JP2541538B2 - Olefin polymerization catalyst - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a catalyst for olefin polymerization. More specifically, the present invention relates to olefins, particularly α-olefins having 3 or more carbon atoms, by using a specific catalyst,
When applied to the above polymerization, the highly stereoregular polymer can be advantageously produced in industrial production under stable polymerization conditions.

BACKGROUND OF THE INVENTION A catalyst for olefin polymerization composed of organoaluminum and a solid catalyst component containing titanium, magnesium and halogen as essential components, which has been proposed hitherto, has extremely high activity, but the stereoregularity of the product polymer becomes a problem. In some cases, it was necessary to use an electron donating compound during the polymerization.

However, such a catalyst that uses 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 increases the polymerization temperature. Since the reaction is accelerated, it is limited to increase the polymerization temperature to increase the polymerization amount (improve the production efficiency).
There is a problem that it is difficult to control the performance of the product polymer, including controlling the molecular weight of the product polymer.

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

Prior Art JP-A-58-138715 discloses a titanium composite (1) containing tetravalent titanium, magnesium, halogen and an electron donor as essential components without using 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. A method is disclosed in which the polymerization is carried out with a catalyst system formed from the solid component obtained and organoaluminum.

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

Therefore, the present inventors, in JP-A-61-19231,
Using a solid catalyst component obtained by contacting a specific silicon alkoxide compound with a component obtained by prepolymerizing an olefin on a solid component containing titanium, magnesium and halogen as essential components, It proposes a method to solve the problems that were present.

Although the technology according to this proposal is effective, it goes without saying that this technology is convenient if there are other effective technologies.

[Outline of Invention]

SUMMARY The present invention provides a catalyst other than the above-mentioned prior art.

That is, the olefin polymerization catalyst according to the present invention comprises the following components (A) and (B).

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

Component (i): Olefin in the presence of an organoaluminum compound and an aluminum compound represented by the general formula AlX ₃ (where X represents halogen) in a solid component containing tetravalent titanium, magnesium and halogen as essential components. Component obtained by contacting with and preliminarily polymerizing.

Component (ii): general formula (However, R ¹ is a branched chain hydrocarbon residue, R ² is the same or different hydrocarbon residue as R ¹ , R ³ is a hydrocarbon residue,
n represents a number of 1 ≦ n ≦ 3), and the component (B) organoaluminum compound.

EFFECTS OF THE INVENTION Since the olefin polymerization catalyst of the present invention does not use an electron-donating compound (external donor) during the polymerization, there is no decrease in the polymerization rate, and therefore there is no problem even if the polymerization temperature is raised without causing a problem. The point is eliminated.

These characteristics are extremely advantageous in industrial production and are important points as the characteristics of the catalyst.

Although the reason why such a catalyst has been obtained has not been sufficiently analyzed, the present inventors believe that it is due to the interaction between a specific silicon compound having a branched hydrocarbon residue and an aluminum halogen compound. There is. Specifically, it is considered that this effect is shown by the large amount of silicon compound contained in the catalyst component due to the action of the aluminum compound.

Further, when the component (A) contains an electron donating compound, unlike the prior art, the electron donating compound has a characteristic that is hardly removed from the component (A), and the component (A) Is considered to contribute to the stability of.

[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” means that, in addition to these two components, an auxiliary component that does not violate the gist of the present invention may be included (details described later).

Component (A) The component (A) of the catalyst of the present invention is a solid catalyst component obtained by bringing the following component (i) and component (ii) into contact with each other. The phrase "obtainable by contacting" also means that, in addition to these two components, an auxiliary component that does not violate the gist of the present invention may be included (details described later).

