkoxymagnesium halide, magnesium oxyhalide, dialkylmagnesium, magnesium oxide, magnesium hydroxide, and magnesium carboxylate. Of these, preferred are magnesium halide, dialkoxymagnesium, and alkoxymagnesium halide.

The titanium compound serving as a titanium source is represented by the general formula Ti (OR
^{4) _4-n} X _n (where R ⁴ is a hydrocarbon residue, preferably of the order of 1 to 10 carbon atoms, X is a halogen,
n shows the number of 0 <= n <= 4. )). Specific _{examples, TiCl 4, TiBr 4, Ti} (OC 2 C 5) Cl 3, Ti (OC 2 H 5) 2 Cl 2, Ti (OC 2 H 5) 3 Cl, Ti (O-iC 3 H 7 ) Cl ₃ , Ti (O-nC ₄ H ₉ ) Cl ₃ , Ti (O-nC ₄ H ₉ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) Br ₃ , Ti (OC ₂ H ₅ ) (OC ₄ H ₉ ) ₂ Cl, 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, a molecular compound obtained by reacting an electron donor described later with TiX ′ ₄ (here, X ′ represents halogen) can also be used. Specific _{examples, TiCl 4 · CH 3 COC 2} H 5, TiCl 4 · CH 3 CO 2 C 2 H 5, TiCl 4 · C 6 H 5 NO 2, TiCl 4 · CH 3 COCl, TiCl 4 · C 6 H ₅ COCl, TiCl ₄ .C ₆ H ₅ CO ₂ C ₂ H ₅ , TiCl ₄ .ClCOC ₂ H ₅ , TiCl ₄ .C ₄ H ₄ O and the like.

Preferred among these titanium compounds are TiCl ₄ , Ti (OEt) ₄ , Ti (OBu) ₄ , Ti (OBu) Cl _{3 and the} like.

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 a halide of aluminum, a halide of silicon, and a halide of phosphorus. You can also.

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

The solid component used in the present invention includes SiCl
₄ , silicon compounds such as CH ₃ SiCl ₃ , polymer silicon compounds such as methyl hydrogen polysiloxane, Al (OiC
_{3 H 7) 3, AlCl 3} , AlBr 3, Al (OC 2 H 5) 3, Al (OCH 3) 2 C
l and other aluminum compounds and B (OCH ₃ ) ₃ , B (OC
_{2 H 5) 3, B (} OC 6 H 5) Other components used in such boron compound ₃ such as is possible, is not permissible that they remain silicon, aluminum and solid component as a component such as 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 for producing the solid component include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, and acids. Examples thereof include oxygen-containing electron donors such as anhydrides, and nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates.

More specifically, (a) a compound having 1 carbon atom such as methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, and isopropylbenzyl alcohol;
To 18 alcohols, (b) phenols having 6 to 25 carbon atoms which may have an alkyl group such as phenol, cresol, xylenol, ethyl phenol, propyl phenol, cumyl phenol, nonyl phenol, naphthol, (c) acetone C3-C15 ketones such as methyl ethyl ketone, methyl isobutyl ketone, acetophenone and benzophenone; (d) C2-C15 aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde and naphthaldehyde; (E) Methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, 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 ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxy benzoate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, γ-butyrolactone, α-valerolactone, coumarin, phthalide, ethylene carbonate, etc. Organic acid esters having 2 to 20 carbon atoms; (f) inorganic acid esters such as silicates such as ethyl silicate, butyl silicate and phenyltriethoxysilane; (g) acetyl chloride;
Acid halides having 2 to 15 carbon atoms such as benzoyl chloride, toluic acid chloride, anisic acid chloride, phthaloyl chloride, phthaloyl isochloride, etc., (thi) methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, Ethers having 2 to 20 carbon atoms such as diphenyl ether; acid amides such as (li) amide 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; and nitriles such as (ル) acetonitrile, benzonitrile, and tolunitrile. Two or more of these electron donors can be used. Among these, organic acid esters and organic acid halides are preferred, and phthalic acid esters and phthalic halides are particularly preferred.

