JPH08157520A - Olefin polymerization catalyst - Google Patents

Abstract

PURPOSE: To provide a catalyst which actively catalyzes the polymerization of an olefin particularly a 3 C or higher olefin to form a highly stereoregular polymer, particularly one having an MFR of 50 or above. CONSTITUTION: This catalyst comprises a solid component of a Ziegler catalyst, essentially consisting of Ti, Mg, halogen and a silicon compound of the formula (wherein R<1> is a bivalent hydrocarbon group which, together with the carbon atom adjacent to the silicon atom, forms a ring; R<2> and R<3> are each a monovalent hydrocarbon group; and 1<=n<=3) and an organoaluminum compound.

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION

FIELD OF THE INVENTION The present invention relates to an olefin polymerization catalyst. More specifically, the present invention uses a novel solid catalyst component, and when applied to the polymerization of an olefin having 3 or more carbon atoms, a highly active and highly stereoregular polymer is obtained. In particular, a catalyst produced even under a polymerization condition which gives a polymer having a small molecular weight (that is, a polymer having a large MFR, for example, one having an MFR of 50 or more) has high stereoregularity. It is about.

[0002]

2. Description of the Related Art Conventionally, a solid component containing titanium, magnesium, halogen and, if necessary, an electron donating compound, a catalyst for olefin polymerization comprising an organoaluminum compound and optionally an electron donating compound are used to obtain a high yield. It is known that polymers with high stereoregularity can be produced at high rates (ie, high catalytic activity).

Recently, when molding a polyolefin polymer, from the viewpoint of economy, it is required to improve the molding speed in order to improve the molding cycle. For that purpose, it is necessary that the polymer has a small molecular weight, but even when the molecular weight is small, the conventional high stereoregularity is required. This is because unless the polyolefin polymer has high stereoregularity, it is difficult to obtain sufficient performance required as a molding material, for example, rigidity.

However, in the conventionally known catalysts, the stereoregularity of the polymer that can be produced decreases as the molecular weight decreases, that is, the MFR increases. For example, when a polymer having a relatively large molecular weight (for example, MFR = 1) is produced, a polymer having high stereoregularity can be obtained, but a condition for producing a polymer having a small molecular weight (for example, MFR = 50 or more) In that case, the stereoregularity is lowered and it is often difficult to obtain a highly stereoregular polymer.

Therefore, in order to solve the above-mentioned problems, for example, a method of using a large amount of an electron-donating compound as an external donor can be considered. In that case, however, the activity is greatly reduced and the cost of the catalyst is increased. Problems are hard to avoid.

[0006]

The problem to be solved by the present invention is to solve the above-mentioned problems. In the present invention, the polymer produced has a relatively small molecular weight, that is, MFR is 50 g. It is intended to provide a catalyst using a novel catalyst component which gives a polymer having high activity and high stereoregularity in / 10 minutes or more.

[0007]

[Means for Solving the Problems]

[Summary of the Invention] <Summary> The present inventors have reached the present invention by discovering that the above-mentioned problems can be solved by using a specific catalyst.

That is, the olefin polymerization catalyst according to the present invention is characterized by comprising the following components (A) and (B). Component (A): A solid component containing titanium, magnesium, halogen and a silicon compound represented by the following general formula as essential components.

Embedded image (Wherein R ¹ is a divalent hydrocarbon group forming a ring with a carbon atom adjacent to a silicon atom, R ² , R ³ and R ⁴
Represents a monovalent hydrocarbon group, and n represents a number of 1 ≦ n ≦ 3). Component (B): Organoaluminum compound

[Effect] When the catalyst using the novel solid catalyst component according to the present invention is used, a polymer having high activity and high stereoregularity can be obtained. Moreover, a polymer having a relatively small molecular weight, that is, having a MFR of 50 g / 10 minutes or more, can be obtained as a polymer having high stereoregularity.
The reason why such an effect is exhibited is not clear at present, but it is considered that a solid catalyst component containing a specific silicon compound component is used.

[Detailed Description of the Invention] <Catalyst for Olefin Polymerization> The catalyst for olefin polymerization according to the present invention comprises a specific component (A) and a specific component (B). Here, “consisting of” does not mean that the components are only those listed (ie, (A) and (B)), but excludes the coexistence of a purposeful third component. do not do.

