JPS5914484B2 - Method for producing catalyst component for α-olefin polymerization - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION BACKGROUND OF THE INVENTION The present invention relates to a method for producing a solid transition metal catalyst component that provides a Ziegler-type catalyst exhibiting high activity C0 for alpha-olefin polymerization.

Conventionally, when polymerizing α-olefins using a conventional Ziegler-type catalyst, such as a combination of titanium trichloride as a solid transition metal component with an organometallic compound such as diethylaluminum chloride, the transition Low activity per metal component.

As a result, catalyst residues, especially transition metal components, remain in the produced α-olefin polymer, and if we are trying to improve the thermal and oxidative stability of the product polymer, catalytic decomposition by alcohol and alkali A complicated purification process such as neutralization, ie, a detouching process, is required. ■Summary of the Invention Summary 35 The object of the present invention is to solve the above-mentioned problems and provide a Ziegler-type catalyst with such high activity that a decatalyzing step is unnecessary.

The present invention attempts to achieve this objective by using a solid transition metal component in which an interaction product of an alkoxytitanium compound and trihydrocarbyl aluminum is supported on a specific carrier. Therefore, the method for producing a catalyst component for α-olefin polymerization according to the present invention includes adding component (1) to component (1) below.
).

Component (1) A solid composition obtained by mixing and pulverizing the following components (1) to (3).

(1) Titanium trichloride (2) Magnesium halide (3) At least one compound represented by the following general formula.

(a) SiXl, (0R1)4? p (here, X1 is a halogen atom, R1 is a hydrocarbon residue, p is an integer from O to 4), (b) CX? (Here, X2 is a halogen atom), (c)
R2COOR3 or R2OH (where R2 and R
3 are the same or different hydrocarbon residues).

Component (11) An interaction product between an alkoxytitanium compound represented by the following general formula (1) and an organoaluminum compound represented by the general formula (4).

(1) Ti(0R)4 (where R is a hydrocarbon residue) (4) AlR? (Here, RO is a hydrocarbon residue.) Effect The Ziegler type 1 catalyst formed by combining the catalyst component according to the present invention with an organometallic compound has a very high activity, that is, the catalyst yield (weight relative to the solid catalyst component used) is very high. Since the amount of polymer produced is high, there is no need to carry out a decatalyzation step on the produced polymer.

In the present invention, it is necessary to support component (11) on component (1). Component (1) alone has ethylene polymerization ability when combined with an organoaluminum compound (Japanese Unexamined Patent Publication No. 5
1-82385), this component (1) is added with the component (
When U) is supported, the yield relative to the catalyst increases by 3 to 4 times. Conventionally,
Even when component (1) is combined with an organoaluminum compound, it itself has almost no α-olefin polymerization ability (even if it does, it is very low). Therefore, it is surprising and completely unexpected that when this component is supported on component (1), the activity of component (1) is greatly enhanced. In addition, as shown in the comparative example below,
In the production of component (1), titanium trichloride is excluded and component (
When n) is supported, the polymerization activity is very low or almost non-existent. This fact indicates that component () in the present invention must contain titanium trichloride, and in this respect it is essentially different from conventionally known magnesium halide carriers. be. In general, in conventional supported catalysts, even if a large excess of liquid transition metal compound is used with respect to the carrier, only a few percent of the transition metal compound is supported, and unsupported transition metal compounds must be removed by washing. Ta. However, the solid catalyst component according to the present invention is effective even when the supported amount of component (I[) is small, and during its production, component (ω) is
and component (1) up to 0.05), and almost the entire amount of component ([) is supported by component (1), so in that case no washing step is required. . Note that when an unsupported component (n) is present in the solid catalyst component according to the present invention, the achieved polymerization activity is not high, and in the case of ethylene polymerization, the density of the resulting polymer is low. Specific explanation 1 Catalyst A. Component (1) (1) Titanium trichloride Titanium trichloride includes titanium tetrachloride reduced with hydrogen [TlCl3(H)] and titanium metal reduced [TiCl3(T)]. ], those reduced with aluminum metal [TiCl3(A)], those reduced with organoaluminium compounds (e.g. titanium trichloride by diethylaluminum chloride reduction), those reduced with silicon hydride compounds (e.g. hydromethylpolysiloxane reduction). There are many other types, such as titanium trichloride).

Although the catalytic performance obtained in the present invention is not necessarily the same (there may be a difference in catalytic activity depending on the type of titanium trichloride used), the so-called Ziegler-catalyst (including Ziegler-Natsuta catalyst)
Any titanium trichloride component that can be used can be used.

