JPH07121970B2 - Method for producing ethylene / propylene copolymer rubber - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing an ethylene / propylene copolymer rubber.

2. Description of the Related Art There is known a method of producing an ethylene / propylene copolymer rubber by copolymerizing ethylene and propylene using a titanium catalyst having a higher activity in place of the conventional vanadium catalyst.

Recently, several methods for producing the copolymer rubber using a magnesium compound-supported titanium-based catalyst have been tried.
They have complicated steps. There is a problem that the bulk density of the obtained polymer is low and there is a problem in practical use.

On the other hand, using a catalyst component in which a titanium component is supported on a metal oxide such as silica, copolymerization of ethylene and propylene, particularly gas phase polymerization, is a method whose main purpose is to obtain a polymer with particularly good particle properties. It has been reported.

For example, the reaction product of (1) metal oxide, (2) magnesium halide and the compound of formula Me (OR) nXz-n, (3) formula Solid compound component ((Japanese Patent Laid-Open No. 59-105008), which is obtained by bringing the silicon compound of (4) and the titanium compound (4) into contact with each other, and the formula MgmT
A catalyst prepared by diluting a composition represented by i (OR) nXp (ED ₈ [X is a halogen and ED is an electron donating compound] with a metal oxide and activating it with an organoaluminum compound (Japanese Patent Laid-Open Publication No. 2000-242242). 59-230011) has been proposed.

Problems to be Solved by the Invention According to the method for producing a copolymer using these metal oxide-supported titanium-based catalysts, it is possible to produce a polymer having a somewhat improved particle property. There is a problem that the amount of polymer produced per catalyst is low.

Means for Solving the Problems Object of the Invention An object of the present invention is to produce an ethylene / propylene copolymer rubber excellent in particle properties using a metal oxide-supported titanium-based catalyst in a high yield. As a result of intensive studies conducted by the present inventors, (A) a metal oxide (A) showing excellent performance as a highly stereoregular catalyst of α-olefin, which was previously developed by the present inventors. The solid obtained by contacting B) dihydrocarbyl magnesium and (C) compound containing a hydrocarbyloxy group is converted into (D)
Using a catalyst component (Japanese Patent Application No. 60-146805) obtained by contacting with a halogen-containing alcohol and further contacting with (E) an electron donating compound and (F) a titanium compound, ethylene and propylene The present invention has been completed by finding that the object of the present invention can be achieved by polymerization.

SUMMARY OF THE INVENTION That is, the present invention relates to (A) an oxide of a metal element selected from the group of metal elements of Groups II to IV of the periodic table of the element, (B) dihydrocarbyl magnesium, and (C) a formula R _n M (OR ¹ ) _4-n (R is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, M is silicon or a carbon atom, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, and 0 ≦ n < The solid obtained by contacting the hydrocarbyloxy group-containing compound represented by (4) is contacted with (D) a halogen-containing alcohol, and further contacted with (E) an electron-donating compound and (F) titanium tetrachloride. A method for producing an ethylene / propylene copolymer rubber having an ethylene content of 15 to 90 mol%, which comprises copolymerizing ethylene and propylene in the presence of a polymerization catalyst comprising the catalyst component thus obtained and an organoaluminum compound. Is the gist.

Raw Material for Preparation of Catalyst Component (A) Metal Oxide The metal oxide used in the present invention is an oxide of an element selected from the group of elements of Group II to Group IV of the periodic table of elements,
For example, B ₂ O ₃ , MgO, Al ₂ O ₃ , SiO ₂ , CaO, T
Examples thereof include iO ₂ , ZnO, ZrO ₂ , SnO ₂ , BaO, ThO _{2 and the} like. Among these, B ₂ O ₃ , MgO, Al ₂ O ₃ , SiO ₂ , TiO ₂ , and ZrO ₂ are preferable, and SiO ₂ is particularly preferable. Furthermore, composite oxides containing these metal oxides, for example _{SiO 2 -MgO, SiO 2 -Al 2} O 3,
_{SiO 2 -TiO 2, SiO 2 -V} 2 O 5, SiO 2 -Cr 2 O 3, SiO 2 -TiO 2 -M
gO etc. may also be used.

The above-mentioned metal oxides and composite oxides are basically desirable to be anhydrous, but it is permissible to mix a trace amount of hydroxides which are usually mixed. Further, it is permissible to mix impurities to the extent that the properties of the metal oxide are not significantly impaired. Acceptable impurities include sodium oxide, potassium oxide,
Examples thereof include oxides, carbonates, sulfates, nitrates and the like of lithium oxide, sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, sodium sulfate, aluminum sulfate, barium sulfate, potassium nitrate, magnesium nitrate, aluminum nitrate and the like.

The shape of these metal oxides is usually powder. Since the shape of the powder such as size and shape often affects the shape of the obtained olefin polymer, it is desirable to adjust it appropriately. It is desirable that the metal oxide be burned at a temperature as high as possible and handled so as not to come into direct contact with the atmosphere, for the purpose of removing poisonous substances before use.

(B) Dihydrocarbyl magnesium The dihydrocarbyl magnesium used in the present invention (hereinafter referred to as organic Mg) is represented by the general formula RMgR '. In the formula, R and R'represent the same or different alkyl, cycloalkyl, aryl and aralkyl groups having 1 to 20 carbon atoms.

Examples of organic Mg include dimethyl magnesium (hereinafter magnesium is abbreviated as Mg), diethyl Mg, ethyl methyl Mg, dipropyl Mg, diisopyropyr Mg, ethylpropyl Mg, dibutyl Mg, diisobutyl Mg, disec-butyl M.
g, di tert-butyl Mg, butyl ethyl Mg, butyl propyl Mg, sec-butyl ethyl Mg, tert-butyl isopropyl Mg, sec-butyl tert-butyl Mg, dizintyl Mg, diisopentyl Mg, ethyl pentyl Mg, isopropyl pentyl Mg, sec- Butylpentyl Mg, Dihexyl Mg, Ethylhexyl Mg, Butylhexyl Mg, tert-Butylhexyl Mg, (2-Ethylbutyl) ethyl Mg, (2,2-Diethylbutyl) ethyl Mg, Diheptyl Mg, Dioctyl Mg, Di2-ethylhexyl Mg , Didecyl Mg, dicyclohexyl
Mg, cyclohexylethyl Mg, butylcyclohexyl M
g, di (methylcyclohexyl) Mg, diphenyl Mg, ethylphenyl Mg, butylphenyl Mg, sec-butylphenyl Mg, ditolyl Mg, ethyltolyl Mg, dixylyl Mg,
Dibenzyl Mg, benzyl tert-butyl Mg, diphenethyl
Mg, ethylphenethyl Mg, etc. are mentioned.