The use amount of each of the above components can be arbitrary as long as the effects of the present invention are recognized, but generally, the following ranges are preferable.

The amount of the titanium compound used is preferably in the range of 1 × 10 ^{−4 to} 1000, and more preferably in the range of 0.01 to 10, in terms of a molar ratio to the amount of the magnesium compound used. When a compound for that purpose is used as a halogen source, the amount used is 1 × 10 5 in molar ratio to the amount of magnesium used, regardless of whether or not the titanium compound and / or the magnesium compound contains halogen. ^{-2 to} 1000, preferably 0.1 to 100.

The amounts of the silicon, aluminum and boron compounds used are in the range of 1 × 10 ^{−3 to} 100, preferably 0.01 to 1, in terms of a molar ratio with respect to the above-mentioned magnesium compounds.

The amount of the electron donating compound used is in the range of 1 × 10 ⁻³ to 10, preferably 0.01 to 5, in a molar ratio to the amount of the magnesium compound.

The solid component for producing the component (i) is produced, for example, by the following production method using the above-mentioned titanium source, magnesium source and halogen source, and if necessary, other components such as an electron donor. .

(A) A method in which a magnesium halide is brought into contact with an electron donor, if necessary, and a titanium-containing compound.

(B) A method in which alumina or magnesia is treated with a phosphorus halide compound, and a magnesium halide, an electron donor, and a titanium halide-containing compound are brought into contact therewith.

(C) A method of contacting a titanium halide compound and / or a silicon halide compound with a solid component obtained by contacting a magnesium halide with a titanium tetraalkoxide and a specific polymer silicon compound.

As the polymer silicon compound, a compound represented by the following formula is suitable.

(Here, R represents a hydrocarbon residue having about 1 to 10 carbon atoms, and n represents a degree of polymerization such that the viscosity of the polymer silicon compound becomes about 1 to 100 centistokes.) Of these, methyl hydrogen Polysiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, ethyl hydrogen polysiloxane, phenyl hydrogen polysiloxane, cyclohexyl hydrogen polysiloxane Are preferred.

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

(E) A method in which an organomagnesium compound such as a Grignard reagent is allowed to react with a halogenating agent, a reducing agent, and the like, and then contacted with an electron donor and a titanium compound as necessary.

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

Component (ii) Component (ii) used to produce component (A) is:
General formula R ¹ _m X _n Si (OR ² ) _4-mn (where R ¹ and R ² are hydrocarbon residues, X is halogen, and m and n are respectively 0 ≦ m ≦ 3 and 0 ≦ n ≦ 3, and 0 ≦ m + n ≦ 3). R ¹ and R ² are each about 1 to 20, preferably 1
To 10 hydrocarbon residues. X is preferably chlorine at least from the viewpoint of economy.

As specific examples, (CH ₃ ) Si (OCH ₃ ) ₃ , (CH ₃ ) Si (OC ₂ H ₅ ) ₃ , (C ₂ H ₅ ) ₂ Si (OCH ₃ ) ₂ , (n-C ₆ H _{11) ) Si (OCH 3) 3,} (C 2 H 5) Si (OC 2 H 5) 3, (n-C 10 H 21) Si (OC 2 H 5) 3, (CH 2 = CH) Si (OCH 3 ) ₃ , Cl (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₃ Cl, (C ₂ H ₅ ) ₂ Si (OC ₂ H ₅ ) ₂ , ( _{C 17 H 35) Si (OCH} 3) 3, Si (OC 2 H 5) 4, (C 6 H 5) Si (OCH 3) 3, Si (OCH 3) 2 Cl 2, (C 6 H 5) 2 Si (OCH ₃ ) ₂ , (C ₆ H ₅ ) (CH ₃ ) Si (OCH ₃ ) ₂ , (C ₆ H ₅ ) Si (OC ₂ H ₅ ) ₃ , (C ₆ H ₅ ) ₂ Si (OC _{2 H 5) 2, NC (CH} 2) 2 Si (OC 2 H 5) 3, (C 6 H 5) (CH 3) Si (OC 2 H 5) 2, (n-C 3 H 7) Si (OC _{2 H 5) 3, (CH} 3) Si (OC 3 H 7) 3, (C 6 H 5) (CH 2) Si (OC 2 H 5) 3, (CH ₃ ) ₃ CSi (CH ₃ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (HC (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, (CH 3) (C 2 H 5) CH-Si (CH 3) (OCH 3) 2, ((CH 3) _{2 CHCH 2) Si (OCH 3} ) 2, C 2 H 5 C (CH 3) 2 Si (CH 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 ) CHSi (OCH ₃ ) _{3 and the} like. Of these, preferred are those in which the carbon at the α-position of R ¹ is secondary or tertiary and a branched chain hydrocarbon residue having 3 to 20 carbon atoms, particularly the carbon at the α-position of R ¹ is tertiary. Carbon number 4 ~
A silicon compound having 10 branched hydrocarbon residues.

