JPH03140308A - Preparation of polymerization catalyst for polyolefin - Google Patents

Abstract

PURPOSE:To prepare the subject highly strong and active catalyst comprising porous spherical particles by stirring the complex compound of a Mg compound with an alcohol in the presence of a surfactant in a solvent at a temperature of >= the melting point, rapidly cooling the stirred suspension, drying the resultant solid particles and subsequently treating the dried solid particles with a halogenated Ti and an electron-donor. CONSTITUTION:A magnesium compound (e.g. magnesium chloride) and an alcohol (e.g. ethanol) are reacted with each other in an inactive organic solvent (e.g. hexane) to prepare a complex compound, which is heated and stirred in the presence of a nonionic surfactant at a temperature range of >= the melting point to give a suspension solution. The suspension solution is rapidly cooled to form a spherical solid component without the evaporation of the alcohol. The solid component is partially dried and subsequently treated with titanium halide (e.g. titanium tetrachloride) and an electron donor (e.g. isobutyl phthalate) to provide the objective polymerization catalyst component.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a polymerized solid catalyst component for polyolefins. More specifically, the present invention relates to a method for producing a solid catalyst component having a large particle size and a spherical shape in a polymerization solid catalyst component for polyolefin.

[Prior art and its problems] Ziegler-Natsuta catalysts are used as polymerization catalysts for polyolefins for boat fishing.

As one of these catalyst systems, a supported catalyst using a magnesium compound as a carrier is known, and numerous patents have been reported showing excellent performance in polymerization activity. In such supported catalysts, it is desirable to control the shape of the catalyst particles, and although some such methods are known, they are insufficient as methods for obtaining spherical solid catalyst components with large particle sizes. There are many things.

Spray drying methods and spray cooling methods are known as such methods. Spray drying method (JP-A-49-
85,999. JP-A-52-38,590, JP-A-58
-45,205. JP 57-198,709, JP 59-131.608, JP 63-289,005)
In this method, a water or alcohol solution of a magnesium compound is sprayed into a heated nitrogen stream, and the water or alcohol is evaporated from the generated droplets by the heated nitrogen to obtain spherical solid carrier particles. This method has the problem that the solvent is continuously and rapidly evaporated from the particles, resulting in particles that are porous and have a disproportionately distributed solvent content.

In addition, spray cooling method (Special table Showa 3-so: +, 5so
) sprays a magnesium compound of the general formula MgC1z.xLOH-ysKY in a molten state into a chamber cooled with a cooled inert liquid fluid to obtain spherical solid carrier particles without evaporation of the solvent. However, the shape of the carrier particles obtained by this method is often insufficient, and furthermore, there is a problem that the particles are broken during the titanium halide treatment.

Yet another method is melt quenching, in which a melt of the carrier component is emulsified in a suitable oil to form spherical molten particles, which are then added to a cooled hydrocarbon medium to rapidly solidify. (Japanese Patent Publication No. 55-H5, 102,
5-135,103, JP-A-56-67.311. Tokukai Showa 5! l-132,929), L, while nudging,
In this method, if the obtained support is not treated with an aluminum compound, the particles of the support are often destroyed during the next titanium halide treatment, and if the support is treated with an aluminum compound, the catalytic activity decreases. The problem was that there were many cases where this was done.

As a result of repeated research to solve the above problems, the present inventor has developed a complex compound obtained by reacting a magnesium compound and an alcohol in an inert organic solvent in the presence of a nonionic surfactant. Heat and stir at a temperature above its melting temperature,
After the suspended solution was rapidly cooled to obtain a spherical carrier without evaporation of alcohol, the carrier was mixed with a specific alcohol/Mg
It has been discovered that by drying to a C12 ratio, particles do not break during titanium halide treatment, and a solid catalyst component with large spherical particle size and excellent catalytic activity can be obtained.Based on this knowledge, the present invention has been developed. reached.

[Means for solving problems] The present invention has the following configurations (1) to (7).

(1) A solution in which a complex compound obtained by reacting a magnesium compound and an alcohol in an inert organic solvent is heated and stirred at a temperature above its melting temperature in the presence of a nonionic surfactant to suspend it. to obtain a spherical solid component without substantial evaporation of the alcohol, partially drying the solid component, and subsequently treating the packed dry solid component with a titanium halide and an electron-donating compound. Characteristic method for producing catalyst components for olefin polymerization.