The solid component containing tetravalent titanium, magnesium and halogen used as the component (i) as essential components is a known solid component. For example, JP-A-53-45688, 5
4-3894, 54-31092, 54-39483, 54-945
No. 91, No. 54-118484, No. 54-131589, No. 55-75411
No. 55, No. 55-90510, No. 55-90511, No. 55-127405,
55-147507, 55-155003, 56-18609, 5
6-70005, 56-72001, 56-86905, 56-90
807, 56-155206, 57-3803, 57-34103
No. 57-92007, No. 57-121003, No. 58-5309,
58-5310, 58-3511, 58-8706, 58-27
732, 58-32604, 58-32605, 58-67703
No. 58-117206, No. 58-127708, No. 58-183708
No. 58-183709, No. 59-149905, No. 59-149906, etc. 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.

In addition, the titanium compound serving as the titanium source has a general formula
Ti (OR ⁴ ) _4-n X _n (wherein R ⁴ is a hydrocarbon residue, preferably having about 1 to 10 carbon atoms, X is halogen, and n is 0 ≦ n ≦ 4 Compounds represented are listed. Specific examples include 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, 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 (OC 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 ] is _4, and the like.

It is also possible to use a molecular compound obtained by reacting TiX ' ₄ (where X'is halogen) with an electric 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, 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, etc.

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

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 , CH ₃ SiCl ₃ , silicon compounds such as methyl hydrogen polysiloxane, Al (O-iC ₃ H ₈ ) ₃ , AlCl ₃ , AlBr ₃ , Al (OC ₂ H ₅ ) ₃ , Al (OCH ₃ ) ₂ Cl Aluminum compounds such as B (OCH ₃ ) ₃ , B (O
Other components of boron compounds such as C ₂ H ₅ ) ₃ and B (OC ₆ H ₅ ) ₃ can also be used, and it is acceptable that these components remain in the solid component as components such as silicon, aluminum and boron. It

Further, an electron donor that can be used as an internal donor of an electron donor when producing this solid component can also be used as an internal donor.

Examples of electron donors (internal donors) that can be used for producing this solid component include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, ethers, acid amides, and 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 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 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 Acid halides having 2 to 15 carbon atoms such as chloride, anisyl chloride, phthaloyl chloride, and isophthaloyl chloride, (thi) methyl ether,
Ethers having 2 to 20 carbon atoms such as ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, acid amic acid such as (li) acetic acid amide, benzoic acid amide, toluic acid amide, and (nu) methyl Amines such as amine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, and tetramethylethylenediamine,
(L) Acetonitrile, benzonitrile, nitrites such as tornitol, and the like can be used. Two or more of these electron donors can be used.

The amount of each component used may be arbitrary as long as the effects of the present invention are recognized, but generally, the following ranges are preferable.

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 having a halogen source is used, regardless of whether the titanium compound and / or the magnesium compound contains halogen, the molar ratio to the amount of magnesium used is 1 × 10 ^{-2 to} 1000. The range is good, and the range is preferably 0.1 to 100. The amount of silicon, aluminum and boron compounds used is preferably in the range of 1 × 10 ^{−3 to} 100, and more preferably 0.01 to 1, in molar ratio with respect to the amount of the above magnesium compound used.

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.

The solid component used in the present invention can be produced by a known method, but the following production method is preferable. Specific examples of the compounds used in these methods are as described above.

(A) A method in which magnesium halide, an electron donor and a titanium-containing compound are co-ground and treated with a specific solvent.

(B) A method of treating alumina or magnesia with a phosphorus halide compound, and then contacting the magnesium halide, the electron donor and the titanium halogen-containing compound.

(C) A method of bringing an electron donor, 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. In this case, as the polymer silicon compound, Those represented by are preferred. In this formula, R is C ₁ -C ₁₀
Hydrocarbon residue of about n, the viscosity of this polymer is 0.1-1
It is a value that will be 00 centistokes.

(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 with a halogenating agent or a titanium halogen compound.

The catalyst component (i) used in the present invention is obtained by bringing the solid component obtained as described above into contact with an olefin in the presence of an organoaluminum compound and an aluminum halogen compound and preliminarily polymerizing the olefin. It is an ingredient.

