JPS61287908A - Production of catalyst component for polymerization of alpha-olefin - Google Patents

Abstract

PURPOSE:To obtain the titled catalyst component having a high ability of stereoregular polymerization and a high activity, by bringing a Mg halide, a specified electron-donating compound, a titanium halide and a liquid component of a high dielectric constant into contact with each other. CONSTITUTION:A magnesium halide-containing solid (A) (e.g., magnesium chloride), an electron-donating compound (B) having a structural part of formula I (wherein R is a 1-12C hydrocarbon or a 2-12C organic group having a structural part of formula II), e.g., 2-ethoxyethyl acetate or 2-methoxyethyl acetate, a titanium halide (C) (e.g., titanium tetrachloride) and a liquid component (D) having a dielectric constant at 20 deg.C>=2 (e.g., 1,2-dichloroethane or o- dichlorobenzene) are brought into contact with each other. In this way, the purpose catalyst component for polymerization of an alpha-olefin (e.g., propylene) is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a method for producing a catalyst component for alpha-olefin polymerization. More specifically, the present invention relates to a method for producing a so-called carrier-type titanium-containing solid catalyst component having a high degree of stereoregulatory polymerization ability and activity for producing an α-olefin polymer having stereoregularity. The carrier-type titanium-containing solid catalyst component according to the present invention is further combined with an organoaluminum compound and used as a catalyst for polymerization of α-olefins.

Prior Art Regarding titanium-supported catalyst systems, it has been known for a long time to add various electron-donating compounds to the catalyst system with the aim of improving the stereoregularity of the polymer (J.
Polymer 5science, PolymerL
etters, 3.855 (1965), a number of catalyst production methods have been proposed, particularly those involving the inclusion of an electron-donating compound in a titanium-supported solid catalyst component. Among electron-donating compounds such as esters, amines, ketones, and ethers, esters, especially esters of polycarboxylic acids with specific structures and esters of monocarboxylic acids with alkyl groups with specific structures, are stereoregular. It has been shown that it is highly effective in obtaining polymers (Japanese Unexamined Patent Application Publication No. 1989-1989).
-94590, JP-A-57-63310, JP-A-5
7-63311 and Japanese Patent Application Laid-Open No. 58-145707) 0 Summary of the Invention The present inventors previously disclosed in Japanese Patent Application No. 58-239098 an electron-donating compound having a specific structure [component (B)] ]
It was revealed that an excellent solid catalyst component for α-olefin polymerization can be produced by using this method.

The present inventors used the same electron-donating compound as that used in the previous application and a liquid component [component (D)] having specific properties.
] The present inventors have discovered that the performance as an α-olefin stereoregular polymerization catalyst component can be further improved by producing a titanium-containing solid catalyst component, and have completed the present invention.

That is, the present invention comprises: Component (A): an electron-donating compound having a magnesium halide-containing solid (wherein 几 is a C2-12 organic residue having a cl-12 formation site), component (C) : Titanium...rogen compound and component (D): Dielectric constant (-
The present invention provides a method for producing a catalyst component for α-olefin polymerization, characterized in that liquid components having a temperature of )≧2 (20° C.) are brought into contact with each other.

Effects of the Invention The use of organic carboxylic acid monoesters as electron-donating compounds to be introduced into solid titanium catalyst components is well known, particularly in the stereoregular polymerization of α-olefins, when organic aluminum compounds and 5i-0- When a cocatalyst consisting of a silicon compound having a C bond and a solid titanium catalyst component are combined to form a Ziegler type catalyst, the organic carboxylic acid monoester contained in the solid titanium catalyst component is an aromatic carboxylic acid ester ( Japanese Patent Publication No. 54-945
90) and R-C-0-R' (at least one convex of R and R' is a saturated or unsaturated branched hydrocarbon residue having 3 to 20 carbon atoms) (JP-A-57 -63310) is known to be effective.