These organic Mg may be a mixture or complex compound with an organic compound of another metal. Other metal organic compounds are
It is represented by the general formula MRn (where M is boron, beryllium, aluminum or zinc, R is an alkyl, cycloalkyl, aryl or aralkyl group having 1 to 20 carbon atoms, and n is the valence of the metal M). Specific examples thereof include triethyl aluminum, tributyl aluminum, triisobutyl aluminum, triphenyl aluminum, triethyl boron, tributyl boron, diethyl beryllium, diisobutyl beryllium, diethyl zinc and dibutyl zinc.

The ratio of the mixture of organic Mg and the organic compound of other metal or the complex compound is usually 5 gram atom or less of the other metal, preferably 2 gram atom or less, per 1 gram atom of magnesium.

(C) Hydrocarbyloxy Group-Containing Compound The hydrocarbyloxy group-containing compound used in the present invention is represented by the formula R _n M (OR ¹ ) _4-n . In the formula, R represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, M represents silicon or a carbon atom R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms, and 0
≦ n <4.

As the hydrocarbon group, an alkyl group such as methyl, ethyl, propyl, i-propyl, butyl, amyl, hexyl, octyl, 2-ethylhexyl and decyl, a cycloalkyl group such as cyclopentyl, cyclohexyl and methylcyclohexyl, allyl, propenyl and butenyl. Alkenyl groups such as, aryl groups such as phenyl, tolyl, xylyl,
Examples include aralkyl such as phenethyl and 3-phenylpropyl. Of these, an alkyl group having 1 to 10 carbon atoms is particularly desirable, and R and R ₁ may be the same or different.

Specific examples of these compounds include Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si (OC ₄ H ₉ ) ₄ and Si contained in the formula Si (OR ¹ ) _{4.
(Oi-C 4 H 9)} 4, Si (OC 6 H 13) 4, Si (OC 8 H 17) 4, Si _{[O · CH 2 CH (C 2} H 5) C 4 H 9 ] _4, Si ( OC ₆ H ₅ ) ₄ ; HSi (OC ₂ H) contained in the formula RSi (OR ¹ ) ₃ ,
_{HSi (OC 4 H 9) 3} , HSi (O 6 CH 13) 3, HSi (OC 6 H 5) 3, CH 3 Si (OCH 3) 3, CH 3 Si (OC
_{2 H 5) 3, CH 3} Si (OC 4 H 9) 3, C 2 H 5 Si (OC 2 H 5) 3, C 4 H 9 Si (OC 2 H 5) 3, C 6 H 5 Si (OC ₂ H ₅ ) ₃ , C ₂ H ₅ Si (OC ₆ H ₅ ) ₃ ; included in formula R ₂ Si (OR ¹ ) ₂ (CH ₃ ) _{2
Si (OCH 3) 2, (} CH 3) 2 Si (OC 2 H 5) 2, (CH 3) 2 Si (OC 3 H 7) 2, (C 2 H 5) 2 Si (OC 2 H 5) 2 , (C ₆ H ₅ ) ₂ Si (OC ₂ H ₅ ) ₂ ; (CH ₃ ) ₃ S contained in the formula R ₃ SiOR ¹
iOCH ₃ , (CH ₃ ) ₃ SiOC ₂ H ₅ , (CH ₃ ) ₃ SiOC ₄ H ₉ , (CH ₃ ) ₃ S
iOC ₆ H ₅ , (C ₂ H ₅ ) SiOC ₂ H ₅ , (C ₆ H ₅ ) ₃ SiOC ₂ H ₅ ; C (OR ¹ )
₄ contained in C (OCH ₃ ) ₄ , C (OC ₂ H ₅ ) ₄ , C (OC ₄ H ₉ ) ₄ , C (OC ₆ H ₁₃ ) ₄ , C (OC ₈ H ₁₇ ) ₄ , C (OC ₆ H ₅ ) ₄ ; HC (OCH ₃ ) ₃ , HC (OC ₂ H ₅ ) ₃ , HC (OC ₃ H ₇ ) ₃ , HC (OC ₄ H ₉ ) ₃ , HC contained in RC (OR ¹ ) _{3 (OC 6 H 13) 3,} HC (O 3 CH 17) 3, HC (OC 6 H 5) 3, CH 3 C (OCH 3) 3, CH 3 C (OC 2 H 5) 3, C 2 H 5 C (OC ₂ H ₅ ) ₃ ;
CH ₃ CH (OCH ₃ ) ₂ , CH ₃ CH (OC ₂ H ₅ ) ₂ , CH ₂ (OCH ₃ ) ₂ , CH ₂ (OC ₂ H ₅ ) ₂ , included in the formula R ₂ C (OR ¹ ) _{2 C 6 H 5 CH (OC 2} H 5) 2 and the like.

(D) Halogen-Containing Alcohol The halogen-containing alcohol used in the present invention is any one or two or more hydrogen atoms other than hydroxyl group in a mono- or polyhydric alcohol having one or two or more hydroxyl groups in one molecule. Means a compound in which is substituted with a halogen atom. Examples of the halogen atom include chlorine, bromine, iodine and fluorine atoms, and chlorine atom is preferable.