Therefore, this titanium trichloride does not need to be pure TiCl3, but may have a large amount of AlCl3 added thereto, such as 1 TiC13(A), for example.

Alternatively, such an auxiliary component may be introduced after the fact, or it may unavoidably or intentionally contain a small amount of unreduced TiCl4, overreduced TiCl2, or an oxidation product of a reducing agent. Good too.

(2) Magnesium halide MgX? (X-halogen atom) Specifically, MgF2, MgCl2, MgBr2, MgT
There are 2.

(3) Alkoxy silicon, halogenated silicon, halogenated hydrocarbon, ester, alcohol (a) Alkoxy silicon compound represented by the following general formula.

SiXlp(0R1)4-, Here, X1 is a halogen atom, R1 is a carbon The hydrogen oxide residue, p is an integer of O to 4.

Hydrocarbon residues include alkyl, cyclic Roalkyl, aralkyl, aryl, a Straight chain, branched chain, saturated, unsaturated Can be saturated or cyclic, carbon It is preferable that the prime number is 8 or less.

Specific examples include tetramethoxysilane, tetraethoxysilane [Si(0Et)4], tetraisofropoxysilane, tetraphthoxysilane, tetraphenoxysilane, diethoxydimethylsilane, diisopropoxydimethylsilane, and triethoxysilane. Examples include methylsilane, dichlorodiethoxysilane, and silicon tetrachloride.

(b) A halogenated carbon compound represented by the following general formula.

CX? X2 is a halogen atom.

Specific examples of halogenated carbon compounds include CCl4, CBr4, CI4, CBrCl3, and the like.

(c) Ester alcohols represented by the following general formula.

R2COOR3, R2OH Here R2 and R3 are hydrocarbon residues Yes, they may be the same or different.

The hydrocarbon residue may be straight chain, branched, saturated, unsaturated, or cyclic, such as alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, alkaryl, aralkyl, etc., and has 1 to 10 carbon atoms. preferable.

Specific examples of esters include ethyl acetate, methyl acetate, ethyl benzoate, ethyl acrylate, methyl methacrylate, and methyl salicylate. Specific examples of alcohols include methyl alcohol, ethyl alcohol, isobutyl alcohol, and normal octyl alcohol. etc.

The above compounds (1) to (3) ((a) to (d)) can be used alone or in combination of two or more types within each group or between each group.

(4) Quantitative ratio The quantitative ratios of components () (1) to (3) may be arbitrary as long as the effects of this invention are recognized.

In general, the respective quantitative ratios of magnesium halide (2) and alkoxy silicon, silicon halide, halogenated carbon, ester, alcohol, etc. (3) to titanium trichloride (1) are determined by the activity of the mixed and pulverized catalyst components, It is determined by the relationship between the aggregate particle size, morphology, and crushing conditions.

Magnesium halide (2) and titanium trichloride (1)
) is 3 or more in molar ratio, preferably 10 to 50, and alkoxy silicon, alcohol, etc. (3) is 0.1 to 45% by weight, preferably 1 to 10% by weight based on the total weight of the three components.
It is preferable to mix and pulverize in a quantitative range of .

(5) Mixed Grinding The mixed grinding of components (1) (1) to (3) above can be carried out using any grinding equipment that allows intimate contact between the three components.

Since mixing and pulverization should be carried out without contact with moisture or air, rotary ball mills, rod mills, impact mills, vibration mills, and other various mills can be used as long as this point is taken into account.

The degree of mixed pulverization only needs to be sufficient to obtain the desired significant improvement effect of mixed pulverization of the three components (1) to (3). Therefore, from this point of view, the pulverization method, pulverization conditions,
What is necessary is to select the grinding time, etc.

For vibration mills, rotary ball mills, etc., the grinding time required to obtain the desired catalyst composition depends on a combination of various conditions such as ball filling rate, crushed sample filling rate, ball diameter, rotation speed or vibration frequency, and grinding temperature. The time required for this will vary, but in general, a product with sufficiently improved catalytic performance can be obtained by pulverizing within 100 hours.

Furthermore, if necessary, pulverization can be carried out either wet or dry.

Regarding the types and amounts of the three components (1) to (3), a typical mixed grinding method is to grind all of them in a mixed state from the beginning. It is also possible to add in portions over time.

B. Component (11) is an interaction product between an alkoxytitanium compound and trihydrocarbyl aluminum.

(1) Alkoxytitanium compound (1) It is expressed by the following general formula.