The prepolymerization conditions of the olefins for producing the component (i) are not particularly limited, but the following conditions are generally preferable. Polymerization temperature is 0 to 80 ° C, preferably 10 to 60 ° C
The polymerization pressure is about atmospheric pressure to about 10 kg / cm ² . The amount of polymerization is preferably 0.001 to 50 grams of olefins, and more preferably 0.1 to 10 grams of olefins, per gram of the solid component.

As the organoaluminum component in the prepolymerization, those generally known for Ziegler type catalysts can be used.

Specific examples include 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) 2 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 ), etc.

Among these, Al (C ₂ H ₅ ) ₃ and Al (iC ₄ H ₉ ) ₃ are preferable. Further, the combined use of trialkylaluminum and alkylaluminum halide, the combined use of trialkylaluminum, alkylaluminum halide and alkylaluminum ethoxide is also effective. As a specific example, Al (C ₂ H ₅ ) ₃ and Al (C ₂ H ₅ ) ₂ Cl
Combination of Al (iC ₄ H ₉ ) ₃ and Al (iC ₄ H ₉ ) ₂ Cl, combination of Al (C ₂ H ₅ ) ₃ and Al (C ₂ H ₅ ) _1.5 Cl _1.5 , Al (C ₂ A combination of H ₅ ) ₃ and Al (C ₂ H ₅ ) ₂ Cl and Al (C ₂ H ₅ ) ₂ (OC ₂ H ₅ ) can be mentioned.

One of the features of the present invention is that the formula AlX ₃ (X:
It means that an aluminum halogen compound of (halogen) coexists. Examples of the aluminum halide used in the prepolymerization include AlCl ₃ , AlBr ₃ , AlI ₃ and the like, but AlCl ₃ and AlBr ₃ are preferable.

The amount of the organoaluminum component used in the prepolymerization is 1 to 20 in terms of Al / Ti (molar ratio) with respect to the Ti component in the solid component,
It is preferably 2 to 10. Further, the amount of the aluminum halogen compound used in the prepolymerization is 0.01 to 100, preferably 0.1 to 1 in a molar ratio with respect to the organic aluminum.
0.

In addition to these, alcohol, ester,
A known electron donor such as a ketone can also be added.

Examples of the olefins used in 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 component (i) obtained by contacting a solid component containing titanium, magnesium and halogen as essential components with an olefin in the presence of an organoaluminum compound to prepolymerize it is obtained.

The component (ii) to be contacted with the above component (i) for producing the component (A) of the catalyst of the present invention has the general formula: (However, R ¹ is a branched chain hydrocarbon residue, R ² is the same or different hydrocarbon residue as R ¹ , R ³ is a hydrocarbon residue,
n is a silicon compound represented by 1 ≦ n ≦ 3).

Here, R ¹ is preferably branched from a carbon atom adjacent to a silicon atom. The branching group in that case is an alkyl group, a cycloalkyl group or an aryl group (for example,
It is preferably a phenyl group or a methyl-substituted phenyl group). More preferable R ¹ is such that the carbon atom adjacent to the silicon atom, that is, the α-position carbon atom is a secondary or tertiary carbon atom. In particular, those having a tertiary carbon atom bonded to a silicon atom are preferable. The prime number of R ¹ is usually 3 to 20, preferably 4 to 10.

R ² is usually a branched or linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. R ³ is usually an aliphatic hydrocarbon group, preferably a linear aliphatic hydrocarbon group having 1 to 4 carbon atoms.

 Specific examples of the silicon compound as the component (ii) are shown below.

The above-mentioned contact conditions of the component (i) and the component (ii) may be arbitrary as long as the effect of the present invention is recognized, but generally, the following conditions are preferable. Contact temperature is -50 to 20
It is about 0 ° 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.
Inert diluents used at this time include aliphatic or aromatic hydrocarbons and halohydrocarbons, polysiloxanes and the like. 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.