However, the effect of the electron-donating compound [component (B)] defined in the present invention was not known at all until now.
Component (A), component (B), component (
By bringing C) and component (D) into contact with each other, the resulting titanium-containing solid catalyst component exhibits excellent activity and stereoregular polymerization performance.

The titanium-containing solid catalyst component of the present invention is produced by bringing component (A), component (B), component (C) and component (D) into contact with each other.

[Component (A)]

Component (A) is a magnesium halide-containing solid. As the halogen, fluorine, chlorine, bromine, and iodine can be used, and among these, chlorine is preferable. ), or from a hydrocarbon solution containing a dissolving agent for magnesium halide (e.g., tetrabutyl titanate, ether, phosphate ester) using known methods (e.g., methyl hydrogen). It also includes solid compounds such as solid acids obtained by precipitation treatment using empolysiloxane and titanium tetrachloride.

[Component (B)]

Component (B) is an electron-donating compound having a structural moiety represented by the following formula in its molecule.

(Here, R is an organic residue having 1 to 12 carbon atoms (C1-12) and 2 to 12 carbon atoms (02-12).) In the above structure, R is a relatively A short chain unbranched hydrocarbon residue is preferred, and the carbon of -0-g- is preferably an unbranched carbon atom. This compound generally has O in parts other than the above-mentioned specific structure.
, S and N which do not have polar atoms are used. It is preferable that the molecule has one smooth molecule.

Preferable compounds among such compounds are those represented by the following formula (B'
).

R''-C-0-R-0-R2 (B) Here, R is the same as R in the above formula, and R1 and R2 are each an alkyl group, -aryl group, or alkyl-substituted aryl group having 1 to 12 carbon atoms. or an aryl-substituted alkyl group.Among the compounds represented by the formula (B'), particularly preferred are lower aliphatic monocarboxylic acids (where R1 has about 1 to 12 carbon atoms) or benzoic acid < al ether of ethylene oxide or propylene oxide adduct (1 mol) of phenyl group), especially lower (00 to C
1□) Alkyl or phenyl or tolyl ether,
It is.

Specific examples of such electron-donating compounds include 2-methoxyethyl-acetate (CH, Co2
CH, CH20CH3), 2-ff-toki'/kfk=
Acetate (CH3CO□CH2cH2oC2H6),
2-7') #S:r-fk-7Set(CH3C
o□CH2CH,QC4H,), 3-methoxyphthyl acetate (CH3CO2(CH2)2CH(OCH3
)CH3), 2-(2-ethoxyethoxy)ethyl-7
Se? -(CHlCO,CH2C)120CH,CH
2QC.

H, ), 2-p-) lyloxyethyl acetate (CI
(3CO2CH2CH20C6H4(CH3)), ethoxylmethyl-acetate (CH3C02a(20C2
H5), 3-ethoxyfurohyltan acetate (CH3C
O2CH2CH2c) (20C2H,), 4-ethoxybutyl-acetate (CH3■2CH2CH2CH2C
H2QC2H,), n-butylcalcium) -/I/=acetate (CH3CO□(CH2CH20)2C-H8
), 2-butoxyethyl-propionate (CHCE
(2C02CH2Q(2Co,H,), 2-isobutoxyethyl-probionate (CH3CH2C02CH2
CH20CH2CH(CH3)2), 2-ethoxyethyl-n-butyrate (C4H, Co2CH2CH2oC
2H5), 2-ethoxyethyl-isobutyrate ((C
H3) 2CHCO2C2CH2Koku2H5), 2-ethoxyethyl-hensoate (C6I
I (20C2H5), 2-impropoxyethyl; benzoate (C6H5CO□C) (on 2CH2α (Q-(
3) 2), p-methoxyphthyl acetate (CH,
C02C) (2-C61140CH1), ethoxyphenylx4-n-j thylbenzony) (CH3(
CH2)3C, H4C0□C6H40C2H4), Tetrahuman
(CH2)2Co2G(2(C4H,O)), etc. Among these, 2-ethoxyethyl acetate and 2-methoxyethyl acetate are preferred.