Examples of these compounds include 2-chloroethanol, 1
-Chloro-2-propanol, 3-chloro-1-propanol, 1-chloro-2-methyl-2-propanol,
4-chloro-1-butanol, 5-chloro-1-pentanol, 6-chloro-1-hexanol, 3-chloro-
1,2-propanediol, 2-chlorocyclohexanol, 4-chlorobenzhydrol, (m, o, p) -chlorobenzyl alcohol, 4-chlorocatechol, 4-chloro- (m, o) -cresol, 6 -Chloro- (m, o) -cresol, 4-chloro-3,5-dimethylphenol, chlorohydroquinone, 2-benzyl-4-chlorophenol, 4-chloro-1-naphthol, (m, o, p)- Chlorphenol, p-chloro-α-methylbenzyl alcohol, 2-chloro-4-phenylphenol, 6-chlorothymol, 4-chlororesorcinol, 2-bromoethanol, 3-bromo-1-propanol, 1-bromo- 2-
Propanol, 1-bromo-2-butanol, 2-bromo-p-cresol, 1-bromo-2-naphthol, 6
-Brom-2-naphthol, (m, o, p) -bromophenol, 4-bromoresorcin, (m, o, p) -fluorophenol, p-iodophenol: 2,2-dichloroethanol, 2, 3-dichloro-1-propanol, 1,3-dichloro-2-propanol, 3-chloro-1- (α-chloromethyl) -1-propanol, 2,3-dibromo-1-propanol, 1,3-dibromo- 2-propanol, 2,4-dibromophenol, 2,4-dibromo-1-naphthol: 2,
2,2-Trichloroethanol, 1,1,1-Trichloro-2-
Propanol-β, β, β-β-trichloro-tert-butanol, 2,3,4-trichlorophenol, 2,4,5-trichlorophenol, 2,4,6-trichlorophenol, 2,4,6-
Tribromophenol, 2,3,5-tribromo-2-hydroxytoluene, 2,3,5-tribromo-4-hydroxytoluene, 2,2,2-trifluoroethanol, α, α,
α-trifluoro-m-cresol, 2,4,6-triiodophenol: 2,3,4,6-tetrachlorophenol, tetrachlorohydroquinone, tetrachlorobisphenol A, tetrabromobisphenol A, 2,2 Examples include 3,3,3-tetrafluoro-1-propanol, 2,3,5,6-tetrafluorophenol, tetrafluororesorcin, and the like.

(E) Electron-donating compound As the electron-donating compound, carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, carboxylic acid halides, alcohols, ethers, ketones, amines,
Examples thereof include amides, nitriles, aldehydes, alcoholates, phosphorus, arsenic and antimony compounds bonded to an organic group through carbon or oxygen, phosphoamides, thioethers, thioesters, carbonic acid esters and the like. Of these, carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, carboxylic acid halides, alcohols and ethers are preferably used.

Specific examples of the carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, pivalic acid, acrylic acid, methacrylic acid, crotonic acid and other aliphatic monocarboxylic acids, malonic acid, succinic acid. , Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, sebacic acid, maleic acid and fumaric acid, aliphatic oxycarboxylic acids such as tartaric acid,
Cyclohexamonocarboxylic acid, cyclohexene monocarboxylic acid, cis-1,2-cyclohexanedicarboxylic acid, alicyclic carboxylic acid such as cis-4-methylcyclohexene-1,2-dicarboxylic acid, benzoic acid, toluic acid, anisic acid , P-tertiary butyl benzoic acid, naphthoic acid, aromatic monocarboxylic acids such as cinnamic acid, phthalic acid, isophthalic acid,
Examples thereof include aromatic polycarboxylic acids such as terephthalic acid, naphthalic acid, trimellitic acid, hemimellitic acid, trimesic acid, pyromellitic acid, and mellitic acid.

As the carboxylic acid anhydride, acid anhydrides of the above carboxylic acids can be used.

As the carboxylic acid ester, mono- or polyvalent esters of the above carboxylic acids can be used, and specific examples thereof include butyl formate, ethyl acetate, butyl acetate, isobutyl isobutyl, propyl pivalate, pivalate isobutyl, and acrylic. Ethyl acid, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, diethyl malonate, diisobutyl malonate, diethyl succinate, dibutyl succinate, diisobutyl succinate, diethyl glutarate, dibutyl glutarate, diisobutyl glutarate,
Diisobutyl adipate, dibutyl sebacate, diisobutyl sebacate, diethyl maleate, dibutyl maleate, diisobutyl maleate, monomethyl fumarate, diethyl fumarate, diisobutyl fumarate, diethyl tartrate, dibutyl tartrate, diisobutyl tartrate, ethyl cyclohexanecarboxylate, Methyl benzoate, ethyl benzoate, methyl p-toluate, ethyl p-tertiary butyl benzoate, ethyl p-anisate, ethyl α-naphthoate, isobutyl α-naphthoate, ethyl cinnamate, monomethyl phthalate. , Monobutyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, dioctyl phthalate, di2-ethylhexyl phthalate, diallyl phthalate, diphenyl phthalate, diethyl isophthalate, isophthalic acid Examples thereof include diisobutyl, diethyl terephthalate, dibutyl terephthalate, diethyl naphthalate, dibutyl naphthalate, triethyl trimellitate, tributyl trimellitate, tetramethyl pyromellitic acid, tetraethyl pyromellitic acid, tetrabutyl pyromellitic acid and the like.

As the carboxylic acid halide, acid halides of the above carboxylic acids can be used, and specific examples thereof include acetic acid chloride, acetic acid bromide, acetic acid iodide, propionic acid chloride, butyric acid chloride, butyric acid bromide, butyric acid iodide, pivalin. Acid chloride, pivalic acid bromide, acrylic acid chloride, acrylic acid bromide, acrylic acid iodide, methacrylic acid chloride,
Methacrylic acid bromide, methacrylic acid iodide, crotonic acid chloride, malonic acid chloride, malonic acid bromide, succinic acid chloride, succinic acid bromide, glutaric acid chloride, glutaric acid bromide, adipic acid chloride,
Adipic acid bromide, sebacic acid chloride, sebacic acid bromide, maleic acid chloride, maleic acid bromide,
Fumaric acid chloride, fumaric acid bromide, tartaric acid chloride, tartaric acid bromide, cyclohexanecarboxylic acid chloride, cyclohexanecarboxylic acid bromide, 1-cyclohexenecarboxylic acid chloride, cis-4-methylcyclohexenecarboxylic acid chloride, cycl-4-methylcyclohexenecarboxylic acid bromide , Benzoyl chloride, benzoyl bromide, p-toluic acid chloride, p-toluic acid bromide, p-anisic acid chloride, p-anisic acid bromide,
α-naphthoic acid chloride, cinnamic acid chloride, cinnamic acid bromide, phthalic acid dichloride, phthalic acid dibromide,
Examples include isophthalic acid dichloride, isophthalic acid dibromide, terephthalic acid dichloride, and naphthalic acid dichloride. Also, adipic acid monomethyl chloride, maleic acid monoethyl chloride, maleic acid monomethyl chloride,
Monoalkyl halides of dicarboxylic acids, such as butyl chloride phthalate, may also be used.