Component (B) Component (B) is an organoaluminum compound. As a specific example Or (Where R ⁵ and R ⁶ may be the same or different and have 1 carbon atom
To about 20 hydrocarbon residues or hydrogen atoms, R ⁷ is a hydrocarbon residue, X is a halogen, and n and m are each 0 ≦ n <
3, 0 <m <3. ). Specifically, (a) trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum,
Trialkyl aluminum such as tridecyl aluminum, (b) Diethyl aluminum monochloride, diisobutylaluminium monochloride, alkyl aluminum halide such as ethyl aluminum sesquichloride, ethyl aluminum dichloride, (c)
Aluminum alkoxides such as diethyl aluminum hydride, diisobutyl aluminum hydride, (d) diethyl aluminum ethoxide, and diethyl aluminum phenoxide can be given.

In addition to these organoaluminum compounds (a) to (c), other organometallic compounds, for example, (Here, 1 ≦ a ≦ 3, R ⁸ and R ⁹ may be the same or different and are a hydrocarbon residue having about 1 to 20 carbon atoms.) The alkylaluminum alkoxide represented by the formula (1) may also be used in combination. For example, a combination of triethyl aluminum and diethyl aluminum ethoxide, a combination of diethyl aluminum monochloride and diethyl aluminum ethoxide, a combination of ethyl aluminum dichloride and ethyl aluminum ethoxide, a combination of triethyl aluminum, diethyl aluminum ethoxide and diethyl aluminum chloride It 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).

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 does not substantially use a solvent. Further, it is also applicable to a system in which continuous polymerization, batch polymerization or preliminary polymerization is carried out. As a polymerization solvent in the case of slurry polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, or toluene is used alone or as a mixture. The polymerization temperature is from room temperature to about 200 ° C., preferably 50 to 150 ° C., the polymerization pressure is normal pressure to about 50 kg / cm ² , and the polymerization time is about 0.5 to 10 hours. Hydrogen can be supplementarily used as a molecular weight regulator at that time.

The olefins polymerized with the catalyst system of the present invention have the general formula R
—CH═CH ₂ (where R is a hydrogen atom, or 1 to 10 carbon atoms)
Is a hydrocarbon residue of, and may have a branching group). Specifically, there are olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1. Preferred are ethylene and propylene. In the case of these polymerizations, up to 50 weight percent relative to ethylene,
Preferably up to 20 weight percent of the above olefins can be copolymerized, and up to 30 weight percent of propylene with respect to the above olefins, especially ethylene. Copolymerization with other copolymerizable monomers (for example, vinyl acetate, diolefin, etc.) can also be performed.

Experimental Example Example 1 [Production of component (A)] A fully dried and nitrogen-substituted 0.4 liter ball mill, filled with 40 12 mmφ stainless steel balls, and MgCl 2.
30 g of ₂ and 23.3 ml of diheptyl phthalate were introduced, and the mixture was pulverized with 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, 26.4 g of the ground composition was introduced into a flask which had been sufficiently replaced with nitrogen, and 25 ml of n-heptane and 75 ml of TiCl ₄ were further introduced and reacted at 100 ° C. for 3 hours. After completion of the reaction, it was thoroughly washed with n-heptane. A part of the obtained solid component was taken out and subjected to compositional analysis. As a result, it was a solid component containing Ti, magnesium and halogen as essential components having a Ti content of 3.12 wt%.

Then an internal volume of 1.5 with stirring and temperature control
Into a liter stainless steel stirring tank, 500 ml of fully dehydrated and deoxygenated n-heptane, 4.2 g of triethylaluminum, 1.2 g of AlCl ₃ 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. When a part of the solid component was taken out and the amount of propylene polymerized was examined, it was 1.12 g of propylene per 1 g of the solid component (i).

50 ml of sufficiently purified n-heptane was introduced into a flask that had been sufficiently replaced with nitrogen, then 5 g of the component (i) obtained above was introduced, and then CH ₃ -C (CH 2) as a silicon compound of the component (ii). 0.34 ml of ₃ ) ₂ -Si (CH ₃ ) (OCH ₃ ) ₂ was introduced and contacted at 30 ° C for 2 hours. After completion of contact, thoroughly wash with n-heptane,
It was set as the component (A).