Component (iii) Component (iii) to constitute the solid catalyst component for the Ziegler-type catalyst is an organoaluminum compound.

As the organic group, about 1 to 10 carbon atoms, preferably 1 to
About 6 hydrocarbyl groups are typical.

The remaining valences (if any) of the metal of the organoaluminum compound, where at least one of the valences is filled with an organic group, are hydrogen, halogen, hydrocarbyloxy (hydrocarbyl has 1 carbon atom). ~ 10,
(Preferably about 1 to 6) or the metal via an oxygen atom (specifically, in the case of methylalumoxane, Others will be satisfied.

Specific examples of such an organoaluminum compound include trimethylaluminum, triethylaluminum, triisobutylaluminum, trin-hexylaluminum, diethylaluminum chloride, diethylaluminum hydride, diethylaluminum ethoxide, ethylaluminum sesquichloride, ethylaluminum dichloride And organoaluminum compounds such as methylaluminoxane. Further specific examples of organoaluminum compounds can be found in the examples of organoaluminum compounds described below as component (B).

Preparation of Solid Catalyst Component (A) The contacting method and amount of the components (i) to (iii) may be any as long as the effects of the present invention are recognized.
Generally, the following conditions are preferred.

The quantitative ratio of the component (i) to the component (ii) is 0.01 to 1000, preferably 0.1 to 10 in terms of the atomic ratio of silicon of the component (ii) to the titanium component constituting the component (i) (silicon / titanium).
The range is 0. The amount ratio of component (iii) to component (i) is in the range of 0.01 to 100, preferably 0.1 to 30, as the metal atom ratio (aluminum / titanium) of the organoaluminum compound.

The contact order and the number of contacts of the components (i) to (iii) are as follows:
Although there is no particular limitation, for example, the following method can be used.

(B) Component (i) → Component (ii) → Component (iii) (b) Component (i) → Component (iii) → Component (ii) (c) Component (i) → Component (ii) + Component ( iii)｝ →
{Component (ii) + component (iii)} (d) {Component (ii) + component (iii)} → component (i) (e) Method of simultaneously contacting components (i), (ii) and (iii) (F) In the methods (a) to (d), a method in which a washing step is performed between each step. The contact temperature is about −50 to 200 ° C., preferably 0 to 100 ° C.
Degree. Examples of the contacting method include a mechanical method using a rotary ball mill, a vibration mill, a jet mill, a medium stirring and pulverizing machine, and a method of contacting by stirring in the presence of an inert diluent. Inert diluents used at this time include aliphatic or aromatic hydrocarbons and halohydrocarbons, polysiloxanes and the like. In addition, at the time of these contacts, other components other than the components (i) to (iii), as long as the effects of the present invention are not impaired,
For example, methyl hydrogen polysiloxane, ethyl borate, aluminum triisopropoxide, aluminum trichloride, silicon tetrachloride, general formula Ti (OR) _4-n X _n (where 0 ≦ n ≦ 4, R is a hydrocarbon residue) It is also possible to add a titanium compound represented by the following formula (X represents a halogen), a trivalent titanium compound, tungsten hexachloride, molybdenum pentachloride or the like.

<Component (B)> The component (B) is an organoaluminum compound represented by the following general formula.