Alcohols are represented by the general formula ROH. In the formula, R is alkyl having 1 to 12 carbons, alkenyl, cycloalkyl, aryl or aralkyl. Specific examples thereof include methanol, ethanol, propanol, isopropanol, butanol isobutanol, pentanol, hexanol, octanol, 2-ethylhexanol, cyclohexanol, bezyl alcohol, allyl alcohol, phenol, cresol, xylenol,
Examples include ethylphenol, isopropylphenol, p-tert-butylphenol and n-octylphenol. Ethers are represented by the general formula ROR '. In the formula, R and R ′ are alkyl having 1 to 12 carbons, alkenyl, cycloalkyl, aryl and aralkyl,
R and R'may be the same or different and may form a ring. Specific examples thereof include diethyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diisoamyl ether, di-2-ethylhexyl ether, diallyl ether, ethyl allyl ether, butyl allyl ether, diphenyl ether, anisole, ethyl phenyl ether. , Tetrahydrofuran and the like. Also, any of the above halogen containing alcohols may be used.

Method for Preparing Catalyst Component The method for preparing the catalyst component used in the present invention is a solid obtained by contacting a metal oxide (component A), an organic Mg (component B) and a hydrocarbyloxy group-containing compound (component C), It comprises contacting with a halogen-containing alcohol (component D), and further contacting with an electron-donating compound (component E) and titanium tetrachloride (component F).

Contact of A component, B component and C component The contact method of A component, B component and C component is (1)
Method of contacting A component and B component and then C component, (2) Method of contacting A component and C component and then B component, (3) Contacting B component and C component After
Method of contacting component A, (4) component A, component B and C
A method of contacting the components at the same time can be mentioned.

The above contact is performed by a method of mixing and stirring in the presence or absence of an inert medium, a method of mechanically co-grinding, or the like. As the inert medium, hydrocarbons such as pentane, hexane, heptane, octane, decane, cyclohexane, benzene, toluene, xylene, 1,2-dichloroethane, 1,2-dichloropropane, carbon tetrachloride, butyl chloride, chloride Halogenated hydrocarbons such as isoamyl, bromobenzene and chlorotoluene can be used.

The contact of A component, B component and C component is usually from -20 ° C to +15
It is carried out at 0 ° C for 0.1 to 100 hours. When the contact is accompanied by heat generation, it is possible to adopt a method in which the respective components are gradually mixed at a low temperature first, and the temperature is raised when the mixing of all the amounts is completed, and the contact is continued. In addition, each contact substance may be washed with the above-mentioned inert medium between each contact, but particularly in the case of the method (1) and the method (2), after the first contact of the two components, Better results can be obtained by contacting the third component without washing.
desirable. The contact ratio of the A component, the B component and the C component is B / A = 0.01 to 10, C / A = 0.01 to 10 and C / B = 0.1 to 10 in molar ratio.
Is.

The solid product obtained by contacting the components A, B and C (hereinafter referred to as the reaction product I) is subjected to the next contact, but if necessary, washed appropriately before the contact. It may be washed with an agent such as the inert medium described above.

Contact between the reaction product I and the component D The contact between the reaction product I and the component D is performed by a method of mixing and stirring in the presence or absence of an inert medium, a method of mechanically co-grinding, etc., but an inert medium is preferable. It is a method of mixing and stirring in the presence of. Examples of the inert medium include the same as those used when the above-mentioned A component, B component and C component are contacted.

The reaction products I and D are usually contacted at -20 ° C to + 150 ° C.
For 0.1 to 100 hours. If the contact involves heat,
It is also possible to employ a method in which the two are gradually contacted at a low temperature first, the temperature is raised when the mixing of all the amounts is completed, and the contact is continued. The component D is used in a molar ratio of 0.1 to 20 mol, preferably 0.5 to 10 mol, relative to the component B in the reaction product I.

The solid product (hereinafter referred to as the reaction product II) obtained by contacting the reaction product I with the component D is subjected to the next contact, but if necessary, prior to the contact, it is suitable. It may be washed with a suitable cleaning agent such as the above-mentioned inert medium.

Contact with E component and F component When the reaction product II is contacted with the electron-donating compound (E component) and titanium tetrachloride (F component), (1) the reaction product II is treated with E
Method of contacting with component F and then with component F, (2)
A method in which the reaction product II is brought into contact with the F component and then brought into contact with the E component, and (3) a method in which the E component and the F component are simultaneously used and brought into contact with the reaction product II can be adopted.

Each of the above-mentioned contact is achieved by a method of mechanically co-milling, a method of mixing and stirring, or the like in the presence or absence of an inert medium. Among these, a method of mixing and stirring in the presence or absence of an inert medium is particularly desirable. As the inert medium, the above compounds can be used.

When the reaction product II is contacted with the E component and the F component by mechanical co-grinding, it is usually at 0 to 200 ° C. for 0.1 to 100 hours,
When mixing and stirring, it is usually carried out at 0 to 200 ° C. for 0.5 to 20 hours. The amount of component E used is 0.005 to 10 gram moles, preferably 0.01 to 1 gram moles per gram atom of magnesium in reaction product II. The amount of the F component used is 1 gram atom of magnesium in the reaction product II,
The amount is 0.1 gram mole or more, preferably 1 to 50 gram mole.