<Component (A)> The component (A) used in the present invention includes titanium, magnesium, halogen and a general formula.

Embedded image It is a solid component containing a silicon compound represented by as an essential component. Here, R ¹ is a divalent hydrocarbon group forming a ring with a hydrocarbon adjacent to a silicon atom,
R ² , R ³ and R ⁴ each represent a monovalent hydrocarbon group, and n represents a number of 1 ≦ n ≦ 3. Where T
With respect to i, Mg, halogen and the silicon compound represented by the above general formula, "containing it as an essential component" means that other than the four components shown above, other purposeful elements may be contained. 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.

When producing the component (A) used in the present invention, a solid component containing titanium, magnesium and halogen can be used, and a known one can be used.
For example, JP-A Nos. 53-45688 and 54-3894.
No. 54, No. 54-31092, No. 54-39483, No. 54-94591, No. 54-118484, No. 54.
-131589, 55-75411, 55-9
0510, 55-90511, 55-1274.
No. 05, No. 55-147507, No. 55-15500.
No. 3, No. 56-18609, No. 56-70005,
56-72001, 56-86905, 56
-90807, 56-155206, 57-3
803, 57-34103, 57-92007.
No. 57-12103, No. 58-5309, No. 58-5310, No. 58-5311, No. 58-87.
06, 58-27732, 58-32604
No. 58, No. 58-32605, No. 58-67703, No. 58-117206, No. 58-127708, No. 5
8-183708, 58-183709, 59
The ones described in Japanese Patent Publication Nos. 149905 and 59-149906 are used.

As the magnesium compound used as the magnesium source in the present invention, magnesium dihalide, dialkoxy magnesium, alkoxy magnesium halide, magnesium oxyhalide, dialkyl magnesium, magnesium oxide, magnesium hydroxide, magnesium carboxylate, etc. Can be given. Among these, magnesium dihalide and dialkoxy magnesium are preferable.

The titanium compound serving as the titanium source has a general formula of Ti (OR ⁵ ) _4-p X _p (wherein R ⁵ is a hydrocarbon residue, preferably having about 1 to 10 carbon atoms, X
Represents halogen and p represents a number of 0 ≦ p ≦ 4). As a specific example, TiCl
₄ , TiBr ₄ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (O
C 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) C
_{l 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 , T
_{i (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, T
_{i (O-nC 6 H 13} ) 4, Ti (O-nC 8 H 17) 4,
Such as Ti _{[OCH 2 CH (C 2 H 5} ) C 4 H 9 ] _4.

A molecular compound obtained by reacting TiX ' ₄ (where X'represents halogen) with an electron donor described later can also be used as the titanium source. Specific examples of such a molecular compound 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, T
iCl ₄ · C ₆ H ₅ COCl, TiCl ₄ · C ₆ H ₅ C
O ₂ C ₂ H ₅ , TiCl ₄ · ClCOC ₂ H ₅ , TiC
l ₄ C ₄ H ₄ O and the like.

Further, TiCl ₃ (including those obtained by reducing TiCl ₄ with H ₂ , reduced with Al metal, or reduced with an organometallic compound), TiBr ₃ , Ti
It is also possible to use titanium compounds such as (OC ₂ H ₅ ) Cl ₂ , TiCl ₂ , and dicyclopentadienyl titanium dichloride. Among these titanium compounds, tetravalent titanium compounds, particularly TiCl ₄ , Ti (OC
₄ H ₉ ) ₄ , Ti (OC ₂ H ₅ ) Cl _{3 and the} like are preferable.

Halogen is the above-mentioned magnesium and
(Or) is supplied from titanium halogen compounds
Common, but other halogen sources such as AlCl₃,
AlBr₃, Al (C₂H_Five) Cl₂, Al (OC
H₃)₂Cl, etc. Aluminum halides and SiC
l_Four, Si (CH₃) Cl₃, Si (i-C₃H₇)₂
Cl ₂, Etc. Silicon halides, PCl_Five, Etc.
Halide of WCl_Five, MoCl_Five,, etc.
It can also be supplied from a known halogenating agent.