Ti(0R)4 Here R is a hydrocarbon residue.

As the hydrocarbon residue, alkyl groups and aryl groups having 1 to 8 carbon atoms can generally be used, but those derived from lower alcohols having 3 to 4 carbon atoms are preferred.

Specific examples include tetraethyl titanate, tetraisopropyl titanate, tetrabutyl titanate, and tetraphenyl titanate.

Tetraisopropyl titanate [Ti(01Pr)4]
, and tetrabutyl titanate [Ti(0Bu)4]
is preferred.

2) Trihuman rainbow carbyl aluminum (4) It is represented by the following general formula.

AlR3 Here, RO is a hydrocarbon residue.

As the hydrocarbon residue, alkyl groups, aryl groups, etc. having 1 to 10 carbon atoms can generally be used, but those having 2 to 6 carbon atoms are preferred.

Specific examples include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n
-hexylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, etc.

Triethylaluminum triisobutylaluminum is preferred.

Compounds (1) and (4) can be used alone or in combination of two or more.

(3) Quantitative ratio The quantitative ratio between compound (!) and (4) can be arbitrary as long as the effects of the present invention are observed.

Generally, the molar ratio of Ti(0R)4 and AlR3 is 0.
A range of 0.01 to 1001, preferably 0.1 to 30 is appropriate.

(4) Interaction substance What is supported on component (1) in the present invention is an interaction substance between compound (1) and (g).

The term "interacting substance" as used herein means various substances ranging from simple adducts or complexes to reactants in which the two are bonded through covalent bonds.

It appears that when the two interact, a complex is formed by coloring or changing color, but the details are unknown.
Therefore, in the present invention, this product will be referred to as an "interactant".

The interaction conditions between the two are such that the effect of the present invention is It can be anything permissible.

Generally, the reaction temperature is 0 to 100°C, preferably 20°C.
A temperature range of ~50°C is suitable, and it is suitable to dilute with an inert solvent and contact compound (1) with compound (4) at a concentration of 1 to 1007, preferably 5 to 1507 per liter of solvent. .

Examples of the inert solvent in this case include hydrocarbons and halogenated hydrocarbons.

Component (11) thus obtained is generally a liquid substance and can be easily mixed with a solvent.

C. Supporting conditions on component (1) (1) Supporting conditions The conditions for supporting component (11) on component (1) may be arbitrary as long as the second effect of the present invention is observed.

Generally, the reaction temperature is suitably in the range of -50 to 200°C, preferably 0 to 100°C, and the components () and (11) are mixed in an inert solvent, preferably with stirring, for 10 to 100°C. All you need to do is keep it in contact for about a minute.

In the present invention, "supporting" means that an interaction occurs between components (1) and (11), and the interaction product of the two is transferred to component ().
This means that the elution of component (1) is virtually unrecognizable even after washing with an inert solvent.

(2) Quantitative ratio The quantitative ratio of components (1) and (n) can be arbitrary as long as the effects of the present invention are recognized.

Generally, the weight ratio of component (]I) to component (1) is 0.
A suitable range is 005 to 501, preferably 0.01 to 10.

When this ratio is up to 0.05, virtually all of component (11) is carried by component (1). (3) Cleaning In the present invention, it is necessary that component (I[) is supported on component (1).

When unsupported or free component (1) is present, the catalyst activity is low, and when ethylene is polymerized, the density of the produced ethylene polymer is low.

Therefore, depending on the loading conditions of component (11) on component (),
Alternatively, when the weight ratio of component (11) to component (1) is large (particularly when this ratio exceeds 0.05), component (11) may be monomerized by an inert solvent relative to component (I[). Component (1) interactants should be washed to remove unsupported or free component (11).

In this case, the solvent may be, for example, carbonized Examples include hydrogen and halogenated hydrocarbons.

--． Polymerization of α-olefins Polymerization of α-olefins is carried out using the usual Ziegler method, except that the transition metal component of the Ziegler type 1 catalyst used is component (1) supported with component (I[) as described above. There is essentially no difference from the case where a type 1 catalyst is used.

(1) Formation of Ziegler Type 1 Catalyst When the solid composition prepared as described above is combined as a transition metal component with an organometallic compound component, a Ziegler Type 1 catalyst for α-olefin polymerization is formed.

(a) Organometallic compound Organometallic compound component of Ziegler type 1 catalyst Gold from Groups of the Periodic Table that can be used as Organometallic compounds of the genus can generally be used.

