JPS61285203A - Catalytic component for olefin polymerization - Google Patents

Abstract

PURPOSE:A catalytic component consisting of a catalytic reaction product of a specific solid composition, a liquid Ti compound and an Si halide, having a high activity and providing a polymer having relatively large particle diameters and controlled particle diameter distribution when it is used for olefin polymerization. CONSTITUTION:(A) A solid composition obtained by bringing a precipitating agent such as TiCl4, etc., into contact with a solution of a catalytic reaction product of a dihalogenated Mg (e.g., MgF2, MgCl2, etc.), a titanium tetra alkoxide [e.g., Ti(OC2H5)4, Ti(O-nC4H9)4, etc.] and/or its polymer (e.g., normal butyl polytitanate, etc.) while stirring at <=flotation limit stirring strength of reaction system is brought into contact with (B) a liquid Ti compound [e.g., TiCl4, Ti(OC2H5)Cl3, etc.] and/or an Si halide (e.g., SiCl4, HSiCl3, etc.), to give the aimed catalytic component.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to transition metal components of so-called Ziegler-type catalysts. According to the present invention, it is possible to obtain a catalyst component for olefin polymerization that is highly active and capable of producing a polymer having a relatively large particle size.

It has been known that a highly active catalyst can be obtained by using a magnesium compound such as magnesium halide, magnesium alkoxide, hydroxymagnesium chloride, dialkylmagnesium, etc. as a carrier component.

By the way, when olefins are combined using a Ziegler type catalyst using such a supported catalyst component (solid catalyst component), the olefin polymer produced is obtained in the form of particles, but the particle size and The particle size distribution depends on the particle state of the solid catalyst component used. On the other hand, it is desirable for the produced olefin polymer particles to have a relatively large particle size and a uniform particle size, as this leads to an improvement in the polymer concentration of the produced polymer slurry and to improved productivity due to easier handling of the polymer slurry. .

However, in the above-mentioned highly active catalysts, it is difficult to control the particle size of the catalyst components, and in many cases the average particle size is 5 to 1.
It is about 0 micron, and the particle size distribution of the catalyst is wide and insufficient.

Therefore, it is currently desired to develop a method for producing a catalyst that has a relatively large average particle size of 10 microns or more and can control the particle size distribution.

Prior art Prior art includes JP-A-49-65999, JP-A-5
4-41985, JP-A-55-2951, JP-A-55-
135102, JP-A-135103, JP-A-Sho 56
-67311 Publication Each basket is mentioned.

In these prior art techniques, the Mg compound as a carrier component is made into fine particles or melted, and then solidified by spray drying, granulation, or rapid cooling. In order to increase the catalyst particle size by these methods, as far as the present inventors know, a large amount of equipment investment is required, and there seems to be a problem that the distribution of the generated catalyst particles is wide.

Summary of the Invention The purpose of the present invention is to provide a solution to the above-mentioned problems, and it attempts to achieve this purpose by using a catalyst component for olefin polymerization, which is composed of the following components (A) and (B). .

Component (A) A solid composition obtained by adding a precipitating agent to a solution of a contact product of magnesium dihalide and titanium tetraalkoxide and/or its polymer. However, the addition of the precipitating agent shall be carried out while stirring at a stirring strength below the floating limit of the reaction system.

Component (B) Liquid titanium compound and/or silicon halogen compound.

Effects When olefin polymerization is carried out using the solid catalyst component according to the present invention as a transition metal catalyst component of a Ziegler catalyst,
A polymer with high activity, relatively large particle size, and controlled particle size distribution can be obtained.

The reason why a highly active polymer with controlled polymer particle properties as described above can be obtained by using the catalyst component of the present invention is not necessarily clear, but one of the important requirements is the stirring conditions during the synthesis of component (A). It is.

The catalyst component according to the invention is a component prepared by a specific method (
It is a contact product of A) and component (B).

Component (A) (1) Composition Component (A) is a solid composition composed of magnesium dihalide, titanium tetraalkoxide and/or a polymer thereof and a precipitating agent (eg, certain polymeric silicon compounds).