The contact between the reaction product II and the F component can be carried out twice or more. The contact method may be the same as above. If necessary, the previous contact product may be washed with an inert medium, and the F component (and the medium) may be newly added to bring it into contact.

Further, when the contact with the F component is performed twice or more, it is possible to contact with each other by an inert hydrocarbon, a halogenated hydrocarbon or a metal halide compound during each contact.

Inert hydrocarbons that can be used are aliphatic, cycloaliphatic and aromatic hydrocarbons. Examples thereof are n-hexane, methylhexane, dimethylhexane, ethylhexane, ethylmethylpentane, n-heptane, methylheptane, trimethylpentanedimethylheptane, ethylheptane, trimethylhexane, trimethylheptane, n-octane, methyloctane, Dimethyl octane, n-undecane, n-dodecane, n-tridecane,
n-tetradecane, n-pentadecane, n-hexadecane, n-octadecane, n-nonadecane, n-eicosane, cyclopentane, cyclohexane, methylcyclopentane, cycloheptane, dimethylcyclopentane, methylcyclohexane, ethylcyclopentane, dimethylcyclohexane, Ethylcyclohexane, cyclooctane, indane, n-butylcyclohexane, isobutylcyclohexane, adamantane, benzene, toluene,
Xylene, ethylbenzene, tetramethylbenzene, n
-Butylbenzene, isobutylbenzene, propyltoluene, decalin, tetralin and the like.

The halogenated hydrocarbons used are mono- and polyhalogenated substitutes of saturated or unsaturated, aliphatic, cycloaliphatic and aromatic hydrocarbons having 1 to 12 carbon atoms. Specific examples of those compounds include aliphatic compounds such as methyl chloride, methyl bromide, methyl iodide, methylene chloride, methylene bromide, methylene iodide, chloroform, bromoform, iodoform, carbon tetrachloride and carbon tetrabromide. Carbon tetraiodide, ethyl chloride, ethyl bromide, ethyl iodide, 1,2-dichloroethane, 1,2-dibromoethane, 1,2-diiodoethane, methyl chloroform, methyl bromoform, methyl iodoform, 1,1,2-trichloroethylene 1,1,2-tribromoethylene, 1,1,2,2-tetrachloroethylene, pentachloroethane, hexachloroethane, hexabromoethane, n-propyl chloride, 1,2-dichloropropane, hexachloropropylene , Octachloropropane,
Decabromobutane, chlorinated paraffin, chlorocyclopropane, tetrachlorocyclopentane, hexachlorocyclopentanediene, hexachlorocyclohexane for alicyclic compounds, chlorobenzene for aromatic compounds,
Examples thereof include bromobenzene, o-dichlorobenzene, p-dichlorobenzene, hexachlorobenzene, hexabromobenzene, benzotrichloride, p-chlorobenzotrichloride and the like. These compounds may be used alone or in combination of two or more.

Metal halide compounds are listed in the periodic table of elements IIIa, IVa
And halides of elements selected from the group of elements of the V a group (hereinafter referred to as metal halides) are B, Al, Ga, In,
Examples include Tl, Si, Ge, Sn, Pb, As, Sb, Bi chlorides, fluorides, bromides, and iodides, particularly BCl ₃ , BBr ₃ , BI ₃ , and AlC.
l ₃ , AlBr ₃ , AlI ₃ , GaCl ₃ , GaBr ₃ , InCl ₃ , TlCl ₃ , SiC
l, SnCl ₄ , SbCl ₅ , SbF _{5 and the} like are preferable.

An inert hydrocarbon, a halogenated hydrocarbon or a metal halide (hereinafter referred to as a G component), which is carried out as required during each contact with the F component performed twice or more.
The contact is conducted at 0 to 200 ° C for 5 minutes to 20 hours, preferably at 20 to 150 ° C for 10 minutes to 5 hours. When the G component is a liquid substance, the reaction product II is 1 to 1 per G component.
It is desirable to use 1,000 g, and when the G component is a solid substance, it is desirable to use it by dissolving the solid G component in a soluble G component. It is desirable to use II in an amount of 0.01 to 100 g per 1 g of G component.

Furthermore, the contact product of the reaction product II and the F component may contact the G component. The contacting method may be the same as the contacting using the G component, which is performed as necessary.

The catalyst component used in the present invention can be produced as described above, and the catalyst component may be hexane, heptane, octane, cyclohexane, benzene, if necessary.
It can be washed with a hydrocarbon such as toluene or xylene, and can be dried if necessary.

Polymerization Catalyst The polymerization catalyst used in the present invention comprises a combination of the catalyst component obtained as described above and an organoaluminum compound.

The organoaluminum compound that can be used is represented by the general formula RnAl
X _3-n (wherein R is an alkyl group or an aryl group, X is a halogen atom, an alkoxy group or a hydrogen atom, and n is 1
It is an arbitrary number in the range of n3. ), For example, a trialkylaluminum, a dialkylaluminum monohalide, a monoalkylaluminum dihalide, an alkylaluminum sesquihalide, a dialkylaluminum monoalkoxide and a dialkylaluminum monohydride, etc., having 1 to 18 carbon atoms,
Particularly preferred is an alkylaluminum compound having 2 to 6 carbon atoms, or a mixture or complex compound thereof. Specifically, such as trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, trialkyl aluminum such as trihexyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum iodide, diisobutyl aluminum chloride, etc. Alkyl aluminum sesquihalides such as dialkyl aluminum monohalide, methyl aluminum dichloride, ethyl aluminum dichloride, methyl aluminum dibromide, ethyl aluminum dibromide, ethyl aluminum diiodide, isobutyl aluminum dichloride, etc., and alkyl aluminum sesquichloride. Dialkyl aluminum monoalkoxides such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, diethyl aluminum phenoxide, dipropyl aluminum ethoxide, diisobutyl aluminum ethoxide, diisobutyl aluminum phenoxide, dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl Examples thereof include dialkyl aluminum hydrides such as aluminum hydride and diisobutyl aluminum hydride. Among these, tolylalkylaluminum is preferable, and triethylaluminum and triisobutylaluminum are particularly preferable. Further, these trialkylaluminums are other organic aluminum compounds, for example, industrially difficult to obtain diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum ethoxide, diethylaluminum hydride or a mixture or complex compound thereof. Etc. can be used together.