Organoaluminum compounds are preferred. As the organic aluminum compound, those represented by the following general formula are suitable.

RR-AAlX4a or R3-AAlXX and RK-B
Mixed organoaluminum compound with Al(0R3)b, (
Here, R6, R7, R8 have the same or different carbon number 1
~20 hydrocarbon residues, X4 is a nowagen atom, A. In particular, the general formula R1-BAl(0R8)b(0<b<3)
An organoaluminum compound represented by the general formula Rg-A
The molar ratio of the organic aluminum compound represented by Al
By using them together in an amount ratio of 10, it is possible to widen the molecular weight distribution of the resulting polymer, and it is possible to produce a polymer that is excellent in extrusion molding suitability, blow molding suitability, and film molding suitability.

Specific examples include (1) trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, tridecylaluminum, (2) diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, ethyl Examples include alkyl aluminum halides such as aluminum dichloride, and (3) alkyl aluminum alkoxides such as diethylaluminum ethoxide, diethylaluminum butoxide, and diethylaluminium phenoxide.

(b) Quantity ratio There is no particular restriction on the amount of the organometallic compound used to form the Ziegler type 1 catalyst, but it is generally preferred that the weight ratio is within the range of 0.5 to 100 relative to the solid catalyst component according to the present invention. .

(2) α-Olefin - represented by the general formula R9-CH-CH2 (where R9 is a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms).

Specific examples include ethylene, propylene, butene-1,
benzene-1, hexene-1,4-methylbenzene-1
and so on.

Particularly preferred are ethylene and propylene.
These α-olefins can be used in combination; specifically, for example, in the case of ethylene, 1
0% by weight, preferably up to 5% by weight of the other α-olefins mentioned above can be used in admixture.

(3) Polymerization In addition to the usual slurry polymerization, solvent-free polymerization, continuous polymerization, batch polymerization, or prepolymerization, which does not substantially use a solvent, is possible.

As the polymerization solvent in the case of slurry polymerization, saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, cyclohexane, benzene, and toluene may be used alone or in mixtures.

The polymerization temperature is about room temperature to 200℃, preferably 50 to 15℃.
0° C., and hydrogen can be used as an auxiliary molecular weight regulator. Experimental Examples Example 1 (1) Component (1) was manufactured in a stainless steel pot with an internal volume of 370 d and a diameter of 127 nm.
Filled with 40 stainless steel balls, TiCl3(A) (unground) manufactured by Toho Titanium Co., Ltd. (unground) 2.07, anhydrous MgCl2l6. Ot, Si(0Et)41.07, and SiCl4l. Of was sealed under N2 atmosphere and ground in a rotating ball mill for 24 hours.

The motor rotation speed was 100 rpm. After grinding,
The mixed and ground solid composition was removed from the pot in the dry box and stored in a sample bottle.

(2) Synthesis of component (11) 100 ml of thoroughly dehydrated and oxygenated n-heptane was mixed with N2
Place triethylaluminum 10 in the replaced flask.
00m9 and 1000m9 of tetrabutoxy titanate were each fed, and the mixture was stirred at room temperature for 1 hour.

(3) Supporting component (I[) on component (1) 100 ml of n-heptane was placed in a flask substituted with N2, 17 of component (1) was added, and 3 ml of the above component ([[) solution was added. and stirred at room temperature for 1 hour.

After that, the catalyst was dried without washing with n-heptane and the Ti content of the catalyst was measured, and it was found to be 2.3% by weight.
It was hot. (4) Polymerization of ethylene In a stainless steel autoclave with an internal volume of 1.51 mm equipped with stirring and temperature control equipment, after repeating vacuum-ethylene displacement several times, thoroughly dehydrated and deoxidized n-heptane was added to
00ml, followed by triethylaluminum 100ml
η and 10η of the solid catalyst component synthesized above were supplied.

The temperature was raised to 85°C, hydrogen was supplied at a partial pressure of 4.5'K9/Cd, and ethylene was further supplied at 4.5k9/Cd to bring the total pressure to 9k9.
/CdG, polymerization was carried out for 2 hours.

These reaction conditions were maintained during the polymerization. However, the pressure, which decreases as the polymerization progresses, was kept constant by introducing only ethylene. After the polymerization was completed, ethylene and hydrogen were released and the contents were taken out from the autoclave, and the polymer slurry was thoroughly filtered and dried in a vacuum dryer overnight. A white polymer of 1927 was obtained.