This solid composition is not a magnesium dihalide or a complex of magnesium dihalide with titanium tetraalkoxide and/or its polymer, but is another solid. At present, its contents have not been fully analyzed, but according to the results of compositional analysis, this solid composition is
It contains titanium, magnesium, halogen, and silicon.

(2) Production component (A) is prepared by mutual contact of magnesium dihalide, titanium tetraalkoxide and/or its polymer, and a precipitating agent.

What) Magnesium dihalide Examples include MgF21MgO12 and MgBr2.

1) Titanium tetraalcosides and their polymers Titanium tetraalkoxides include, for example, Ti(002
H5)4, Ti(0-103H7)4. Ti(0
-no4E4)4,'ri(0-no3u7)4. T
i(0-104H,), , Ti(OOH20H(O
H,)2]4, Ti(00(CIIB)B)4
, Ti (0-n03 Hsl) 4, Ti
(0-n06H13) 4, Ti (0-n07H□5)
4. T1[0CH20H(C2H5)04H7:14
,and so on. Among these, Ti(QC
2HIs)4 and Ti(0-no, H9)4.

Examples of titanium tetraalkoxide polymers include those represented by the following formula.

Here, R2-R11 are the same or different hydrocarbon residues, preferably aliphatic or aromatic hydrocarbons having 1 to 10 carbon atoms, especially aliphatic hydrocarbons having 2 to 6 carbon atoms. n represents a number of 2 or more, particularly a number up to 20. The value of n is desirably selected so that the polytitanate itself or in liquid form as a solution can be subjected to the contact step with other components. A suitable n for handling is 2 to 14. Preferably 2
~ About 10.

It is. A specific example of such a polytitanate is normal butyl polytitanate.

(n-2 to 10), hexyl polytitanate (n-m
2-10), normal octyl polytitanate (n-2
~10) and so on. Among these, normal butyl polytitanate is preferred.

(c) Precipitating Agent As the precipitating agent, a halogenating agent such as titanium tetrachloride or silicon tetrachloride, or a polymeric silicon compound can be used.

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

■Formula -8i-0- Here, R1 has a carbon number of about 1 to 1O, especially about 1 to 6,
is a hydrocarbon residue.

Specific examples of polymeric silicon compounds having such structural units include methylhydropolysiloxane, ethylhydropolysiloxane, phenylhydropolysiloxane,
Examples include cyclohexylhydropolysiloxane.

The degree of polymerization is not particularly limited, but considering handling, the viscosity is from 10 centistokes to 1
00 centistokes is preferable. Furthermore, although the terminal structure of the hydropolysiloxane does not have a large effect, it is preferable that the terminal structure is capped with an inert group such as a trialkylsilyl group.

In addition to these components, alcohols and/or organic acid esters can also be used in small amounts, and are also preferred. Specific examples of suitable alcohols and esters are given in, for example, Japanese Patent Publication No. 54-23394 and Japanese Patent Publication No. 5
No. 9-80406 and other publications.

B) Contact of each component (amount ratio) The amount of each component used may be arbitrary as long as the effect of the present invention is recognized, but it is generally preferred to be within the following range.

The amount of titanium tetraalkoxide and/or its polymer to be used is preferably within the range of 0.1 to 10, preferably within the range of 1 to 4, more preferably 2 in molar ratio to magnesium dihalide. It is within the range of ~3.

It is preferred to select a suitable quantitative ratio so that the magnesium dihalide is dissolved in the titanium tetraalkoxide and/or its polymer.

The amount of the precipitating agent, such as a polymeric silicon compound, is I
It is preferably within the range of 1 to 100, preferably 0.1 to 10, and more preferably 1 to 4.

(Contact method) Component (A) of the present invention is obtained by contacting the three components described above. Contacting the three components can be carried out by any generally known method. Generally -100℃
The contact may be made within a temperature range of ~200°C. The contact time is usually about 10 minutes to 20 hours.

Component (M) of the present invention is produced by bringing a precipitating agent into contact with a liquid contact product of magnesium diphenologenide, titanium tetraalkoxide and/or its polymer.