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

The silicon compound used to produce component (A) in the present invention has the general formula

[Chemical 4] (Wherein R ¹ is a divalent hydrocarbon group forming a ring with a carbon atom adjacent to a silicon atom, R ² , R ³ and R ⁴
Are each a monovalent hydrocarbon group, and n is a compound represented by 1 ≦ n ≦ 3). This silicon compound may be a mixture of two or more kinds. In the silicon compound represented by the above general formula, R ¹ is preferably a divalent hydrocarbon residue forming a ring with a carbon atom adjacent to a silicon atom having 4 to 20 carbon atoms, and R 1
² is a branched or linear saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. R ³ is an aliphatic hydrocarbon residue, preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms.

Specific examples of the silicon compound that can be used in the present invention are as follows.

Embedded image

The solid components used in the present invention are the above-mentioned essential components.
In addition to Al (O-iC₃H₇)₃Aluminum compound such as
Thing and B (OCH₃)₃, B (OC₂H_Five)₃, B
(OC ₆H_Five)₃Use of other compounds such as boron compounds such as
Is also possible, these are aluminum and boron etc.
It can be left as a component in the solid component.

Further, when producing this solid component,
It can also be produced using a known electron donor as an internal donor, which is a preferred embodiment.

As electron donors (internal donors) that can be used to produce this solid component, alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic and inorganic acids, ethers, acid amides And oxygen-containing electron donors such as acid anhydrides, nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates.

More specifically, (a) methanol, ethanol, propanol, pentanol, hexanol,
Octanol, dotecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol,
C1-C18 alcohols such as isopropylbenzyl alcohol, (b) phenol, cresol,
6 to 2 carbon atoms which may have an alkyl group such as xylenol, ethylphenol, propylphenol, isopropylphenol, nonylphenol and naphthol
5 phenols, (c) acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and other ketones having 3 to 15 carbon atoms, (d)
Aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octyl aldehyde, benzaldehyde, tolualdehyde, naphthaldehyde,
(E) Methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, cellosolve acetate, ethyl propionate, methyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, Methyl methacrylate, ethyl crotonate, cyclohexane, ethyl carboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, cellosolve benzoate. Methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate,
γ-butyrolactone, α-valerolactone, coumarin,
C2 to C20 organic acid esters such as phthalide and ethylene carbonate, (f) ethyl silicate, butyl silicate,
Phenyltriethoxysilane, t- butyl methyl dimethoxy _{silane, C 2 H 5 C (CH} 3) 2 Si (OC
Inorganic acid esters such as silicic acid esters such as ₂ H ₅ ) ₂ (excluding silicon compounds of the above general formula), (to) acetyl chloride, benzoyl chloride, toluyl chloride, anisic chloride, phthaloyl chloride, isochloride C2 to C15 acid halides such as phthaloyl,
(H) ethers having 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether, and acid amides such as (li) acetic acid amide, benzoic acid amide and toluic acid amide Kind,
(Nu) methylamine, ethylamine, diethylamine,
Tributylamine, piperidine, tribenzylamine,
Examples thereof include amines such as aniline, pyridine, picoline and tetramethylethylenediamine, and nitriles such as (l) acetonitrile, benzonitrile and tolunitrile. Two or more kinds of these electron donors can be used. Among these, preferred are organic acid esters, inorganic acid esters and organic acid halides,
Particularly preferred are phthalic acid esters, acetic acid cellosolve esters, phthalic acid halides and silicic acid esters.

As described above, the component (A) of the present invention contains optional components in addition to the above-mentioned essential components, if necessary. Compounds of (A) Vinylsilane compound As the vinylsilane compound, monosilane (SiH ₄ ) is used.
Where at least one hydrogen atom is vinyl (CH ₂ = CH
-) And some of the remaining hydrogen atoms are replaced with halogen (preferably Cl), alkyl (preferably having from 1 to 12 carbon atoms), aryl (preferably phenyl), etc. Showing a different structure, more specifically, CH ₂ ═CH—SiH ₃ , CH _{2
= CH-SiH 2 (CH 3} ), CH 2 = CH-SiH
_{(CH 3) 2, CH 2} = CH-Si (CH 3) 3, CH
_{2 = CH-SiCl 3, CH} 2 = CH-SiCl 2 (C
_{H 3), CH 2 = CH} -SiCl (CH 3) H, CH 2
_{= CH-SiCl (C 2 H} 5) 2, CH 2 = CH-Si
_{(C 2 H 5) 3,} CH 2 = CH-Si (CH 3) (C 2
_{H 5) 2, CH 2 =} CH-Si (C 6 H 5) (CH 3)
_{2, CH 2 = CH-Si} (CH 3) 2 (C 6 H 4 C
_{H 3), (CH 2 =} CH) (CH 3) 2 -Si-O-S
_{i (CH 3) 2 (CH} = CH 2), (CH 2 = CH) 2
SiCl ₂ , (CH ₂ = CH) ₂ Si (CH ₃ ) _2, etc.,
Can be illustrated. Of these, vinylsilane containing no oxygen is preferable.