[Component (C)]

Component (C1: is a halogen compound of titanium.

Suitable titanium halogen compounds include trivalent and tetravalent titanium halogen compounds, particularly preferably tetravalent titanium halogen compounds. As the halogen, chlorine is preferred. Preferred titanium halogen compounds have the general formula Ti (OR;' )nCL4. Among the compounds represented by (r is a C1-C6 hydrocarbon residue), it is n-O or 1. Specific examples include titanium tetrachloride and titanium trichlorobutoxy.

[Component (D)]

Component (D) Fi is a liquid component having a dielectric constant of 2 or more at 20°C. However, liquid components that have strong reactivity with the halogen compounds of titanium in the titanium-containing solid components, such as active hydrogen, carbonyl groups, and nitrile groups, should be excluded. Specifically, aromatic hydrocarbons represented by benzene, toluene, ethylbenzene, xylene, styrene, tetrahydronaphthalene, etc., aliphatic or cyclic hydrocarbons represented by cyclohexane, methylcyclohexane, 1-hexene, decahydronaphthalene, etc. Aliphatic hydrocarbons, chlorobenzene, bromobenzene, benzene iodide, 0-dichlorobenzene, ethyl chloride, n-propyl chloride, n-butyl chloride, isobutyl chloride, tert chloride
-butyl, n-amyl chloride, isoamyl chloride, ethyl bromide, n-propyl bromide, isopropyl bromide, n-butyl bromide, inbutyl bromide, tert-butyl bromide, 1,2
-dichloroethane, 1.1.2-) dichloroethane,
1.1,2.2-tetrachloroethylene, hexachloroethane, 1,2-cyfuromoethane, 1,1.2-)ripromoethane, 1,1,2.2-tetrabromoethane,
Halogenated hydrocarbons represented by phenyltrichloromethane, ether compounds represented by dibutyl ether, diynebutyl ether, anil, phenylethyl ether, phenylpropyl ether, phenyltrichlorosilane, diphenyldichlorosilane, triphenylchlorosilane, Examples include halogenosilane compounds represented by hexachlorodisilane, methyltrichlorosilane, and tetrachlorosilane.

Among these, especially 1,2-dichloroethane.

-Preference is given to using dichlorobenzene.

The above liquid components can be used alone or in combination of two or more.

[Quantity ratio]

The component ratios of the four components (A) to (D) are arbitrary and not critical as long as the effects of the present invention are recognized.

Generally, component (B) has a molar ratio of electron donating compound component (B) to magnesium halogen compound present in component (A) [component (B)/Mg] of 0.00.
It is used in a ratio of 1 to 6, preferably 0.001 to 0.6.

Component (C) can be used in a wide range of proportions, but generally the amount of titanium atoms contained in the titanium-containing solid catalyst component produced by various methods is 0.5 to 15% by weight, preferably 0.5% by weight.
It is preferable to adjust the weight so that it falls within the weight limit of 5 to 10 mm.

Component (D) can also be used in a wide range of ratios, but generally the molar ratio of component (D) to the magnesium halogen compound in component (A) [component (D)/Mg] is 0.5 or more, preferably Used in 2 or more.

[Preparation of titanium-containing solid catalyst component]

In the titanium-containing solid catalyst component of the present invention, component (A), component (B), component (C), and component (D) are brought into contact with each other. Component (A), component (B), and component (C) can be obtained by contacting component (D) with a titanium-containing solid component that is obtained by contacting them all at once or in stages or once or multiple times. It is also possible to use a method in which component (D) is present in the step of contacting.