In the present invention, the conditions for contacting the precipitating agent at that time are important, and in the present invention, the floating limit stirring strength (
nf) It is necessary to contact with the stirring intensity below.

The lower limit of the stirring intensity is nf/15, preferably /1o,
It is.

Here, the floating limit stirring strength (nf) means the lowest stirring strength within a range where precipitates do not stay at the bottom of the tank.In the present invention, a precipitating agent is added to precipitate solid components. This means the floating limit stirring strength at the final stage of the process.

Normally, the stirring strength is controlled by the rotation speed of the stirring blade, and the rotation speed at the floating limit stirring strength (nf) can be determined by the following formula' (Chemical Engineering 17.144 (1953))
.

scale factor - tank diameter (m), +ip - particle diameter (mm), lar particle density (g/am"), 8 - liquid density CI cm3), μ - liquid viscosity (centiboise), Vp' m particles Bulk volume v9
-Particle true volume Conventionally known stirring is usually carried out at a rotational speed considerably higher than the above-mentioned nf, but the present invention is characterized by stirring at a rotational speed lower than nf.

Normally, stirring at a rotation speed of less than nf would result in a broad particle size distribution, which is undesirable, but in the present invention, surprisingly, the particle size distribution does not become broad. , particles with a sharp distribution can be obtained. The cause of this is currently under investigation.

Contacting the three components can also be carried out in the presence of a dispersion medium. Examples of the dispersion medium in this case include hydrocarbons, halogenated hydrocarbons, dialkylsiloxanes, and the like. Specific examples of hydrocarbons include hexane, heptane, toluene,
Specific examples of halogenated hydrocarbons include n-butyl chloride, II2 dichloroethylene,
Examples include carbon tetrachloride and chlorobenzene, and specific examples of dialkylpolysiloxane include dimethylpolysiloxane and methyl-phenylpolysiloxane.

In the present invention, the term "contact product solution of magnesium halide and titanium tetraalkoxide and/or its polymer" refers to solutions that are solid in nature, in addition to solutions using the above dispersion medium as a solvent. The titanium tetraalkoxide and/or its polymer obtained by liquefying magnesium halide are treated as a solvent, and the liquid contact product itself is also treated as a solution.

Component (B) Component (B) is a liquid titanium compound and/or a silicon halogen compound.

(1) Liquid titanium compounds Here, “liquid” refers to not only those that are liquid themselves (including those that are complexed and become liquid), but also those that are liquid as a solution. include.

Typical compounds include formula Ti(OR)4. , nXn
(Here, R is a hydrocarbon residue, preferably having 1 to 1 carbon atoms.
0, or represents a halogen, where n is ok
Indicates the number of +. ) can be mentioned.

Specific examples include Ti014, TiBr4, T
i(QC!2H,)C13, Ti(00□HIs)2, , Ti(Of:!2El,)301, Ti(0-
10, PI,)Cyu8, Ti(0-n04Hg)013
, Ti(0-n04H,)2012 , Ti(Q
C2H5)Br3,Ti(00□H,)(004Hg)
201, Ti(0-n04H@)30U, Ti(
0-0,H,)Oyu,,Ti(0-1c!4H,)2C
1□, Ti(QC5H11)(n,,Ti(0('gH
13) 01B, Ti(002H,)4, Ti(0-n
o, R7)4, Ti(0-103H7)4, Ti(0
-nc, H,)4. Ti(0-10,H,)4,Ti
(OOH20H(OH,),)4. Ti(0-0(C
H3)3)4, Ti(0-n05H1□)4. Ti(
0-n05H1□)4, Ti(0-n07H15)4
, T1[0C111(C3H,), ]4, T1[00)
1(OH8)C4H, ]4, Ti(0-nOBH□7)
4% ”(0-n010FL21)45Ti(00)1
,0H(02H,)04El,)4, etc.

Further, this titanium compound may be a molecular compound obtained by reacting TiX4' (here, xl represents a halogen) with an electron donor. Specific examples include Ti IJ, -cH30
0(!2H,.