(B) Organometallic compounds of metals of groups I to III of the periodic table As organometallic compounds of metals of groups I to III of the periodic table,
It has at least one organic group-metal bond. In that case, the organic group has about 1 to 10 carbon atoms, preferably 1 to 10 carbon atoms.
Approximately 6 hydrocarbyl groups are typical. The remaining valence (if any) of the metal of the organometallic compound in which at least one of the valences is satisfied by an organic group is a hydrogen atom, a halogen atom, a hydrocarbyloxy group (a hydrocarbyl group has 1 to 1 carbon atoms). About 10, preferably 1-6
Degree), or the metal through an oxygen atom (specifically, —O—Al (CH ₃ ) in the case of methylalumoxane)
-) Others are satisfied.

Specific examples of such organometallic compounds include (a) organolithium compounds such as methyllithium, n-butyllithium and tert-butyllithium, (ii) butylethylmagnesium, dibutylmagnesium and hexylethylmagnesium. , Butylmagnesium chloride,
Organomagnesium compounds such as tert-butylmagnesium bromide, (c) diethylzinc, organozinc compounds such as dibutylzinc, (d) trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-
Hexyl aluminum, diethyl aluminum chloride, diethyl aluminum hydride, diethyl aluminum ethoxide, ethyl aluminum sesquichloride,
Organic aluminum compounds such as ethylaluminum dichloride and methylaluminoxane can be mentioned. Of these, organoaluminum compounds, particularly trialkylaluminum compounds, are preferred.

The above optional components may be used alone or in combination of two or more. The effect of the present invention is enhanced by using these optional components.

Production of Component (A) The component (A) is prepared by contacting each component constituting the component (A) or the above optional components stepwise or temporarily with each other, preferably in the middle and ( Or) It can be prepared by finally washing with an organic solvent such as a hydrocarbon or a halohydrocarbon. In that case,
A solid product containing Ti, Mg and halogen as essential components may be first produced and then contacted with a silicon compound represented by the general formula (so-called two-step process), or T
It is also possible to use a method (so-called one-step method) in which component (A) is produced all at once by making the silicon compound already exist in the process of producing a solid product containing i, Mg and halogen as essential components. The preferred method is the former.

The contact conditions of the respective components constituting the above-mentioned component (A) may be arbitrary as long as the effects of the present invention are recognized, but the following conditions are generally preferred. The contact temperature is about -50 to 200 ° C, preferably 0 to 100 ° C,
Is. Examples of the contacting 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 amount of each component constituting the component (A) may be any amount as long as the effects of the present invention are recognized, but in general, the following range is 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 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. The range of ^{-2 to} 1000 is preferable, and the range of 0.1 to 100 is preferable.

The amount of the silicon compound used is 0.01 to 1000, preferably 0.1 to 10, in terms of the atomic ratio of silicon to the titanium component constituting the component (A) (silicon / titanium).
It is within the range of 0.

When the vinylsilane compound is used, the amount used is preferably in the range of 0.001 to 1000, and more preferably in the range of 0.01 to 100 in terms of molar ratio to the titanium component constituting the component (A). Is. When using aluminum and boron compounds, the amount used is
1 in molar ratio to the amount of the above magnesium compound used
The range of × 10 ^{-3 to} 100 is preferable, and 0.01 is preferable.
Within the range of 1 to 1.

When the electron-donating compound is used, its amount is preferably in the range of 1 × 10 ^-3 to 10 with respect to the amount of the above-mentioned magnesium compound to be used, preferably 0.01-5. Within the range of.