Formula ^{_{R 3 3-a H a Al}} ( provided that, R ³ is 6 to 20 carbon atoms, preferably hydrocarbon residue 8 to 12, a number of 0 ≦ a ≦ 1.) The organic Specific examples of the aluminum compound include tri-n-hexyl aluminum, tri-n-octyl aluminum, tri-n-decyl aluminum, di-n-hexyl aluminum hydride, di-n-octyl aluminum hydride, and the like.

Component (B) is used in a molar ratio (Al / Ti) of component (A) to titanium component of 0.1 to 1000, preferably 1 to 10%.
0, is in the range.

[II] Olefin Polymerization The olefin polymerization method according to the present invention comprises contacting the above-mentioned catalyst with an olefin at a temperature of 150 ° C. or higher to polymerize it.

The upper limit of the polymerization temperature is about 300 ° C, and a particularly preferred polymerization temperature is 150 to 250 ° C.

Olefin polymerization can be carried out according to a liquid phase solventless polymerization, a solution polymerization or a gas phase polymerization method using substantially no solvent. As the solvent when using the polymerization solvent,
Inert solvents such as hexane, heptane, cyclohexane, toluene, octane, decane, paraffin and white kerosene can be used.

The polymerization pressure is not particularly limited, but is usually 1 to 1000 kg / c.
It is about m ² G.

The polymerization can be carried out by any of continuous polymerization and batch polymerization. At the time of polymerization, hydrogen can be used as a molecular weight regulator as an auxiliary.

The α-olefin polymerized in the present invention has the general formula R-CH =
CH ₂ (where R is a hydrocarbon residue having 1 to 10 carbon atoms,
It may have a branched group. Which is an α-olefin having 3 or more carbon atoms, specifically, propylene, butene-1, pentene-1, hexene-1, 3-methyl-
Butene-1, 4-methylpentene-1 and the like. Among these, propylene, 3-methyl-butene-1, and 4-methylpentene-1 are preferred, and propylene is particularly preferred.

These α-olefins can be used alone or in combination of two or more.

[Production of component (A)]

200 ml of dehydrated and deoxygenated n-heptane was introduced into a flask sufficiently purged with nitrogen, and then MgCl ₂ was added thereto.
0.4 mol and 0.8 mol of Ti (O-nC ₄ H ₉ ) ₄ were introduced and reacted at 95 ° C. for 2 hours. After completion of the reaction, the temperature was lowered to 40 ° C., and then 48 ml of methylhydropolysiloxane (of 20 centistokes) was introduced and reacted for 3 hours.
The generated solid component was washed with n-heptane to obtain a solid component.

Then, 50 ml of n-heptane purified in the same manner as above was introduced into a flask sufficiently purged with nitrogen, and 0.24 mol of the solid component synthesized above was introduced in terms of Mg atoms. Then, 25 mol of n-heptane and 0.8 mol of SiCl ₄ were mixed, introduced into the flask at 30 ° 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.

50 ml of sufficiently purified n-heptane was introduced into a flask sufficiently purged with nitrogen, then 5 g of the solid component obtained above was introduced, and then (CH ₃ ) ₃ CSi (CH ₃ ) was used as the silicon compound of component (ii). ₃ ) 2.8 ml of (OCH ₃ ) ₂ was introduced, and 4.5 g of triethylaluminum as the component (iii) was further introduced, followed by contact at 30 ° C. for 2 hours. After the completion of the contact, this was sufficiently washed with n-heptane to obtain Component (A).

(Polymerization of propylene)

In a 1.5 liter stainless steel autoclave with stirring and temperature control, 500 ml of fully dehydrated and deoxygenated n-paraffin, 50 mg of tri-n-octylaluminum as component (B) and the component prepared above 100 mg of (A) was introduced, the pressure of propylene was 5 kg / cm ² G, and the polymerization temperature
Polymerization was performed at 170 ° C. for 2 hours. After completion of the polymerization, the obtained polymer solution is treated with ethanol,
The polymer was separated from n-paraffin and dried to obtain a polymer. As a result, 36.1 grams of a polymer was obtained.
The portion of this polymer that dissolves in xylene at 20 ° C (hereinafter CX
When S) was examined, it was 3.02% by weight.