T1014-OH3Co,O,! 1. ．． Ti014-C
, H, No□, T101. -C! E13C! 001,
Ti1l,・O,H,C! 001, TiC Yu, Fist c,
a, co□C! ,H,,Ti 014・0100□02
! 1. , Ti114.04H40, etc.

(2) Silicon halogen compound represented by the formula R: -nSiXn (where R1 represents hydrogen, a hydrocarbon residue, or an alkoxy group, X represents a halogen, and n is a number of 1×4). Compounds that can be used can be used.

As a specific example, 5il14.111E11013, f
:H381013, SiBr4, (02H,)
2E+1012, (OH3), EliC! l, 8
1(○aa3)ax3.81(QC2111,)tJ,
, 5i(00,H,)2012, etc. In addition, together with these compounds, the polymer silicon compound used when synthesizing the component (Al) can also be used.

Preparation of Catalyst Component The catalyst component of the present invention is a contact product of component (A) and component (Hyun).

(1) Amount Ratio The amount of each component to be used may be arbitrary as long as the effects of the present invention are observed, but it is generally preferred to be within the following range.

The amount of component (B) used is 1X10 to 100 in molar ratio to the magnesium dihalide constituting component (B).
It is preferably within the range of I x 10-2 to 10.

(2) Contact method The catalyst component of the present invention is obtained by bringing the above-mentioned component (A) and component (gradient) into contact with each other.
What is necessary is just to carry out within the temperature range of 00 degreeC - 200 degreeC. The contact time is usually about 10 minutes to 20 hours.

Component (A) and component (B) are preferably brought into contact with each other under stirring, and may also be brought into contact by mechanical grinding using a ball mill, vibration mill, or the like.

The contact between the component μ) and the component (gradient) can also be carried out in the presence of a dispersion medium.
) can be selected from those exemplified as those to be used when manufacturing.

Polymerization of Olefins (1) Formation of Catalyst The catalyst component of the present invention can be used in the polymerization of olefins in combination with an organometallic compound as a cocatalyst.

Any of the organometallic compounds of metals of Groups 1 to 1 of the Periodic Table, which are known as cocatalysts, can be used.

Particularly preferred are organic aluminum compounds.

Specific examples of organoaluminum compounds include the formula R
AIXn or R, Al(OR8)In (where R6 and R7 may be the same or different and have 1 to 2 carbon atoms)
0 or so hydrocarbon residue or hydrogen R8 is the above hydrocarbon residue, X is halogen, n and m are each 0 and n<2
, Q < m < 1. ). Specific examples include the following. What) Trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, etc. (b) Diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride Alkyl aluminum halides such as (c) dialkyl aluminum hydrides such as diethyl aluminum hydride, diisobutyl aluminum hydride, (c) alkyl aluminum alkoxides such as diethylaluminum ethoxide, diethyl aluminum ethoxide, diethylaluminum phenox, etc.

In addition to these organoaluminum compounds (B) to (C), other organometallic compounds, such as R:-YuAyu(OR)a(1<
R' and RIO are hydrocarbon residues having about 1 to 20 carbon atoms, which may be the same or different. ) can also be used in combination with an alkyl aluminum alkoxide. For example, a combination of triethylaluminum and diethylaluminum ethoxide, a combination of diethylaluminum monochloride and diethyl-aluminum ethoxide, a combination of ethylaluminum dichloride and ethylaluminum jetoxide, a combination of triethylaluminum, diethylaluminium ethoxide and diethylaluminum chloride. Can be used in combination with

There are no particular restrictions on the amount of these organometallic compounds used, but
0.5 to 100 in weight ratio to the solid catalyst component of the present invention
It is preferably within the range of 0.

In order to improve the stereoregularity of an olefin polymer having 3 or more carbon atoms, it is effective to add and coexist an electron-donating compound such as an ether, ester, amine, or silane compound during one polymerization. The amount of the electron-donating compound used for this purpose is 0.0000 to 1 mole of the organoaluminum compound.
0.001 to 2 mol, preferably 0.01 to 1 mol. Specific examples of electron-donating compounds used for such purposes include, for example, JP-A-55-127406 and JP-A-Sho.
6-l39511 and JP-A-57-63310.