This means that 19200y of polymer was obtained per 1y of solid catalyst component (catalyst yield (7PE/7 solid catalyst component)
-19200). For this polymer, ASTM-D
Load 2.16 at 190℃ by method of l238-65T
The melt index (MT2) of k9 was measured. M.I.
It was 2-1.6. Comparative Example 1 Ethylene polymerization was carried out under exactly the same conditions as in Example 1, except that component (1) produced in Example 1 was used as a solid catalyst component without being supported with component (]I). .

A 55V polymer was obtained.

The yield to catalyst (7PE/7 solid catalyst) was as low as -5500. Example 2 In the synthesis of component ([[) in (2) of Example 1, the component ([[
) was synthesized and supported on component (1), and ethylene polymerization was carried out in exactly the same manner as in Example 1 except for the synthesis and loading of ethylene on component (1).

The results are shown in Table 1. Comparative Example 2 A solid catalyst was produced in exactly the same manner as in Example 1 except that TiCl3 was omitted in the production of component (1), and ethylene was polymerized under exactly the same conditions. .

Only 1.57 polymers were obtained. Example 3 100 η of the solid catalyst component produced in Example 1 and 100 m9 of triethylaluminum were each placed in 300 ml of heptane in a 1F flask, and propylene polymerization was carried out at 70° C. and normal pressure.

Polymerization was stopped after 1 hour.

A 8y polymer was obtained.

1.1. (The content of boiling n-heptane insolubles was 45%.

Example 4 (1) Component (1) manufactured in a stainless steel pot with an internal volume of 370 cr1 at 12 mT
Filled with 40 nφ stainless steel balls, TiCl3(A) manufactured by Toho Titanium Co., Ltd. (unground) 2.07, anhydrous MgCl2l6. O7, S1 (0Et) 41.0f
7 was sealed under N2 atmosphere and ground in a rotating ball mill for 24 hours.

The motor rotation speed was 100 rpm. After grinding,
The mixed and ground solid composition was removed from the pot in the dry box and stored in a sample bottle.

(2) Synthesis of component(s) Thoroughly dehydrated and oxygenated n-heptane (100ml) was mixed with N2
Place triethylaluminum 10 in the replaced flask.
00Tf19 and tetrabutoxy titanate 100W
19 were respectively supplied and stirred at room temperature for 1 hour.

(3) Supporting component (11) on component (1) Add 100 ml of n-heptane to a flask substituted with N2, and add 100 ml of component () to component (1).
7 were supplied, and further 30 ml of the above component (11) solution was supplied.

Stirred at room temperature for 1 hour. Thereafter, unsupported components were thoroughly removed with n-heptane. After drying, the catalyst Ti
When the content was measured, it was 2.3% by weight.

(4) Polymerization of ethylene Into a stainless steel autoclave with an internal volume of 1.51 and equipped with a stirring and temperature control device, after repeating vacuum-ethylene displacement several times, 800 ml of sufficiently dehydrated and oxygenated n-heptane was supplied, Subsequently, 10 m9 of triethylaluminum 100TI19 and the solid catalyst component synthesized as described above were supplied.

The temperature was raised to 85°C, hydrogen was supplied at a partial pressure of 4.5 kg/Cd, and ethylene was supplied at a partial pressure of 4.5 kg/Cd, resulting in a total pressure of 9k9/Cd.
Cd.

Polymerization was carried out for 2 hours.

These reaction conditions were maintained during the polymerization. However, the pressure, which decreases as the polymerization progresses, was kept constant by introducing only ethylene. After the polymerization was completed, ethylene and hydrogen were released, the contents were taken out from the autoclave, the polymer slurry was thoroughly filtered, and it was dried in a vacuum dryer overnight. 196 tons of white polymer was obtained.

Yield to catalyst (t-PE/7 solid catalyst components) = 19600
The melt index (MI2) of this polymer was measured at 190° C. under a load of 2.161<g by the method of ASTM-Dl23865T. MI2=1.5. When the density of the polymer was measured, it was 0.962 (7
/(-!l). Comparative Example 4 Components of Example 4 ()
A solid catalyst was produced in exactly the same manner as in the production of Component (1) except for TiCl3,
Polymerization of ethylene was carried out under exactly the same conditions.

Only 2.07 polymers were obtained. Example 8 300 d of heptane in 11 flasks each containing 100η of the solid catalyst component produced in Example 4 and 100η of triethylaluminumComparative Example 3 Supporting component (n) on component (4) produced in Example 4 Ethylene polymerization was carried out under exactly the same conditions as in Example 4, except that the catalyst was used as it was as a solid catalyst component.