Component (B) The organoaluminum compound used in the present invention is a compound represented by the following general formula. R ⁶ _3-m AlX _m (wherein R ⁶ has 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms)
Hydrocarbon residue, X is hydrogen or halogen, and m is 0
≤ m ≤ 2 respectively) Specific examples of such compounds include (a) trialkyl such as trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, and tridecyl aluminum. Alkyl aluminum halides such as aluminum, (b) diethyl aluminum monochloride, diisobutyl aluminum monochloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, (c) diethyl aluminum hydride,
Diisobutylaluminum hydride, and of these, (a) trialkylaluminum is preferable.

In addition to these organoaluminum compounds (a) to (c), other organometallic compounds such as R ⁷ _3-q Al (O
R ⁸ ) _q (where 1 ≦ q ≦ 3, R ⁷ and R ⁸ may be the same or different and have 1 to 20 carbon atoms, preferably 1 to
Alkyl aluminum alkoxide represented by 12 of the hydrocarbon residue) can also be used in combination.

For example, combination of triethylaluminum and diethylaluminum ethoxide, combination of diethylaluminum monochloride and diethylaluminum ethoxide, combination of ethylaluminum dichloride and ethylaluminum diethoxide, triethylaluminum and diethylaluminum ethoxide. It can be used in combination with diethyl aluminum chloride. Further, alumoxanes such as methyl alumoxane, ethyl alumoxane, isobutyl alumoxane and the like can also be used.
When the organoaluminum compound is used in combination, it is particularly preferably used in combination with trialkylaluminum. That is, (a)
And (ii) and (ii) and (iii), (ii) and alkyl aluminum alkoxide, and (ii) and alumoxane.

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

<Use of Catalyst / Polymerization> The catalyst according to the present invention is used for olefin polymerization. That is, not only is it applied to ordinary slurry polymerization, but it is also applied to liquid phase solventless polymerization (bulk polymerization), solution polymerization or gas phase polymerization method that does not substantially use a solvent. Also, continuous polymerization,
It can also be applied to batch polymerization or prepolymerization. As the polymerization solvent in the case of slurry polymerization, hexane, heptane, pentane, cyclohexane, benzene,
Saturated aliphatic or aromatic hydrocarbons such as toluene may be used alone or as a mixture. Polymerization temperature is from room temperature to 150
° C. approximately, preferably 50 to 100 ° C., the polymerization pressure is atmospheric pressure ~300kg / cm ^2, preferably about atmospheric pressure to
It is 50 kg / cm ² , and hydrogen can be supplementarily used as a molecular weight regulator at that time.

Further, in order to control the stereoregularity of the obtained polymer, a known ester as a fourth component at the time of polymerization,
An electron-donating compound such as ether or amine can also be used. In the case of slurry polymerization, the amount of component (A) used is preferably in the range of 0.001 to 0.1 gram, and component (A) / liter solvent.

The α-olefins polymerized by the catalyst system of the present invention are represented by the general formula R-CH = CH ₂ (wherein R is hydrogen or a hydrocarbon residue having 1 to 10 carbon atoms, and a branched group is May be present). Specifically, there are olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1. Preferred are ethylene and propylene.
In addition to homopolymerization of these α-olefins, copolymerization,
For example, it is possible to copolymerize propylene with up to 30% by weight, based on propylene, of the abovementioned olefins, in particular ethylene. Copolymerization with other copolymerizable monomers (for example, cyclic olefin, diolefin, etc.) can also be performed.

The catalyst system of the present invention is suitable for homopolymerization or copolymerization of olefins, but particularly when homopolymerization or copolymerization of propylene has a low molecular weight, that is, a high MFR, for example, 50 to 300 g / 10 minutes, Preferably 50-100g
High stereoregularity is obtained even in a propylene polymer of / 10 minutes.

[0043]

[Examples] Example-1 [Production of component (A)]
200 ml dehydrated and deoxygenated n-heptane
Was introduced, and then MgCl₂0.4 mol and Ti
(O-nC_FourH ₉)_FourWas introduced at 0.8 mol, and 2
Allowed to react for hours. After the reaction was completed, the temperature was lowered to 40 ° C. and then
Ide methylhydropolysiloxane (20 centistoke
48 ml) and let them react for 3 hours
Was. The solid component produced was washed with n-heptane. Just
In a flask thoroughly replaced with nitrogen, and purify in the same manner as above.
50 ml of n-heptane was introduced and synthesized as above.
0.24 mol of the obtained solid component was introduced in terms of Mg atom.
Then add 25 ml of n-heptane to SiCl_Four 
Mix 0.4 mol and transfer to a flask at 30 ℃ for 30 minutes.
It was put in and reacted at 70 ° C. for 3 hours. After completion of the reaction,
It was washed with putan.