(3) Olefin The olefin polymerized by the catalyst system of the present invention has the general formula R-O
H,C! H2 (where R is a hydrogen atom or a carbon number of 1 to
10 hydrocarbon residues, which may have a branched group). Specifically, ethylene, propylene, butene-1, pentene-1, hexene-1,4-
There are olefins such as methylpentene-1. Preferred are ethylene and propylene. In these polymerizations, it is possible to carry out copolymerizations with up to 50% by weight, preferably 20% by weight, based on ethylene, of the abovementioned olefins, and up to 30% by weight, based on propylene, of the abovementioned olefins, in particular ethylene, can be copolymerized with Copolymerization with other copolymerizable monomers (eg vinyl acetate, diolefins) can also be carried out.

(3) Polymerization The catalyst system of the present invention is applicable not only to ordinary slurry polymerization, but also to liquid-phase solvent-free polymerization, solution polymerization, or gas-phase polymerization that uses substantially no solvent. be done. It is also applicable to continuous polymerization, batch polymerization, or prepolymerization methods. As the polymerization solvent in the case of slurry polymerization, saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, and toluene are used alone or in mixtures.

Polymerization temperature is from room temperature to about 200°C, preferably 50°C
~150°C, and hydrogen can be used as an auxiliary molecular weight regulator at that time.

Experimental Examples Example-1 (1) Component (Synthesis of Al) 100 milliliters of dehydrated and deoxygenated n-hebutane was introduced into a flask with an inner diameter of 10 am that was sufficiently purged with nitrogen, and then 20.1 mol of MgCl and Ti (0- n0a1
3s ) 4 was introduced in an amount of 0.2 mol, and the mixture was reacted at 95° C. for 1 hour.

The diameter of the stirring blade used at that time was scm. After the reaction was completed, the temperature was lowered to 40°C, 15 ml of methylhydrogenpolysiloxane was introduced, and the stirring speed was 2°.
The reaction conditions were adjusted to r, p, and m, and the reaction was allowed to proceed for 3 hours.

After the reaction was completed, the produced solid component was washed with D-heptane, a portion of which was taken out, and the average particle size was measured by a sedimentation method, and found to be 24.5 microns.

In addition, the floating limit stirring strength equivalent rotation speed nf is 104r, 1
: It was 10m.

(2) Production of catalyst component The above component (mu) was introduced into a sufficiently purified flask. n-hebutane 50ml) II: Ti014
4.4 ml and 12 ml of methylhydrodiene polysiloxane were mixed, introduced into 7 flasks at 30°C, and reacted at 70°C for 2 hours. After the reaction was completed, it was washed with n-hebutane to obtain a catalyst component.

The T1 content in the catalyst component was 14.5 weight percent.

(3) Polymerization of ethylene Into a 1.5-liter stainless steel autoclave equipped with stirring and temperature control equipment, 800 milliliters of thoroughly dehydrated and deoxygenated n-hebutane was introduced, followed by 100 milligrams of triethylaluminum. , 5 milligrams of the catalyst component synthesized above was introduced.

The temperature was raised to 85°C, hydrogen was introduced at a partial pressure of 4 kg/cm2, and ethylene was introduced at a partial pressure of 5 kg/am2, resulting in a total pressure of 9 k.
g/am2G. Polymerization was carried out for 3 hours. These conditions were kept constant during the polymerization. After the polymerization was completed, ethylene and hydrogen were purged, the contents were taken out from the autoclave, and the polymer slurry was filtered and dried overnight. 71 grams of polymer was obtained. MFR-4
,3 (6710 minutes), polymer bulk specific gravity -0,42 (g/
cc), and the average polymer particle size was -483 microns.