In addition, after contacting component (D), component (B)
, it is also possible to re-contact component (C) and it can be obtained by various preparation methods. Some specific preparation methods are as follows.

i), MgX2 (□・magnesium rogenide) and component (B) are mixed and pulverized, and the resulting pulverized product and component (
q and the mixture of component (D) are brought into contact in a liquid phase.

ii) Component (A), component (B) and (C) are mixed and pulverized, and the obtained pulverized product and component (D) are brought into contact with each other in a liquid phase.

1ii) A hydrocarbon solution containing MgX2 is prepared using a dissolving agent such as alcohol, ether, titanium alkoxide, or trialkyl phosphate, and this solution is brought into contact with a titanium or silicon halogenating agent to dissolve the solid. precipitation (formation of component (A)), and this precipitated solid and component (B)
) and component (C) sequentially or simultaneously in a liquid phase, and further contacted with component (D).

In the method of iv), 1ii), MgX obtained
Component (B) is added to a hydrocarbon solution containing 2, and this solution is brought into contact with a halogenating agent to precipitate a solid (component (B)
The precipitated solid is brought into contact with component (C) in a liquid phase, and further brought into contact with a mixture of component (C) and component (D).

v), MgX2 is dissolved in a hydrocarbon solvent using butyl titanate, reacted with methylhydrodiene polysiloxane to precipitate a solid, contacting the precipitated solid containing MgX2 with component (B), and further dissolving component (C). ) and component (D) are brought into contact sequentially or simultaneously.

The feature of the present invention is that an electron-donating compound having a specific molecular structure is used, and the dielectric constant is 2 at 20°C.
As long as this image component is used, its effects will be exhibited in other methods for preparing various titanium-containing solid catalyst components. Therefore, the method for producing the titanium-containing solid catalyst component of the present invention is not limited to the method exemplified above.

[Polymerization of α-olefin]

The titanium-containing solid catalyst component of the present invention can be used in the polymerization of α-olefins by combining it with an organoaluminum compound.

The organoaluminum compound has the general formula AIR,X, -1(
However, 几 is a hydrocarbon residue having 1 to 12 carbon atoms, X is a halogen, and n is a compound represented by Own≦3.

Such organoaluminum compounds include, for example, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, triisohexylaluminum, trioctylaluminum, Examples include diethylaluminum hydride, diisobutylaluminum hydride, diethylaluminum monochloride, and ethylaluminum sesquichloride. Of course, two or more of these aluminum compounds can also be used in combination.

Among these, trialkyl aluminum is preferred;
Particularly preferred is triethylaluminum.

When carrying out a polymerization reaction of α-olefins having 3 or more carbon atoms, this is added to the catalyst system consisting of the titanium-containing solid catalyst component and the organoaluminum compound according to the present invention for the purpose of improving the stereoregularity of the resulting polymer. Many compounds that have been proposed to be used in Ziegler polymerization catalysts and have effects on stereoregularity can be further added. Compounds used for this purpose include aromatic monocarboxylic acid esters, organosilicon compounds having an -8i-OJ- bond, and nitrogen or oxygen heterocyclic compounds having an alkyl substituent. Specifically, for example, ethyl benzoate, ethyl p-toluate, ethyl p-anisate, phenyltrimethoxysilane,
Phenyltriethoxysilane, diphenyldimethoxysilane, diphenyljethoxysilane, t-butylmethyldimethoxysilane, tetraethylsilicate, 2,2.
These include 6°6-tetramethylbiperidine, 2,2.6.6-titramethylbilane, and the like.

The ratio of the titanium-containing solid catalyst component to the organoaluminum compound used can vary over a wide range, but is generally between 1 and 1,000, preferably between 10 and 500 (molar ratio) per titanium atom contained in the solid catalyst component. Organoaluminum compounds can be used in

When using the titanium-containing solid catalyst component of the present invention, even a very small amount of the above-mentioned stereoregulatory improver used for the purpose of improving the stereoregularity of the α-olefin polymer can achieve the purpose. However, usually 0.001 to 1 mol per mol of organoaluminum compound,
It is preferably used in a ratio of 0.01 to 0.5 mol.