Example 2 Production of Component (A) 200 ml of dehydrated and deoxygenated n-heptane was introduced into a flask sufficiently purged with nitrogen, and then MgCl ₂ was added.
0.4 mol and 0.8 mol of Ti (O-nC ₄ H ₉ ) ₄ were introduced and reacted at 95 ° C. for 2 hours. After completion of the reaction, the temperature was lowered to 40 ° C., and then 48 ml of methylhydropolysiloxane (of 20 centistokes) was introduced and reacted 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 sufficiently purged with nitrogen, and 0.24 mol of the solid component synthesized above was introduced in terms of Mg atoms. Subsequently, 0.4 ml of SiCl ₄ was mixed with 25 ml of n-heptane, 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. Then phthalic acid chloride was added to 25 ml of n-heptane.
024 moles were mixed, introduced into a 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
20 ml was introduced and reacted at 80 ° C. for 6 hours.
After the completion of the reaction, the resultant was sufficiently washed with n-heptane. This had a titanium content of 1.21 weight percent.

50 ml of sufficiently purified n-heptane was introduced into a flask sufficiently purged with nitrogen, then 5 g of the component (i) obtained above was introduced, and then (CH ₃ ) ₃ CSi as a silicon compound of the component (ii) 2.4 ml of (CH ₃ ) (OCH ₃ ) ₂ were introduced, then 0.52 ml of TiCl _{4 and} 3.0 g of triethylaluminum as the component (iii) were introduced, and contacted at 30 ° C. for 2 hours. After the end of contact, n
-Washed thoroughly with heptane to obtain component (A).

(Polymerization of propylene)

Propylene was polymerized in exactly the same manner as in Example 1, except that the amount of tri-n-octylaluminum was changed to 70 milligrams. The result was 51.3 grams of polymer, CXS = 2.22% by weight.

Example 3 In the polymerization of propylene in Example 2, the polymerization temperature was set to 16
The polymerization of propylene was carried out in exactly the same manner, except that the temperature was brought to 0 ° C and 45 milligrams of tri-n-decyl aluminum was used instead of tri-n-octyl aluminum. The result was 51.6 grams of polymer, CXS = 2.13% by weight.
Met.

Example 4 In the polymerization of propylene in Example 1, the polymerization temperature was set to 19
The polymerization of propylene was carried out in exactly the same manner except that the temperature was adjusted to 0 ° C., and 30 mg of tri-n-decyl aluminum was used as the component (B) instead of tri-n-octyl aluminum. The result is 28.9 grams of polymer,
CXS was 2.23% by weight.

Comparative Example 1 Polymerization was carried out in exactly the same manner as in Example 1, except that triethylaluminum was used instead of tri-n-octylaluminum. The result was only 1.1 grams of polymer.

[Brief description of the drawings]

FIG. 1 is to assist in understanding the technical contents of the present invention relating to the Ziegler catalyst.

Claims (1)

(57) [Claims] 1. A process for producing an olefin polymer, wherein an olefin is brought into contact with a catalyst comprising a combination of the following components (A) and (B) at a temperature of 150 ° C. or higher to carry out polymerization. Component (A) A contact product of the following components (i), (ii) and (iii): Component (i) A solid component for a Ziegler-type catalyst containing titanium, magnesium and halogen as essential components, Component (ii) General Formula R ¹ _m X _n Si (OR ² ) _4-mn (where R ¹ and R ² are hydrocarbon residues, X is halogen, and m and n are 0 ≦ m ≦ 3 and 0, respectively)
≦ n ≦ 3, and 0 ≦ m + n ≦ 3. A) a silicon compound represented by the following formula: component (iii) an organoaluminum compound; and component (B) an organoaluminum compound represented by the following general formula. Formula _{^{R 3 3-a H a Al}} ( provided that, R ³ is the number of the hydrocarbon residue having 6 to 20 carbon atoms, a is 0 ≦ a ≦ 1.)