Example 2 (1) Synthesis of component (A) Into a flask purified in the same manner as in Example 1, milliliter of n-hebutane purified in the same manner was introduced, and then Mg012 and Ti were added in the same manner as in Example 1. (0-nc4H,)
4 and react in the same way. The diameter of the stirring blade used at that time was g cm.

After the reaction was completed, the temperature was lowered to 35° C., 30 ml of methylhydrodiene polysiloxane was introduced, and the reaction was carried out for 3 hours at a stirring speed of 15 r, p, m. After the reaction was completed, the produced solid component was washed with n-heptane, a portion of which was taken out, and the average particle size was measured by a sedimentation method and found to be 25.8 microns.

Note that the nf equivalent rotational speed was ioo r, pm.

(2) Production of catalyst component The above component μ) was introduced into a sufficiently purified flask in the same manner as in Example-1. T in 10ml of n-hebutane
Mix 11.5ml of i0141, e'C30
The mixture was introduced into the flask within a few minutes, and reacted at 50° C. for 2 hours. After the reaction was completed, it was washed with n-hebutane to obtain a catalyst component. The T1 content in the catalyst component was 1000% by weight.

(3) Polymerization of ethylene Ethylene was polymerized in exactly the same manner as in Example 1, except that 100 mg of triethylaluminum and 50 mg of diethylaluminum chloride were used instead of 100 mg of triethylaluminum.

156.3 grams of polymer was obtained. MFR-4,
3 (g/10 min), polymer bulk specific gravity -0.40 (g/c
c), the polymer average particle size was -625 microns.

Example-3 (1) Synthesis of component (4) Into a flask purified in the same manner as in Example-1, 150 ml of n-hebutane purified in the same manner was introduced, and then 1c MgCl2 and T1 were added in the same manner as in Example-1. (0-nc
4Hs)4 was introduced, and further 7 ml of n-BuOHO was introduced, and the reaction was carried out in the same manner as in Example 1.

Note that the diameter of the stirring blade at that time was 6 cm, and the stirring rotation speed was 10 r, p, m. After the reaction was completed, it was washed with n-hebutane to obtain component (A). Its component (A)
The average particle size was 26.2 microns.

In addition, the floating limit stirring strength complementary rotation speed nf is 107r,
It was p, m.

(2) Production of catalyst component Component (A) synthesized above was introduced into a sufficiently purified flask. Then add 8 to 10 ml of n-heptane.
Mix 10143.2 mm') liters and heat at 30℃3
The mixture was introduced into the flask at 0 minutes, and reacted at 50°C for 2 hours.

Next, add TiC148 to 750 ml of n-hebuta,
0 ml was mixed and introduced into a flask at 30°C for 30 minutes, and reacted at 50°C for 2 hours. After the reaction was completed, it was washed with n-hebutane to obtain a catalyst component.

The T1 content in the catalyst component was 5.14 weight percent.

(3) Polymerization of ethylene Under the polymerization conditions of Example-1, the amount of triethylaluminum used was 150 mm! Polymerization was carried out in exactly the same manner except that the amount was changed to 7 grams. 221 grams of polymer was obtained. 1
1 [FR-4,8 (gylo content), polymer bulk specific gravity -0
, 42 (gyoa), and the polymer average particle size was -558 microns.

Example-4 (1) Production of catalyst component Component (A) was synthesized in the same manner as in Example-1. Then n-
Mix 10 ml of heptane with 1 ml of 81C147, and introduce into a flask at 30°C for 1 hour.
The reaction was carried out at ℃ for 2 hours. After the reaction was completed, it was washed with n-hebutane and used as a catalyst component. Ti content in catalyst component is 3.78
Weight percent.

(2) Polymerization of ethylene Under the polymerization conditions of Example-1, 200 μl of triisobutylaluminum was used instead of triethylaluminum.
Ethylene polymerization was carried out in exactly the same manner except that J-gram was used.

81 grams of polymer was obtained.

MFR-7,3 (g710 min), polymer bulk specific gravity -0,
44 (IC/'9L polymer average particle size -498 microns.