A polymer of 55y was obtained.

The yield to catalyst (7·PE/7 solid catalyst component) was as low as 5,500. Example 5 Component ([I) was synthesized and supported on component (1) in exactly the same manner as in the synthesis of component (1) in (2) of Example 4, except that tetrabutoxy titanate was changed to tetraisopropoxy titanate. Ethylene polymerization was carried out in the same manner as in Example 4 except for washing and washing.

The results are shown in Table 2. Examples 6 to 7 In supporting component (11) on component (1) in Example 4 (3), the weight ratio of component (1) to component (1) was 0.
．． Ethylene polymerization was carried out under exactly the same conditions as in Example 4 except that the values were 1 and 5.0.

The results are shown in Table-3. Example 12 (1) Production of component (1) A stainless steel pot with an internal volume of 370 d was filled with 40 stainless steel poles of 12 mm diameter, and TiCl3(A) manufactured by Toho Titanium Co., Ltd. (unpulverized) 4.07, anhydrous. M of
gCl2l2. O7 and SiCl44. O7 was milled in a rotating ball mill under N2 atmosphere for 24 hours.

The motor rotation speed was 100 rpm.

After the pulverization was completed, the mixed pulverized solid composition was taken out from the pot in the dry box and stored in a sample bottle.

(2) Supporting component (]]) on component (1) Interaction between component (1) 17 in 100 ml of degassed and dehydrated n-heptane, tetrabutoxytitanate synthesized in Example 4, and triethylaluminum (weight ratio -1:1) was fed in an amount of 0.3y, and stirred at room temperature for 1 hour.

After that, thoroughly wash with n-heptane and convert to component 1 (
n) was carried out. Thoroughly clean a stainless steel autoclave with an internal volume of 1.5 cm equipped with an ethylene polymerization stirring and temperature control device, thoroughly dehydrate it, and
800 ml of deoxygenated n-heptane, 500 ml each of diethylaluminum ethoxide and diethylaluminum chloride, and 10 ml of the solid catalyst component synthesized above were fed.

Polymerization was carried out at a polymerization temperature of 85° C., a hydrogen partial pressure of 5.4 kg/Cd, an ethylene partial pressure of 3.6 kg/Cd, and a polymerization time of 2 hours. During the polymerization, these reaction conditions were maintained. However, the pressure, which decreased as the polymerization progressed, was kept constant by additionally introducing only ethylene. After the polymerization was completed, ethylene and hydrogen gas were released, the autoclave was taken out, and the polymer slurry was passed through a sieve and dried overnight. 1217 white polymers were obtained.

This means that 12,100 y of polymer was obtained per 1 y of solid composition (catalyst yield (7・PE/7 components (1
)12100). Polymer density was 0.277/CC. This polymer was subjected to a load of 2 at 190°C according to the method of ASTM-Dl238-65T.

When the melt index of 16k9 and 10.0k9 (MI2 and MIlO, respectively) was measured, MI2=0
．． 30, and the FR value (MIl
O/MI2) was 18.0.

Example 13 (1) Production of component (1) In the production of component (1) in Example 1, Si(0Et)4 and SiCl4 were replaced with Si(0Et)4 and SiCl4.
It was produced in exactly the same manner except that Et)2C12 was used at 1.7V.

Further, the loading of component (1) onto component (1) was carried out in exactly the same manner, and the polymerization of ethylene was carried out in exactly the same manner. A white polymer of 176y was obtained.

Catalyst yield (7PE/7 solid catalyst components) Melt index was 1.7.

Claims (1)

[Scope of Claims] 1. A method for producing a catalyst component for α-olefin polymerization, which comprises supporting component (II) on component (I) below. Component (I) A solid composition obtained by mixing and pulverizing the following components (1) to (3). (1) Titanium trichloride (2) Magnesium halide (3) At least one compound represented by the following general formula (a) SiX^1p(OR^1)_4_-_p (where X^1 is , a halogen atom, R^1 is a hydrocarbon residue,
p is an integer from 0 to 4. ) (b) CX^2_4 (Here, X^2 is a halogen atom) (c) R^2
COOR^3, or R^2OH (where R^2 and R^3 are the same or different hydrocarbon residues) component (II) an alkoxytitanium compound represented by the following general formula (i) and general formula (ii) (i) Ti(OR)_4 (where R is a hydrocarbon residue) (ii) AlR^0_3 (here, R^0 is a hydrocarbon residue) basis).