(2) The method according to item 1 above, wherein the reaction of a magnesium compound and an alcohol in an inert organic solvent is carried out in the presence of an electron donor.

(3) The composition of the magnesium compound-alcohol complex is the general formula, MgC1t・nROH-pED (where R is 1 carbon number
~10 alkyl groups, rr3.0-6.0, E
D is an electron donor, p-0 to 2,0. ) The manufacturing method according to item 1 above.

(4) the quenching does not involve substantial evaporation of the alcohol;
Moreover, the suspension is rapidly brought into contact with an inert organic solvent that has been cooled to a temperature low enough to solidify the complex particles, and the starting material magnesium compound -
Same composition as alcohol complex (-formula MgC11・nRO
)1-pED, where R is an alkyl group having 1 to 10 carbon atoms, n=3.0 to 6.0, and ED is an electron donor p=0
~2.0. ) The manufacturing method according to item 1 above, for obtaining a spherical solid component having the following properties.

(5) The composition of the solid component after being partially dried is the general formula k1gc12·mROH-pED (where a is a carbon number 1 to 1017) furkyl group, ■ -0,4 to 2.0, and ED is an electron donor, p=0 to 2.0. ) is the above′! The manufacturing method described in Section J1.

(fi) A reaction between a dry solid component and a titanium halide is performed to form a reaction between Ti in the titanium halide and MgCl2 in the solid component.
Ratio between 1 and 100, 5 minutes to 6 at -20 to 200℃
The manufacturing method according to item 1 above, in which the reaction is carried out for a period of time.

(7) The reaction between the dry solid catalyst component and the electron-donating compound is carried out at a molar ratio of the compound and MgCl2 of 0.01 to 0.8;
The manufacturing method according to item 1 above, which is carried out at -20 to 200°C for 5 minutes to 6 hours.

That is, a typical structure of the present invention is obtained by reacting a magnesium compound, an alcohol, and an electron donor compound in an inert organic solvent.
ED (however, 8 is an alkyl group having 1 to 10 carbon atoms, n=
3.0 to 6.0, ED is electron donor, p・0 to 2
．． It is 0. ) is heated and stirred in the presence of a nonionic surfactant at a temperature above its melting temperature, and the suspended solution is rapidly cooled to form the above complex compound without substantial evaporation of the alcohol. After obtaining a spherical solid component having the same composition as the composition, the solid component has the general formula, MgCl2
・■ROH-pED (However, R is an alkyl group having 1 to 10 carbon atoms, m-0.4 to 2.0, and ED is an electron donor, p-0 to 2.0.) This is a method for producing a catalyst component for olefin polymerization, which is characterized in that the packed dry solid component is partially dried until dry, and then the packed dried solid component is treated with a titanium halide and an electron-donating compound.

The magnesium compound used in the present invention is anhydrous magnesium chloride, which may contain a trace amount of water as contained in commercially available products, and the alcohols used (represented by the formula Roll, where R is Carbon number 1-10
is an alkyl group. ), specific examples include methanol, ethanol, n-propyl alcohol, -propyl alcohol, butyl alcohol, and 2-ethylhexyl alcohol. Among these, ethanol is preferably used. It is also possible to use a mixture of 2 fl or more of these alcohols.

The inert organic solvent used in the present invention is inert to the magnesium compound, alcohol, and the complex compound formed by the reaction of these, and has such a high affinity that a suspension of complex particles cannot be formed in the molten state. In particular, aliphatic hydrocarbons such as hexane, heptane, octane, nonane, decane, kerosene and liquid paraffin, aromatic carbons such as benzene, toluene, xylene and cumene. Hydrogen, halogenated hydrocarbons such as 1,2-dichloroethane, chlorobenzene and dichlorobenzene.

In the present invention, a complex compound is produced by reacting a magnesium compound and an alcohol in an inert organic solvent, and the molar ratio of alcohol/magnesium chloride is 3.
It ranges from 0 to 6.0. In addition, an electron donor, which will be described later, may be added during this reaction, and the amount of addition may be determined by adjusting the amount of electron donor/
The molar ratio of magnesium chloride is in the range of O to 2.0.