Example 5 Polymerization of propylene was carried out using the catalyst component synthesized in Example 2. Sufficient dehydration and dehydration was carried out in a stainless steel autoclave with an internal volume of 1.5 liters equipped with a stirring and temperature control device. 125 milligrams of triethylaluminum, 53.6 milligrams of diphenyldimethoxysilane, and 15 milligrams of the catalyst component synthesized in Example 2 were introduced into 500 milliliters of oxygenated n-hebutane. Then,
H! 40 mi! The temperature and pressure were increased, and the polymerization pressure was 5 kg/cm"G.

Polymerization was carried out at a polymerization temperature of -75°C and a polymerization time of -2 hours. After the polymerization was completed, the resulting polymer slurry was separated by filtration, and the polymer was dried.

95 grams of polymer was obtained. 5 from one f superfluous liquid
．． Five grams of polymer was obtained. From the boiling hebutane extraction test, all products 1. I is 86.9 weight percent, M
FR-9,6 (g/10 min), polymer bulk specific gravity" 0-
44 (g/cc), and the average polymer particle size was -371 microns.

Example 6 Using the apparatus for gas phase polymerization disclosed in Example 1 described in JP-A-57-73011, sufficiently purified polyethylene powder was charged into the apparatus, and then triethylaluminum was added. 100 milligrams of the catalyst component synthesized in Example-1 and 10 milligrams of the catalyst component synthesized in Example-1 were introduced. Then H2
1.2 kg/am" of ethylene was introduced at 85°C, and the total pressure was 9 kg/cm" at 85°C.
．． Polymerization was carried out for 5 hours. 154 grams of polymer was obtained. MFR-1,9 (gylo minute), polymer average particle size-
It was 503 microns.

Comparative Example-1 (1) Production of catalyst component In the production of the catalyst component of Example-1, the stirring rotation speed at the time of contact with methylhydrodiene polysiloxane was 30 Or,
The production was carried out in exactly the same manner except that p and m were changed. After the reaction was completed, the produced solid component was washed with n-hebutane, a portion was taken out, and the average particle size was measured and found to be 8.7 microns. Note that n is 104 r, p, and m.

(2) Polymerization of ethylene Ethylene polymerization was carried out under exactly the same conditions as in Example-1. 79 grams of polymer were obtained o MFR-4,
3 (g/10 min), polymer bulk specific gravity -0.46 (g/c
c), the polymer average particle size was -182 microns.

Example-7 (1) Production of component (A) In the production of component (A) in Example-1, the reaction of MgCl2 and τ1(0-nc4H*)4 was carried out in the same manner as in Example-1. After the reaction was completed, the temperature was lowered to 10°C, and 2 mol of 5iC140 was introduced over 1 hour at a stirring rotation speed of 2 Or, p, m, and the mixture was reacted at 30°C for 3 hours. After the reaction was completed, it was thoroughly washed with n-hebutane. Average particle size -17,
6 microns, and the Ti content was 1.55 weight percent.

Note that n4 was 106 r, p, m.

(2) Polymerization of ethylene Polymerization was carried out under the same conditions as in Example-1.

85 grams of polymer was obtained with MFR-5,1 (g/
10 minutes), polymer bulk specific gravity -0.39 (g/cc),
Polymer average particle size was -421 microns.

Example-8 Ethylene-butene-1 copolymerization In the polymerization of Example-1, ethylene-butene-1 containing 10 volume percent butene-1 instead of ethylene was used.
1 mixed gas was used and the polymerization temperature was 75°C.
Polymerization was carried out in the same manner. 103 grams of polymer was obtained, MFR - 7.3 (g/10 min), polymer average particle size - 526 microns, polymer bulk density 0.41 (
g/cc).

Claims (1)

[Scope of Claims] A catalyst component for olefin polymerization, which is a contact product of the following components (A) to (B). Component (A) A solid composition obtained by adding a precipitating agent to a solution of a contact product of magnesium dihalide and titanium tetraalkoxide and/or its polymer. However, the addition of the precipitating agent shall be carried out while stirring the reaction system at a stirring strength lower than the floating limit stirring strength. Component (B) Liquid titanium compound and/or silicon halide.