The order and number of times the titanium-containing solid catalyst component, organoaluminium compound, and steric control improver are brought into contact with each other is arbitrary.

Further, the titanium-containing solid catalyst component according to the present invention can be subjected to a preliminary contact treatment (so-called prepolymerization treatment) with a small amount of olefin in the coexistence of an organoaluminum compound prior to polymerization of the α-olefin. The olefins that can be used in the prepolymerization treatment may be the same α-olefin used in the polymerization, or they may be different α-olefins.

The olefins used for polymerization include ethylene, propylene, 1-butene, 1-hexene, and 4-methylpentene.
1, etc., and these can be not only homopolymerized but also random copolymerized or block copolymerized with each other. Further, regarding copolymerization, polyunsaturated compounds such as conjugated dienes and non-conjugated dienes can also be used as copolymerized olefins.

Possible polymerization methods include a so-called slurry polymerization method using an inert hydrocarbon such as hexane or heptane as a solvent, a liquid phase polymerization method using a liquefied monomer as a solvent, or a gas phase polymerization method where the monomer exists as a gas phase. .

The polymerization temperature is generally about 20 to 150°C, preferably 40°C.
~100℃, polymerization pressure is atmospheric pressure ~100 atm,
Preferably the pressure is about atmospheric pressure to 50 atm. The molecular weight of the polymer is mainly controlled by a method using hydrogen.

Example 1 (Production of titanium-containing solid catalyst component) Dehydrated and deoxygenated n-hebutane 50- was introduced into a -fc300mj flask which had been sufficiently purged with nitrogen, and then MgC12 (
0.1 mol of magnesium chloride), Ti (OBu)
After introducing 0.2 mol of 4 (tetraphthoxytitanium), 9
A hydrocarbon solution of MgCl2 was prepared by reacting at 0°C for 2 hours. Next, 12d of methylhydrodienepolysiloxane (20CpS) was added and reacted at 40°C for 3 hours, and about 401 greyish white solids were precipitated.

When this precipitated solid was thoroughly washed with n-hebutane and analyzed, it was found that this precipitated solid contained 12.1 weight range of MgCl2.

20 f! from this precipitated solid! (MgC62=2.4
29) was sampled, diluted in n-hebutane 80-, and 0.37 d (
CH1Co2CH2CH20C2H6/Mg-0,11
molar ratio) and diluted in n-hebutane 50-
Add Cl41.0- and react at room temperature for 1 hour. After the reaction is complete, the product is washed with n-hebutane. Next, T
Add 1.7d of i C70 and react at 50°C for 1 hour. Wash the product with n-hebutane. Next, TiCl
2 was added and reacted at 70°C for 1 hour. The product is washed with n-hebutane to obtain a titanium-containing solid component.

50 d of 1,2-dichloroethane is added to the obtained titanium-containing solid component, and contact treatment is carried out at 80° C. for 1 hour. After removing the supernatant, TICZ425 rnl was added and reacted at 80°C for 2 hours. The supernatant was removed, and 25% of TIC70 was added and reacted at 80°C for 2 hours.

After the reaction is complete, wash the solid by decantation (
(5 times with 200 g of n-hebutane) to obtain the desired titanium-containing solid catalyst component slurry. When a portion of this slurry was sampled and analyzed after n-hebutane was evaporated to dryness, it was found that the solid contained 3.37% titanium.

(Polymerization of propylene) (a) Polymerization-1 In an autoclave with an internal volume of 1 liter and equipped with a stirring device, 500 N of dried and degassed n-heptane and 107 N of diphenyldimethoxysilane were placed. , triethylaluminum 250μ (8i/At=0.2 molar ratio) and 0.5μ in terms of Ti atoms from the titanium-containing solid catalyst component slurry obtained in Example 1 above were introduced in this order under a propylene atmosphere, Polymerization was started by adding 150-hydrogen. Polymerization is carried out using a propylene pressure cuff Kq/cf! G, conducted under the conditions of 70°C/3 hours.