The amount of inert organic solvent used is 0.1 to 10 L, preferably 0.3 to 5 L, per log of magnesium chloride.There is no particular restriction on the reaction salinity and reaction time, but the temperature is important for complex formation. Temperatures above 70° C. are preferably used in order to allow the reaction to occur rapidly and to subsequently suspend the resulting complex in molten form in an inert organic solvent.

In the present invention, a surfactant is present when the complex is suspended in the above-mentioned inert organic solvent. The surfactant is an oil-soluble one, preferably a nonionic surfactant. For example, sorbitan aliphatic ester, polyoxyethylene sorbitan aliphatic ester, polyoxyethylene aliphatic ester, etc. Sorbitan trioleate, sorbitan tristearate, propylene glycol monostearate, sorbitan sesquioleate, sorbitan monooleate, sorbitan distearate, propylene glycol monolaurate, sorbitan monostearate, diethylene glycol monostearate, diethylene glycol monolaurate ,
Examples include sorbitan monopalmitate and sorbitan monolaurate.

The amount of surfactant used should be sufficient to emulsify and suspend the complex of the magnesium compound and alcohol in the inert organic solvent, and the concentration in the inert organic solvent should be from 0.01 to
50g/l, preferably in the range of 0.1 to 30g/l.

In the present invention, by heating the above complex in an inert organic solvent in the presence of a nonionic surfactant at a temperature equal to or higher than its melting temperature and stirring, a suspension containing the complex particles in a molten state can be obtained. A liquid can be formed. The heating temperature is not particularly limited as long as it is at least the temperature at which the complex melts, but a temperature of 70° C. or higher is preferably used. The complex particles in the emulsified suspension state have a spherical shape with a size ranging from about 1 to 200 μm.

The suspension can be rapidly cooled to obtain a spherical solid component without substantial evaporation of the alcohol. As a method for rapid cooling, a method is preferably used in which the suspension is brought into immediate contact with an inert organic solvent that has been cooled to a low enough temperature to solidify the complex particles. The inert organic solvent used here can be selected from the inert organic solvents listed above. The temperature of this solvent is not particularly limited as long as it is cooled to a low enough temperature to solidify the complex particles in a molten state, but it is preferably used after being cooled to 0° C. or lower.

The solidified particles can be separated and collected by methods such as filtration and centrifugation. The composition of the obtained solid component is the same as that of the raw material magnesium compound-alcohol solution, and the solid particles have a particle size of about 1 to 150 μm and are spherical.

The method of drying the above-mentioned solid components used in the present invention is bubbling with inert gas at room temperature, bubbling with heated inert gas, or drying at room temperature or by heating under reduced pressure. Furthermore, nitrogen is preferably used as an inert gas that may be used in combination with the above drying methods. The drying conditions were such that the composition of the solid component after drying was MgC1,・mROH-pE.
D (wherein R is an alkyl group having 1 to 10 carbon atoms, -10.4 to 2.0, El) is an electron donor, p-0 to
It is 2.0. ) must be selected so that it falls within the range.

If l becomes larger than 2.0 in the solid component composition after drying, the solid particles will be destroyed in the subsequent titanium halide treatment, and the particles will become irregularly shaped fine powder.

Moreover, when the country becomes smaller than 0.4, the catalyst activity decreases significantly. Further, in order to avoid rapid evaporation of alcohol, the drying temperature is preferably low, and the drying time is preferably at least 2 to 3 hours. Under these conditions, preferably the drying time is 5 to 1,000
The drying time and drying temperature range from room temperature to 90°C.

Specific examples of the halogenated titanium used in the present invention include titanium tetrachloride, titanium tetrabromide, methoxytitanium trichloride, phenoxytitanium trichloride, dimethoxytitanium dichloride, trimethoxytitanium chloride, etc. .

Preferably, titanium tetrachloride is used. The above titanium halide may be used after being diluted with an inert solvent.

Specifically, inert solvents include hexane, heptane,
Aliphatic hydrocarbons such as decane, aromatic hydrocarbons such as benzene, toluene, xylene, etc., halogens such as carbon tetrachloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, 0-dichlorobenzene, etc. Examples include hydrogenated hydrocarbons. Preferably, 1,2-dichloroethane is used.