Further, an organoaluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom can also be used. Examples of such compounds include (C ₂ H ₅ ) ₂ AlOAl
_{(C 2 H 5) 2,} (C 4 H 9) 2 AlOAl (C 4 H 9) 2, Can be illustrated.

Further, the organoaluminum compound may be used alone or in combination with an electron donating compound. As the electron-donating compound, any compound may be used as long as it is a compound used as the E component at the time of preparing the catalyst component, and other electron-donating compounds such as organosilicon compounds and heteroatoms such as nitrogen, sulfur, oxygen and phosphorus can be used. An electron donating compound containing can also be used.

Specific examples of the organic silicon compound include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, tetraphenoxysilane, tetra (p-methylphenoxy) silane, tetrabenzyloxysilane, methyltrimethoxylane, Methyltriethoxysilane, methyltributoxysilane, methyltriphenoxysilane, ethyltriethoxysilane, ethyltriisobutoxysilane, ethyltriphenoxysilane,
Butyltrimethoxysilane, butyltriethoxysilane, butyltributoxysilane, butyltriphenoxysilane, isobutyltriisobutoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane,
Benzyltriphenoxysilane, methyltriallyloxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, dimethyldihexyloxysilane, dimethyldiphenoxysilane, diethyldiethoxysilane, diethyldiisobu Toxysilane, diethyldiphenoxysilane, dibutyldiisopropoxysilane, dibutyldibutoxysilane, dibutyldiphenoxysilane, diisobutyldiethoxysilane, diisobutyldiisobutoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldisilane Butoxysilane, dibenzyldiethoxysilane, divinyldiphenoxysilane, diallyldipropoxysilane, diphenyldiallyloxysilane, Ruch enyl dimethoxysilane, chloro phenylalanine diethoxy silane and the like.

Specific examples of the atom-donating compound containing a hetero atom include:
As the compound containing a nitrogen atom, 2,2,6,6-tetramethylpiperidine, 2,6-dimethylpiperidine, 2,6-diethylpiperidine, 2,6-diisopropylpiperidine, 2,2,5,5
-Tetramethylpyrrolidine, 2,5-dimethylpyrrolidine, 2,5-diethylpyrrolidine, 2,5-diisopropylpyrrolidine, 2-methylpyridine, 3-methylpyridine,
4-methylpyridine, 1,2,4-trimethylpiperidine,
2,5-dimethylpiperidine, methyl nicotinate, ethyl nicotinate, nicotinic acid amide, benzoic acid amide, 2-
Methylpyrrole, 2,5-dimethylpyrrole, imidazole, toluic acid amide, benzonitrile, acetonitrile, aniline, paratoluidine, altotoluidine, metatoluidine, triethylamine, diethylamine, dibutylamine, tetramethylenediamine, tributylamine, etc. are sulfur atoms. As the compound containing, thiophenol, thiophene, ethyl 2-thiophenecarboxylate,
Ethyl 2-thiophenecarboxylate, 2-methylthiophene, methyl mercaptan, ethyl mercaptan, isopropyl mercaptan, butyl mercaptan, diethyl thioether, diphenyl thioether, methyl benzene sulphonate, methyl sulphate, ethyl sulphate, etc. are oxygen atoms. As a compound containing, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 2-ethyltetrahydrofuran, dioxane, dimethyl ether, diethyl ether, dibutyl ether, diisoaluminum ether, diphenyl ether, anisole, acetophenone, acetone, methyl ethyl ketone, acetylacetone. , 2-ethyl furarate,
2-Furoyl isoamyl, 2-methyl furarate, 2-propyl phthalate, etc. are compounds containing a phosphorus atom, such as triphenyl phosphine, tributyl phosphine, triphenyl phosphite, tribenzyl phosphite, diethyl phosphite, Examples thereof include diphenyl phosphate.

Two or more kinds of these electron donating compounds may be used.
Further, these electron donating compounds may be used when an organoaluminum compound is used in combination with a catalyst component, or may be used after being contacted with the organoaluminum compound in advance.

The amount of the organoaluminum compound used with respect to the catalyst component is
Usually 1 to 2000 per 1 gram atom of titanium in the catalyst component.
Gram moles, especially 20 to 500 grams moles are desirable.

The ratio of the organoaluminum compound to the electron-donating compound is 0.1 to 40, preferably 1 to 2 of the organoaluminum compound as aluminum per mol of the electron-donating compound.
Selected in the range of 5 gram atoms.

The catalyst component used in the present invention is an organoaluminum compound, and optionally in the presence of an electron donating compound,
Prepolymerize ethylene and / or propylene to give a polymer of ethylene and / or propylene of 0 g per 1 g of the catalyst component.
It is possible to use 1 to 100 g, preferably 1 to 50 g of the catalyst component. As the prepolymerization method, an ordinary olefin polymerization method using a Ziegler-Natsuta type catalyst can be adopted.

Copolymerization of ethylene and propylene As for the copolymerization of ethylene and propylene, the copolymerization method of ethylene and propylene according to the olefin copolymerization method using a typical Ziegler-Natsuta type catalyst can be adopted, but propylene is used as a bulk medium. Polymerization methods and gas phase polymerization methods are particularly desirable.

The copolymerization temperature is usually −80 ° C. to + 150 ° C., preferably 0 to 8
It is in the range of 0 ° C. The copolymerization may be carried out under pressure up to 60 atm. The ethylene / propylene copolymer rubber obtained by the method of the present invention has an ethylene content of 15 to 90 mol%, but in order to obtain such a range, the use ratio of ethylene and propylene during copolymerization is In the case of bulk polymerization with ethylene / propylene (molar ratio) and propylene as a medium,
0.01 to 1.0 in the liquid phase, 0.03 to 3.0 in the case of gas phase polymerization
It is achieved by adjusting to.