After the polymerization was completed, the remaining monomer was purged, the polymer slurry was distributed from house to house, and the amount of each produced polymer was determined by drying the powdered polymer and concentrating the F solution.

Stereoregularity of this powder polymer (hereinafter referred to as product II)
was determined by boiling n-hebutane extraction test. In addition, the total II (ratio of the amount of boiling n-hebutane-insoluble polymer to the total amount of polymer produced) is determined by the relational expression: total II - amount of powder polymer x product II / (amount of powder polymer + amount of concentrated polymer) I asked for it. These results are shown in Table-1.

(b) Polymerization-2 Polymerization-2 was conducted under propylene polymerization conditions 7 Vq/amIC
r.

Polymerization-1 except that the temperature was 70°C/8 hours and the titanium-containing solid catalyst component slurry was 0.3 capes in terms of Ti atoms.
It was carried out under exactly the same conditions.

These results are shown in Table-1.

(c) Polymerization-3 In polymerization-3, t was used instead of diphenyldimethoxysilane.
ert-butylmethyldimethoxysilane 7.28rq
The polymerization was carried out under exactly the same conditions as Polymerization-1 except that the molar ratio was 0.2 (si, 12 = 0.2 molar ratio). These results are shown in Table-1.

Example 2 The operation of contacting a titanium-containing solid component obtained in the same manner as in Example 1 with TICt425- at 80°C for 2 hours was repeated twice, the supernatant was removed, and the solid was washed with hebutane by decantation. After that, 50 rnt of 1,2-dichloroethane was added and contact treatment was performed at 75°C for 1 hour (contact treatment of titanium-containing solid component and component (D)).
. After the reaction was completed, the solid was washed by decantation to obtain the desired titanium-containing solid catalyst component slurry. (
(Ti content: 3.30% by weight) Using the obtained titanium-containing solid catalyst component, propylene was polymerized in the same manner as in Polymerization-1 of Example 1.

The results are shown below.

Activity 29.4 x 10.4 (rpp/r
Ti ) 9.700 (fpp/f solid catalyst) Atactic production rate 0.53 (壬) Product I I
98.5 (ch) All I I
98.0 (Excellent) MF 1.7
3 (f/10 min) BD O,
43 (t/Cr-) Examples 3 to 6 When producing a titanium-containing solid catalyst component, the following steps were taken, except that the type of liquid component defined as component (D) and the contact treatment temperature were changed as shown in Table 2. A titanium-containing solid catalyst component was produced under the same conditions and method as in Example-1.

Polyimposition of propylene was carried out under the same conditions as in Polymerization-1 except that the titanium-containing solid catalyst components obtained above were used. These results are shown in Table-2.

Example 7 In producing a titanium-containing solid catalyst component, the titanium-containing solid component obtained in Example 1 is treated with a mixture of 1,2-dichloroethane 25- and Ti CL425- added at 80° C. for 2 hours. After removing the supernatant, further TiCt, 25
- was added and the treatment was carried out at 80°C for 2 hours. After this treatment, the solid was washed by decantation (5 times with 200 g of n-heptane) to obtain the desired titanium-containing solid catalyst component slurry. Polymerization of propylene was carried out under the same conditions as Polymerization-1 except that this titanium-containing solid catalyst component was used. The results are shown in Table-2.

(Left below) Comparative Example-1 When producing a titanium-containing solid catalyst component, n-heptane 50-, which has a dielectric constant of 1.92, was added in place of the liquid component defined as component (D) and heated at 90°C. A titanium-containing solid catalyst component was produced under the same conditions and method as in Example-1, except that the treatment was carried out for 1 hour.

Polymerization of propylene was carried out in the same manner as Polymerization-1 except that this catalyst component was used. The results are shown in Table-3.