Electron-donating compounds used (simultaneously) during the titanium halide treatment of the present invention include carboxylic acids, ethers, esters, ketones, aldehydes, acid anhydrides, amines, nitriles, phosphines, and the like. Among these, esters are preferably used. Specifically, methyl benzoate, ethyl benzoate, methyl toluate, ethyl toluate, methyl anisate, ethyl anisate, phenyl anisate, dimethyl phthalate, diethyl phthalate,
Examples include di-n-butyl phthalate and di-i-butyl phthalate. Preferably, di-n-butyl phthalate and sheet butyl phthalate can be used.

In the reaction of the dry solid component obtained above according to the method of the present invention with titanium halide, the molar ratio of Ti in the titanium halide to MgCl in the solid component is 1 to 10.
0, preferably 3-50. In addition, the molar ratio of the electron donating compound and MgCl in the solid component is 0.01 to 0.
．． 8. The reaction temperature is preferably 0.05 to 0.7, -20 to 200°C, preferably 50 to 150°C. The reaction time is 5 minutes to 6 hours, preferably 10 minutes to
It is 5 hours. This reaction may be repeated any number of times within the above reaction conditions, and the electron donating compound may or may not be added, but must be added at least once in any reaction. .

After the reaction, the solid is separated into layers by filtration or decantation, and then washed with an inert hydrocarbon solvent to remove unreacted substances or by-products.

Specific examples of the solvent used in the cleaning include hexane, heptane, octane, nonane, decane, kerosene, and the like. Preferably hexane or heptane. The solid catalyst component thus obtained can be dried and stored in the form of a powder, or it can be stored as suspended in the above-mentioned inert hydrocarbon solvent.

The solid catalyst component obtained above can be used as a catalyst for olefin polymerization by combining with an organoaluminum compound and an organosilicon compound. Specific examples of the organoaluminum compound include triethylaluminum, trilopropylaluminum, trinybutylaluminum, diethylaluminum ethoxide, dimethylaluminum chloride, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, and the like. can. Preferred is triethylaluminum.

Specific examples of the organosilicon compound include methyltrimethoxysilane, t-butyltrimethoxysilane, t-butyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, methylethyldimethoxysilane, and methylphenyldiethoxysilane. Examples include silane, dimethyldimethoxysilane, dimethyljethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, di-t-butyldimethoxysilane, diphenyldimethoxysilane, trimethylmethoxysilane, and trimethylethoxysilane. Preferred are diphenyldimethoxysilane and di-t-butyldimethoxysilane.

The amount of the fat aluminum compound used is 10 to 1,000 mol, preferably 50 to 500 mol, per 1 mol of titanium in the solid catalyst component. The amount of organosilicon compound used is 0.0 per mole of organoaluminum compound.
The amount is 1 to 2 mol, preferably 0.05 to 1 mol.

The olefins used in the polymerization reaction in the present invention include ethylene, propylene, l-butene, and! -pentene, l-
hexene, 1-octene, 1-decene, 1-dodecene,
l-tetradecene, l-hexadecene, l-octadecene, 1-eicosene, 4-methyl-1-pentene, 3-
Methyl-1-pentene and the like. The polymerization of these olefins includes not only homopolymerization but also copolymerization with one type of other olefins or 2f1 or more.

Further, the above-mentioned catalyst according to the present invention includes the above-mentioned olefins and butadiene, 1.4-hexadiene, 1.4-pentadiene, 1.7-octadiene, 1,8-nonadiene,
! , 9-decadiene, isoprene, styrene, cyclopropane, cyclobutene, cyclohexene, norbornene, dicyclopentadiene, etc.

Polymerization can be carried out in the liquid phase or in the gas phase. When polymerizing in a liquid phase, for example, hexane, heptane,
An inert hydrocarbon solvent such as octane, nonane, decane, kerosene, etc. may be used as the polymerization medium, and it is also possible to use a liquefied olefin itself such as liquefied propylene, liquefied butene, etc. as the solvent.

The polymerization temperature is 40 to 200°C, preferably 50 to 150°C.
It is ℃. Ii combined pressure is atmospheric pressure ~ loOkg/c+a
2G, preferably 5 to 50 to 88 m'G, may be carried out in a batch, semi-continuous or continuous manner, but industrially preferred is a continuous polymerization. It is also possible to perform the polymerization by multistage polymerization using different polymerization conditions.