[Polymerization of propylene]

In a stainless steel autoclave with an internal volume of 1.5 liters 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, 60 ml of hydrogen was introduced, the temperature was raised, and the pressure was raised to carry out polymerization under the conditions of polymerization pressure = 5 kg / cm ² G, 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, 138.6 grams of polymer was obtained. One filtrate yielded 1.1 grams of polymer.

From the boiling heptane extraction test, the total product II (hereinafter abbreviated as T-II) was 97.9 parts by weight. MFR = 2.0g /
After 10 minutes, the bulk density of the polymer was 0.42 g / cc.

Example 2 [Production of Component (A)] 200 ml of dehydrated and deoxygenated n-heptane was introduced into a flask sufficiently replaced 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 (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 in Example 1 was introduced into a flask which had been sufficiently replaced with nitrogen, and 0.24 mol of the solid component synthesized above was converted in terms of Mg atom. Then, 25 ml of n-heptane was mixed with 0.4 mol of SiCl ₄ and the mixture was introduced into the flask at 30 ° C. for 30 minutes.
Allowed to react for hours. After the completion of the reaction, the resultant was washed with n-heptane. Then, 25 ml of n-heptane was mixed with 0.016 mol of diheptyl phthalate, and the mixture was introduced into the flask at 70 ° C for 30 minutes and reacted at 70 ° C for 1 hour. After completion of the reaction, n-
Wash with heptane. Then, 100 ml of TiCl ₄ was introduced and the reaction was carried out at 100 ° C. for 3 hours. After completion of the reaction, n
-Wash thoroughly with heptane. The titanium content of this product is
It was 2.61 weight percent. This was used as a solid component for producing the component (i).

Using this solid component, component (i) was produced under the same conditions as in Example 1 except that the introduction time of propylene was 90 minutes. The amount of propylene prepolymerized as the obtained component (i) was 3.31 g per 1 g of the solid component.
The composition of the solid component (i) was analyzed to find that the titanium content was 2.41 weight percent, the diheptyl phthalate content was 8.43 weight percent, and the aluminum content was 2.
It was 21 weight percent.

Then, the component (i) and the component (ii) were contacted. The contact was performed in the same manner as in Example 1 except that the amount of the silicon compound as the component (ii) used in Example 1 was changed to 0.81 ml. After the contact was completed, it was thoroughly washed with n-heptane to obtain a component (A). Composition analysis of the solid component of component (A) revealed that the titanium content was 2.40 weight percent, the diheptyl phthalate content was 8.41 weight percent, and the (tC ₄ H ₉ ) (CH ₃ ) Si (OCH ₃ ) ₂ content was 7.96. The weight percent and the aluminum content were 2.03 weight percent.

[Polymerization of propylene]

Use 250 parts of component (B) triethylaluminum
Polymerization was performed under the same conditions as in Example 1 except that the amount was milligram.

The result was 238.3 grams of polymer, MFR = 1.
9g / 10min, T-II = 98.8wt%, polymer bulk specific gravity = 0.47g /
It was cc.

Example 3 [Production of Component (A)] In the production of the component (A) of Example 2, phthalic acid chloride was used instead of diheptyl phthalate, and TiCl ₄ was used.
Use 20 ml of SiCl ₄ instead of 110
A solid component was produced in the same manner as in Example 2 except that the treatment was carried out at 6 ° C for 6 hours.

Using the solid component prepared above, the amount of triethylaluminum used is 3.2 grams and the amount of AlCl ₃ used is 1.
Prepolymerization was performed in the same manner as in Example 1 except that the amount was changed to 7 grams.

At this time, the amount of propylene polymerized was 1.01 g per 1 g of the solid component. [Component (i)].

Then, the component (ii) was contacted with the component (i) in the same manner as in Example 1 except that the amount of the silicon compound used was 1.6 ml and the component (i) obtained as described above was used. went. After the contact was completed, it was thoroughly washed with n-heptane to obtain the component (A).