Comparative Example 2 In producing a titanium-containing solid catalyst component, 0.40 d of known ethyl benzoate (C,H3CO2C2H5
/Mg = 0.11 molar ratio)
A titanium-containing solid catalyst component was produced under the same conditions and method as in Example 1.

Polymerization of propylene was carried out in the same manner as in [Polymerization] except that this catalyst component was used.

Comparative Example-3 In producing a titanium-containing solid catalyst component, the known ethylbenzony) 0.40-(C6H5CO2C2H5/
Example-1 except that Mg = 0.11 molar ratio) was added.
A titanium-containing solid catalyst component was produced under the same conditions and method as described above.

Polymerization of propylene was carried out in the same manner as Polymerization-1 except that this catalyst component was used. The results are shown in Table-3.

(The following is a blank space) Example 8 (Production of a titanium-containing solid catalyst component and its prepolymerization treated catalyst) A titanium-containing solid catalyst component was produced using the method and conditions of Example 2, and a prepolymerization treatment was performed. The prepolymerization treatment was performed using 3t of titanium-containing solid catalyst component (Ti'H13,30w
Prepare n-hebutane slurry using t4).
After adding 0.47 t of triethylaluminum (At/Ti (molar ratio) = 2) at a temperature of 10° C., propylene 62 was introduced and contacted over a period of 20 minutes.

Using the prepolymerized catalyst of the present invention thus obtained, 7
Polymerization of propylene was carried out in the same manner as in Polymerization-1 of Example-1 by introducing the catalyst component under the temperature condition of 0°C.

The results obtained are shown below.

Activity 27.3 x 10.4 (rpp/f
Ti )9.000 (fpp/r solid catalyst) Atactic production rate 0.40 (B) Product I I 98.6 (Excellent) Total I I
98.2 (壬) MFR+, 23 (r/10 minutes) BD O, 45 (r/CC) Patent applicant: Mitsubishi Yuka Co., Ltd., Patent Attorney Hidetoshi Furukawa, Representative Patent Attorney Masahisa Hase Procedural amendment (Spontaneous) a July 17, 1985 L Indication of the case 1985 Patent Application No. 131241 2 Title of the invention Process for producing a catalyst component for α-olefin polymerization 1 Person making the amendment Relationship to the case Patent applicant Address: 2-5-2 Marunouchi, Chiyoda-ku, Tokyo Name (6
05) Mitsubishi Yuka Co., Ltd. 4, Agent address: Mitsubishi Yuka Co., Ltd., 2-5-2 Marunouchi, Chiyoda-ku, Tokyo, 11, Name (8401) Patent attorney Hidetoshi Furukawa ((1 other person) & amendments) 2 yen 7 ゝ - Contents of amendment (1) l"' on page 24, line 15 of the specification cylinder 29.4 X
10.4 (ppp/riTi) J is replaced with “29
．． 4 Correct it as X1♂-(ripp/pTi)J.

(2) l'-27, 3X 1 on page 31, line 16 of the specification tube
(L4(f-pp/fT1)J is r2
7.3 Correct as X10'(j'Pp/PTi)J.

(3) Table-1 on page 23 of the specification, Table-2 on page 27
and Table 3 on page 30 are corrected as shown in the attached sheets.

that's all (Attachment) (Attachment)

Claims (1)

[Claims] (1) Component (A): Solid containing magnesium halide, Component (B): Electron-donating compound having the structural site shown by ▲Mathematical formula, chemical formula, table, etc. (However, R is carbonization of C_1_ to_1_2) C that has a hydrogen residue or a structural site indicated by ▲There are mathematical formulas, chemical formulas, tables, etc.▼
_2_ to _1_2), component (C): titanium halogen compound, and component (D
): a liquid component having a dielectric constant (ε)≧2 (20° C.): A method for producing a catalyst component for α-olefin polymerization, which comprises bringing into contact with each other.