In order to control the polymer molecular weight, it is effective to add a molecular weight controlling agent such as hydrogen to the polymerization system.

〔Effect of the invention〕

If the method of the present invention is used, the particle shape of the solid component obtained by the quenching method will not be destroyed even during the treatment of titanium halide, and the solid catalyst will have a large particle size and a spherical shape with excellent catalytic activity. ingredients are obtained. By using a catalyst using this catalyst component for olefin polymerization, a polyolefin with good particle size and particle size distribution can be obtained.

[Example] Next, the present invention will be specifically explained using examples.

Example 1 (a) Preparation of solid catalyst component Kerosene 46 was placed in a SuS autoclave purged with nitrogen.
7 rin! , Susoil P-55 (Matsuzai Sekiyu Co., Ltd.) 233 ml 1, anhydrous gcl 14 Jg, dry ethanol 35.
2 Garden 2, Emazol 5-20 (manufactured by Kao Corporation, sorbitan distearate) 6g 1 diisobutyl phthalate (DB
P) 5.8■it was inserted. This mixture was heated to 100° C. while stirring to dissolve it. After stirring for 1 hour, while continuing stirring, 2 L of purified hexane previously cooled to -30° C. was introduced using a Teflon tube with an inner diameter of 4 mm, and the mixture was transferred to a SUS autoclave. The product was collected by filtration and washed with hexane to obtain 45 g of a solid component. The solid particles are spherical and the particle size is 10-5
From the analysis result of 0 μm, the composition of this solid component is the same as that of the starting solution: JCh4EtO)l-0,130BP.
Met.

15 g of the obtained solid component was heated at room temperature for 155 hours.
From the 6 analysis results of air drying using nitrogen at a flow rate of 2 It/win, the composition of the obtained dry solid component was MgC.
1,.1.5EtOH.O,13[IBP.

In a glass flask, 5 g of dry solid ingredients, 40 g of titanium tetrachloride, 60 mj of purified 1,2-dichloroethane
After stirring and heating to 100° C., 1.7 μl of diisobutyl phthalate was added. After heating at 100°C for 2 hours, the liquid phase was removed using a decanterizer, and titanium tetrachloride 4 (Is It, purified 1.2-
60 x 1 dichloroethane was added. 1 at 100℃
After heating for a period of time, the liquid phase was removed using decane, washed with purified hexane, and then dried to obtain a solid catalyst component.

(b) Production of olefin polymer In a 3L SUS autoclave purged with nitrogen, 1.5L of hexane, 3■■ol of triethylaluminum, 0.45■mob solid catalyst of diphenyldimethoxysilane 2
After adding 0mg, the total pressure is 1kg/c■2G at room temperature.
Propylene was continuously introduced so that the amount of polymerization was maintained, and polymerization was carried out for 10 minutes. Thereafter, the temperature was raised to 70° C., and a hydrogen 150 layer 1 was introduced. Propylene was continuously introduced at 70° C. so that the total pressure was 7 kg/cm2G, and polymerization was carried out for 2 hours.

Unreacted propylene was discharged, and after filtration, the obtained polypropylene was dried. 168 g was obtained, and the catalyst activity was 8300 g4P/g-cat. The hexane soluble portion was 0.7% by weight of the total amount of polypropylene obtained, and the bulk density was 0.35 g7all. Ta. The obtained polymer was spherical and had an average particle size of 1000 μm.

Example 2 (a) Preparation of solid catalyst component The same procedure as in Example 1 was carried out except that the drying time of the solid component was changed to 195 hours. The composition of the solid component after drying is as follows:
It was MgCl,.0.9EtOH.0.1311BP.

(b) Production of olefin polymer Propylene was polymerized in the same manner as in Example 1 using the above solid catalyst. 130 g of polypropylene was obtained, the catalyst activity was 6500 g4P/rCat, the hexane soluble portion was 1.1% by weight of the total amount of polypropylene obtained.
The bulk density was 0.34 g/Jt. The obtained polymer was spherical and had an average particle size of 1010 μm.

Example 3 (a) Preparation of solid catalyst component Kerosene 467sj2 and Smoyl P-55 (@Matsuzai Oil Co., Ltd.) 2 were placed in a 5υS autoclave that had been purged with nitrogen It.
33sjl, 14.3g of anhydrous MgCl, 35.2g of dry ethanol, Emazol 5-20 (Kao-
6 g of sorbitan distearate (manufactured by Co., Ltd.) was added. The mixture was heated to 100° C. while stirring.