The copolymerization reaction can be carried out in a continuous system or a batch system,
It may be performed in one step, or may be performed in two or more steps.

Effect of the Invention By the method of the present invention, an ethylene / propylene copolymer rubber having good particle properties can be produced in a high yield. Therefore, the decatalysis step can be omitted.

EXAMPLES Next, the present invention will be specifically described with reference to Examples. However,
The invention is not limited to the examples. The percentages (%) shown in the examples are by weight unless otherwise specified.

The ethylene content in the polymer was measured by infrared spectrum analysis. Melt Index (MI) is ASTM D 1238
The bulk density was measured according to ASTM D 1895-69 Method A, respectively. Heat of fusion manufactured by Perkin Elmer
It was measured using DSC II c. The true density is ASTM D 15
Measured according to 05.

Example 1 Preparation of catalyst component Contact between silicon oxide and n-butylethylmagnesium A 200 ml flask equipped with a dropping funnel and a stirrer was replaced with nitrogen gas. In this flask, add silicon oxide (DAVI
SON, trade name G-952, specific surface area 302 m ² / g, pore volume
1.54 cm ³ / g, average pore radius 204Å) (hereinafter referred to as SiO ₂ ) in a nitrogen stream at 200 ° C for 2 hours, then 700 ° C
5 g of the product baked for 5 hours and 40 ml of n-heptane were added. Furthermore, n-butylethylmagnesium (hereinafter, BEM
Say. 20% n-heptane solution (trade name: MAGALA BEM, manufactured by Texas Alkyls) (26.8 mmol as BEM) was added, and the mixture was stirred at 90 ° C. for 1 hour.

Contact with tetraethoxysilane After cooling the above suspension to 0 ° C., a solution of 11.2 g (53.6 mmol) of tetraethoxysilane dissolved in 20 ml of n-heptane was added dropwise from the dropping funnel over 30 minutes. After the dropping was completed, the temperature was raised to 50 ° C. over 2 hours, and stirring was continued at 50 ° C. for 1 hour. After completion of the reaction, the supernatant was removed by decantation, the produced solid was washed with 60 ml of n-heptane at room temperature, and the supernatant was removed by decantation. This washing treatment with n-heptane was further performed 4 times.

Contact with 2,2,2-trichloroethanol To the above solid, 50 ml of n-heptane was added to make a suspension, and 8.0 g (53.6 mmol) of 2,2,2-trichloroethanol was added to 10 ml of n-heptane. The solution dissolved in heptane was added dropwise from the dropping funnel over 30 minutes at 0 ° C. After completion of the dropping, the temperature was raised to 60 ° C. over 1 hour, and stirring was continued at 60 ° C. for 1 hour. After completion of the reaction, the mixture was washed twice with 60 ml of n-heptane and three times with 60 ml of toluene at room temperature. When the obtained solid (solid component I) was analyzed, Si
It contained O ₂ 36.6%, magnesium 5.1% and chlorine 38.5%. The specific surface area of this solid is 257 m ² / g, and the pore solution is 0.7
It was 6 cm ³ / g.

Contact with di-n-butyl phthalate and titanium tetrachloride To the solid component I obtained above, 15 ml of toluene and 0.6 g of di-n-butyl phthalate were added and reacted at 50 ° C for 2 hours. Next, after adding 40 ml of titanium tetrachloride and reacting at 120 ° C. for 2 hours, the supernatant was removed by decantation, 60 ml of toluene was added, and the mixture was washed at 120 ° C. for 15 minutes. After washing again with this toluene, 15 ml of toluene and 40 ml of titanium tetrachloride were added, and the reaction was carried out at 120 ° C. for 2 hours.

The solid material obtained was treated with 60 ml of n-hexane at room temperature for 8 hours.
Washed twice. Dry for 1 hour at room temperature under reduced pressure
8.3 g of catalyst component (a) was obtained. This catalyst component contains SiO ₂
53.5%, magnesium 7.4%, chlorine 24.6%, titanium 2.7%
Was included.

Copolymerization of ethylene and propylene A glass ampoule and triethylaluminum (TEAL) containing 800 ml of liquid propylene and 10 mg of catalyst component (a) in an autoclave of 1.5 with nitrogen replacement, equipped with a stirrer.
10 mmol was added. The contents are then heated to 40 ° C. and hydrogen 2 and ethylene / propylene in the liquid phase = 0.
25.4kg / cm ² by adding ethylene so that it becomes 14 (molar ratio)
Pressurized to. The stirrer was rotated to divide the glass ampoule to start the copolymerization. The ethylene / propylene ratio in the liquid phase during the polymerization was maintained at 0.14 by feeding ethylene. One hour later,
The polymer obtained by depressurizing was taken out and dried. The polymerization activity was 14.3 kg / g-catalyst component (a) -hour. The obtained polymer was spherical and had a bulk density of 0.36 g / cm ³ , MI
It had a 0.26 g / 10 min and a true density of 0.878 g / cm ³ . The ethylene content was 69 mol% and the heat of fusion was 3.6 cal / g.

Examples 2 to 6 Copolymerization of ethylene and propylene was carried out in the same manner as in Example 1 except that the ethylene / propylene ratio, the polymerization temperature and the like were changed as shown in Table 1. The results are shown in Table 1.

Example 7 Instead of TEAL, triisobutylaluminum (TIBA
Copolymerization of ethylene and propylene was carried out in the same manner as in Example 1 except that L) was used. The results are shown in Table 1.

Examples 8 to 11 Instead of TEAL alone, a mixture of TEAL and phenyltriethoxysilane (PES) was used as shown in Table 1 and the copolymerization conditions were as shown in Table 1 Copolymerization of ethylene and propylene was carried out in the same manner as in 1. The results are shown in Table 1.

Examples 12 to 15 Preparation of catalyst component Di-n-phthalate used in the preparation of the catalyst component of Example 1
Catalyst components (b) to (e) having a titanium content shown below were prepared in the same manner as in Example 1 except that the electron donating compound shown below was used instead of butyl.

Copolymerization of Ethylene and Propylene Copolymerization of ethylene and propylene was carried out in the same manner as in Example 1 except that the catalyst component obtained above was used, and the results are shown in Table 1.