Then as a silicon compound

[Chemical 6] 2.1 ml of was introduced and contacted at 30 ° C. for 2 hours. After the contact was completed, it was thoroughly washed with n-heptane to obtain a component (A). When a part of it was taken out and the composition was analyzed, the Ti content was 2.6 wt%,

[Chemical 7] Content = 9.7 wt%.

[Polymerization of Propylene] In a stainless steel autoclave having an internal volume of 1.5 liter equipped with a stirring and temperature control device, 500 ml of sufficiently dehydrated and deoxidized n-heptane and triethylaluminum as component (B) were added. 100 milligrams and 15 milligrams of component (A) prepared above, then 400 grams of hydrogen
Introduce milliliter, raise temperature and pressure, polymerization pressure = 5 kg /
The polymerization operation was performed under the conditions of cm ² G, polymerization temperature = 70 ° 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, 182.3 g of polymer was obtained. Further, 0.26 g of a polymer was obtained from the filtrate. From the boiling heptane extraction test, all products I.V. I (hereinafter T
-I. (Abbreviated as I) was 98.9 weight percent.
MFR = 71.6 g / 10 min, polymer bulk specific gravity = 0.4
It was 8 g / cc.

Example 2 [Production of Component (A)] 5 Substituted with Well Purified Nitrogen
In a 00 ml flask, place Mg (OC ₂H_Five)₂
20 g, 100 milliliters of purified toluene
Then TiCl_Four Introduce 60 ml, 7
Raise the temperature to 0 ° C, then add 3.2 ml of cellosolve acetate.
Introduced in torr, heated to 100 ° C., and reacted for 3 hours. Anti
After completion of the reaction, the reaction product was thoroughly washed with n-heptane. That
Later, TiCl_Four Introduce 100 ml,
The reaction was carried out at 110 ° C for 3 hours. After the reaction, n-hepta
Solid to produce component (A) after thorough washing with
As an ingredient.

Similar to the synthesis of the component (A) of Example-1,
Into a well-purified flask, 50 ml of n-heptane was introduced, and then 5 g of the solid component obtained above was introduced.

Embedded image 2.4 ml was introduced, and then Al (n-C ₆ H
₁₃ ) 1.8 g of each of ₃ ) ₃ was introduced, and they were contacted at 70 ° C. for 2 hours. After the contact was completed, it was thoroughly washed with n-heptane to obtain a component (A). When I analyzed the composition of a part,
Titanium content = 2.7 wt%,

[Chemical 9] Content = 11.8 wt%.

[Polymerization of Propylene] Polymerization was carried out in the same manner as in Example 1 except that the polymerization temperature was changed to 75 ° C. 171.8 grams of polymer were obtained, T-I. I = 98.3 wt%, MFR = 49.
It was 7 g / 10 minutes, and the bulk density of the polymer was 0.42 g / cc.

Examples 3 to 6 Polymerization of propylene was carried out in the same manner as in the production of the component (A) of Example-2, except that the compounds shown in Table 1 were used as the silicon compound. The same procedure as in Example-2 was performed. Table 1 shows the results.

Comparative Examples 1 to 2 In the production of the component (A) of Example-1, the compounds shown in Table 2 were used as the silicon compound,
Component (A) was produced in exactly the same manner as in 1, and propylene was polymerized in exactly the same manner. The results are shown in Table 2.

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

[Brief description of drawings]

FIG. 1 helps to understand the technical content of the present invention regarding a Ziegler catalyst.

Claims (1)

[Claims] 1. A catalyst for olefin polymerization, comprising the following components (A) and (B): Component (A): A solid component containing titanium, magnesium, halogen and a silicon compound represented by the following general formula as essential components. Embedded image (Wherein R ¹ is a divalent hydrocarbon group forming a ring with a carbon atom adjacent to a silicon atom, R ² , R ³ and R ⁴
Represents a monovalent hydrocarbon group, and n represents a number of 1 ≦ n ≦ 3). Component (B): Organoaluminum compound