After stirring for 1 hour, while continuing stirring, 2 L of purified hexane previously cooled to -30° C. was introduced using a Teflon tube with an inner diameter of 4 mm, and the mixture was transferred to a SuS autoclave. The product was collected by filtration and washed with hexane to obtain 38 g of solid component. The solid particles were spherical and had a particle size of 10-70 μm.

Further, from the analysis results, the composition of this solid component was the same as that of the starting solution: Mgct, 4Et011.

15 g of the obtained solid component was heated at room temperature for 165 hours.

From the analysis results of air drying using nitrogen at a flow rate of 2λ/sin, the composition of the obtained dry solid component is MgCl2
- It was 1.4EtOH.

In a glass flask, 5 g of dry solid ingredients, 4 osi of titanium tetrachloride, 60 x 1 of 1,2-dichloroethane manufactured by N.
were mixed and heated to 100°C while stirring, then heated at 100°C for 2 hours to which 1.7 sJ1 of diisobutyl phthalate was added, and the liquid phase was removed by decantation.
Again, 40sJ2 of titanium tetrachloride and 6011 of purified 1,2-dichloroethane were added. After heating at 100° C. for 1 hour, the liquid phase was removed by decantation, washed with purified hexane, and then dried to obtain a solid catalyst component.

(b) Production of olefin polymer Place chitin in a 3L SuS autoclave purged with nitrogen.1. SL, triethyl aluminum 31 mol
After adding 0.45 m O1 of diphenyldimethoxysilane and 25 mg of solid catalyst, the total pressure was 1 kg/c at room temperature.
Propylene was continuously introduced so that the amount of
Polymerized for minutes. After that, the temperature was raised to 70℃, and 150ml of hydrogen was added.
A was introduced. Propylene was continuously introduced at 70° C. so that the total pressure was 7 kg/cw'G, and polymerization was carried out for 2 hours.

Unreacted propylene was discharged, and after filtration, the obtained polypropylene was dried. 150 g was obtained, and the catalyst activity was 75 QOrsPP/rscat. The hexane soluble portion was 2.2% by weight of the total amount of polypropylene obtained.
, and the bulk density was 0.30 g/mβ. The obtained polymer was spherical and had an average particle size of 1410 microns.

Comparative Example 1 (a) Preparation of solid catalyst component The same procedure as in Example 1 was carried out except that the drying time of the solid component was changed to 540 hours. The composition of the solid component after drying is as follows:
MgC1,・0. It was IEtOH・0.13DBP.

(b) Production of olefin polymer Propylene was polymerized in the same manner as in Example 1 using the above solid catalyst. 14 g of polypropylene was obtained, the catalytic activity was 700 g-PP/g-cat, the hexane soluble portion was 10.5% by weight of the total amount of polypropylene obtained, and the bulk density was o, 3+ g /fflβ. The resulting polymer was spherical with an average particle size of 490μ.
It was Zeng.

Comparative Example 2 (a) Preparation of solid catalyst component Example 1 except that the drying time of the solid component was 31 hours.
I did the same thing. The composition of the solid component after drying is M
gC1,.2.8EtOH.0.13D8P.

When this dry solid component was subjected to titanium halide treatment, the carrier was destroyed and the shape became small particles with irregular shapes.

(b) Production of olefin polymer Propylene was polymerized in the same manner as in Example 1 using the above solid catalyst. 82 g of polypropylene was obtained, and the catalytic activity was 4100 g-PP/g.cat. The hexane soluble portion was 3.5% by weight of the total amount of polypropylene obtained, and the bulk density was 0.26 g. /+1.

The obtained polymer was amorphous and had an average particle size of 63 Ou layers.

Comparative Example 3 (a) Preparation of solid catalyst component Kerosene 4 was placed in a nitrogen-substituted SUS autoclave.
67mJ2, Smoil p-5s (@Matsuzai Oil Co., Ltd.) 2
33■λ, 14.3g of anhydrous MgCl2, 35.2aIL of dry ethanol, 68% of Emazol 5-20 (manufactured by Kao ■, sorbitane distearate), and 5.8sJ2 of diisobutyl phthalate (DBP) were added. The mixture was heated to 100° C. while stirring. After stirring for 1 hour, the mixture was transferred to a SUS autoclave using a Teflon tube with an inner diameter of 4 layers, into which 2 L of silk hexane previously cooled to -30° C. was introduced while stirring was continued.