Example 16 Preparation of catalyst component A titanium content of 3.3 was obtained in the same manner as in Example 1 except that Al ₂ O ₃ calcined in a nitrogen stream at 200 ° C. for 2 hours and 700 ° C. for 5 hours was used instead of SiO _2. % Catalyst component (f) was prepared.

Copolymerization of ethylene and propylene Except that ethylene / propylene = 0.18 (molar ratio),
Copolymerization of ethylene and propylene was carried out in the same manner as in Example 1, and the results are shown in Table 1.

Examples 17 and 18 Preparation of catalyst component A catalyst component (g) and a catalyst component (h) were prepared in the same manner as in Example 1 except that the organic Mg shown below was used instead of BEM.

Copolymerization of ethylene and propylene Using the catalyst component obtained above, the copolymerization conditions are as follows:
Copolymerization of ethylene and propylene was carried out in the same manner as in Example 1 except that the results were shown in the table, and the results are shown in Table 1.

Examples 19 and 20 Preparation of catalyst component A catalyst component (i) and a catalyst component (j) were prepared in the same manner as in Example 1 except that the hydrocarbyloxy group-containing compound shown below was used instead of tetraethoxysilane. .

Copolymerization of ethylene and propylene Using the catalyst component obtained above, the copolymerization conditions are as follows:
Copolymerization of ethylene and propylene was carried out in the same manner as in Example 1 except that the results were shown in the table, and the results are shown in Table 1.

Examples 21, 22 Preparation of catalyst component Catalyst component (k) and catalyst component (l) were prepared in the same manner as in Example 1 except that the halogen-containing alcohol shown below was used instead of 2,2,2-trichloroethanol. ) Was prepared.

Copolymerization of ethylene and propylene Using the catalyst component obtained above, the copolymerization conditions are as follows:
Copolymerization of ethylene and propylene was carried out in the same manner as in Example 1 except that the results were shown in the table, and the results are shown in Table 1.

Example 23 Prepolymerization of Propylene 100 ml of n-heptane was placed in a 200 ml flask equipped with a stirrer and sufficiently replaced with nitrogen, and then catalyst component (a) 1
g, TEAL 0.1 mmol and PES 0.01 mmol were added. While stirring the system, propylene was introduced and prepolymerization was carried out at room temperature. The solid phase portion was washed 5 times with 50 ml of n-hexane and then dried at room temperature. 25 g of propylene was polymerized and incorporated per 1 g of the catalyst component (a).

Copolymerization of Ethylene and Propylene Copolymerization of ethylene and propylene was carried out in the same manner as in Example 1 except that the above-mentioned prepolymerized catalyst component was used and the copolymerization conditions were as shown in Table 1. First
Shown in the table.

Example 24 Prepolymerization of Propylene Prepolymerization of propylene was carried out in the same manner as in Example 23.
The amount of preliminary polymerization per 1 g of the catalyst component (a) was 10.2 g.

Vapor phase polymerization of ethylene and propylene 200g of the prepolymerized catalyst component obtained above and TEA were placed in an autoclave 5 equipped with a stirrer and sufficiently replaced with nitrogen.
L. 0.17 mmol and PES 0.05 mmol were added. Next, the molar ratio of ethylene / propylene / hydrogen in the system is always 3/6/1
Each gas is supplied at 60 ℃, total pressure 20kg / c
Copolymerization of ethylene and propylene was carried out at m ² . After 1 hour, the pressure was lowered and the polymer was taken out.

The polymerization activity was 5.0 kg / g-catalyst component (a) -hour.
The polymer obtained is spherical and has a bulk density of 0.40 g / c.
m ³ , MI 0.82 g / 10 minutes, ethylene content 72 mol%, heat of fusion 5.
It was 8 cal / g.

Comparative Example Preparation of Catalyst Components A 200 ml flask equipped with a dropping funnel and a stirrer was replaced with nitrogen gas. Anhydrous magnesium chloride in this flask
After adding 0.7 g and 40 ml of tetrahydrofuran, 0.46 g of titanium tetrachloride was added dropwise at room temperature over 30 minutes. Then 60 ℃
And heated for 30 minutes to form a uniform solution.

TEAL was added to a slurry obtained by mixing 8 g of SiO ₂ (calcined at 600 ° C. under a nitrogen atmosphere for 5 hours) and 50 ml of n-hexane used in Example 1.
3.1 ml of a 20% n-hexane solution of was added dropwise over 15 minutes. The resulting mixture was blown with nitrogen gas at 60 ° C. for 4 hours,
A free flowing powder was obtained.

Next, this treated SiO ₂ powder was added to the solution obtained above, dried for 15 minutes, and then blown with nitrogen gas at 60 ° C. for 4 hours to obtain a dry powdery catalyst component (m) having a titanium content of 4.1%. ) Was prepared.

Copolymerization of ethylene and propylene Using the catalyst component (m) obtained above, ethylene /
Copolymerization of ethylene and propylene was carried out in the same manner as in Example 1 except that propylene = 0.11 (molar ratio), and the results are shown in Table 1.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart showing the method of the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Koji Maruyama 2-13-8, Chuo, Kamifukuoka City, Saitama Prefecture (72) Inventor Haruo Mizukami 71 Higashifukai, Nagareyama City, Chiba Prefecture

Claims (1)

[Claims] 1. An oxide of a metal element selected from the group of metal elements of groups II to IV of the periodic table of the element (A), (B) dihydrocarbyl magnesium and (C) the formula R _n M (OR ¹ ) _4-n
(R is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, M is a silicon or carbon atom, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms,
0 ≦ n <4. ) Is obtained by contacting the solid obtained by contacting the hydrocarbyloxy group-containing compound represented by the formula (D) with a halogen-containing alcohol (D), and further by contacting (E) an electron-donating compound and (F) titanium tetrachloride. A method for producing an ethylene / propylene copolymer rubber having an ethylene content of 15 to 90 mol%, which comprises copolymerizing ethylene and propylene in the presence of a polymerization catalyst containing the catalyst component and an organoaluminum compound.