[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 polymerization temperature was changed to 80 ° C. The result was 154.2 grams of polymer, MFR =
2.2 g / 10 minutes, TI-1 = 99.0 weight percent, and polymer bulk specific gravity = 0.49 g / cc.

Examples 4 to 7 In the production of the component (A) of Example 2, as a silicon compound of the component (ii), CH ₃ -C (CH ₃ ) _2- Si (CH ₃ ) (OCH ₃ ) ₂ was used instead of the table. A catalyst was produced in the same manner as in Example 2 except that the compound shown in 1 was used to polymerize propylene. The results are shown in Table-1.

Example 8 [Production of component (A)] 200 ml of dehydrated and deoxygenated n-heptane was introduced into a flask thoroughly 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 the reaction was completed, the temperature was lowered to 35 ° C, and 1,3,5,7-
60 ml of tetramethylcyclotetrasiloxane was introduced and reacted for 5 hours. The resulting solid component was washed with n-heptane.

Then, n-heptane was added to a flask that had been sufficiently replaced with nitrogen.
Introduce 100 ml and add the solid component synthesized above to Mg
0.12 mol was introduced in terms of atoms. Next, 0.24 mol of SiCl ₄ was introduced at 20 ° C. for 30 minutes, and the reaction was carried out at 50 ° C. for 3 hours. After completion of the reaction, it was washed with n-heptane to obtain a solid component for producing the component (i). The titanium content in this solid component was 4.48 weight percent.

Using this solid component, prepolymerized component (i) was produced in the same manner as in Example 2 except that the prepolymerization temperature was 15 ° C. The polymerization amount of the obtained component (i) propylene was 0.96.
It was gram.

The component (i) and the component (ii) were contacted in the same manner as in Example 1 except that the component (i) was used and the amount of the silicon compound as the component (ii) used was 1.9 ml. After contact is over,
It was thoroughly washed with n-heptane to obtain a component (A).

[Polymerization of propylene]

Polymerization was carried out 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. under the propylene polymerization conditions of Example 2. As a result, 115 g of polymer was obtained, and MFR = 3.8 g / 10
Min, T-II = 96.2 weight percent, polymer bulk specific gravity =
It was 0.48 g / cc.

Example 9 Component (A) was produced under the same conditions as in Example 2 except that ethyl benzoate was used instead of diheptyl phthalate in the production of component (A) of Example 2. Polymerization of propylene was also carried out in the same manner as in Example 2. As a result, 9
6.8 g of polymer was obtained, MFR = 4.3 g / 10 min, T-
II = 95.0 weight percent, polymer bulk specific gravity = 0.44 g / cc
Met.

Comparative Example 1 In the production of the component (i) of Example 3, Al during prepolymerization was used.
Polymerization of propylene was also carried out in the same manner except that Cl ₃ was not used. 141 grams of polymer were obtained, MFR = 2.9 g / 10 min, T-II = 98.3 weight percent, and polymer bulk specific gravity = 0.47 g / cc.

Examples 10 to 12 In the production of the component (i) of Example 2, during prepolymerization
Except that the amount of AlCl ₃ used was changed as shown in Table-2,
In the same manner, propylene was polymerized. The results are shown in Table-2.

[Brief description of drawings]

FIG. 1 is for helping the understanding of the technical contents of the present invention regarding the Ziegler catalyst.

Claims (1)

(57) [Claims] 1. An olefin polymerization catalyst comprising the following components (A) and (B). Component (A) A solid component obtained by contacting the following components (i) to (ii). Component (i): Olefin in the presence of an organoaluminum compound and an aluminum compound represented by the general formula AlX ₃ (where X represents halogen) in a solid component containing tetravalent titanium, magnesium and halogen as essential components. Component obtained by contacting with and preliminarily polymerizing. Component (ii): general formula (However, R ¹ is a branched chain hydrocarbon residue, R ² is the same or different hydrocarbon residue as R ¹ , R ³ is a hydrocarbon residue,
n represents a number of 1 ≦ n ≦ 3), and the component (B) organoaluminum compound.