The product was collected by filtration and washed with hexane to obtain 45 g of a solid component. The solid particles are spherical, and the spherical diameter is 1
It was 0 to 50 μm. Also, from the analysis results, the composition of this dry solid component is the same as that of the starting solution, KgCI, 4EtO
H.(1,13D8P).

In a glass flask, 10 g of solid ingredients and 10 g of hexane
Add 01λ and add triethylaluminum 1 at 5℃ while stirring.
After adding 7.2 au dropwise, the mixture was stirred at 25°C for 1 hour, and further stirred at 80°C for 3 hours. The solid portion was collected by filtration and thoroughly washed with hexane.

In a glass flask, 60 liters of 1,2-dichloroethane made from 5 g% titanium tetrachloride 40-1.9 was mixed with the above solid component and heated to 100°C with stirring, followed by 1.7 liters of diisobutyl phthalate. added.

After heating at 100°C for 2 hours, the liquid phase was removed by decantation and titanium tetrachloride 40-1, purified 1.
2-dichloroethane! i0mjl was added. 100℃
After heating for 1 hour, the liquid phase was removed by decantation, washed with purified hexane, and dried to obtain a solid catalyst component.

(b) Production of olefin polymer Propylene was polymerized in the same manner as in Example 1 using the above solid catalyst. 280 g of polypropylene was obtained, the catalyst activity was 1400 g-PP7 g-Cat, the hexane soluble portion was 6.7% by weight of the total amount of polypropylene obtained, and the bulk density was 0.32 g/sJ ! Met. The obtained polymer has an amorphous shape and an average particle size of StOμ
■I wiped it off.

[Brief explanation of the drawing]

The 1st rM is a process diagram (flow sheet) for producing an olefin polymer using the catalyst according to the method of the present invention. that's all

Claims (7)

[Claims] (1) A solution obtained by heating and stirring a complex compound obtained by reacting a magnesium compound and an alcohol in an inert organic solvent in the presence of a nonionic surfactant at a temperature above its melting temperature to suspend it. quenching to obtain a spherical solid component without substantial evaporation of the alcohol, partially drying the solid component, and then treating the dry solid component with a titanium halide and an electron-donating compound. A method for producing a catalyst component for olefin polymerization, characterized by: (2) The manufacturing method according to claim 1, wherein the reaction of a magnesium compound and an alcohol in an inert organic solvent is carried out in the presence of an electron donor. (3) The composition of the magnesium compound-alcohol complex is the general formula, MgCl_2・nROH-pED (where R is 1 carbon number
~10 alkyl groups, n=3.0-6.0, ED
is an electron donor, p=0 to 2.0. ) The manufacturing method according to claim 1. (4) the quenching does not involve substantial evaporation of the alcohol;
Moreover, the suspension is rapidly brought into contact with an inert organic solvent that has been cooled to a temperature low enough to solidify the complex particles, and the starting material magnesium compound -
Same composition as alcohol complex (general formula MgCl_2・nR
OH-pED, where R is an alkyl group having 1 to 10 carbon atoms, n = 3.0 to 6.0, and ED is an electron donor p = 0
~2.0. ) A method according to claim 1 for obtaining a spherical solid component having the following properties. (5) The composition of the solid component after partially drying is the general formula, MgCl_2・mROH・pED (where R is 1 carbon number
~10 alkyl groups, m=0.4-2.0, ED
is an electron donor, p=0 to 2.0. ) The manufacturing method according to claim 1. (6) The reaction between the dry solid component and the titanium halide is performed using Ti in the titanium halide and MgCl_2 in the solid component.
Ratio between 1 and 100, 5 minutes to 6 at -20 to 200℃
The manufacturing method according to claim 1, which involves a time reaction. (7) The reaction between the dry solid catalyst component and the electron-donating compound is carried out at a molar ratio of 0.01 to 0.8 between the compound and MgCl_2.
The manufacturing method according to claim 1, which is carried out at -20 to 200°C for 5 minutes to 6 hours.