CA1248511A - Catalyst component for polymerization of olefins - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

A catalyst component for the polymerization of olefins which is prepared by contacting (1) a contact reaction product of (a) a metal oxide, (b) a dihydrocarbyl magnesium, and (c) a halogen-containing alcohol held with (d) an electron-donating compound, and (e) a titanium compound.

Description

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1 FIELD OF_THE INVENTION

2 This invention relates to a catalyst component for the

3 polymerization of olefins and, to the catalyst system comprising the

4 catalyst component, and to the process of polymerizing olefins, especially olefins having 3 or more carbon atoms, in the presence of 6 the catalyst system.
7 BACKGROUND OF THE INVENTION:
8 Concerning Ziegler-Natta type catalysts which are effective 9 in polymerizing olefins, catalyst components having transition metals deposited on a variety of carriers have been developed for the purpose 11 of improving catalyst activity per unit amount of catalyst or decreas-12 ing residues originating in catalyst and persisting in produced 13 polymer.
14 A plurality of catalyst components using silica, alumina~ and other similar metal oxides as carriers for deposition of transition 16 metals have been proposed. Most of them are intended for polymeriza-17 tion of ethylene. A very few of them are intended for polymeriza-18 tion of alpha-olefins such as propylene.
19 As concerns catalyst compositions for the polymerization of propylene, a catalyst component comprising a reaction product of a 21 metal oxide and a magnesium dialkoxide brought in contact with an 22 electron-donating compound and a tetravalent titanium halide (specifi-23 cation of Japanese Patent Application Laid-open SHO 58[1973]-162,607) 24 and a catalyst component comprising a reaction product of an inorganic oxide and a magnesium hydrocarbyl halide compound brought in contact 26 with a Lewis base compound and titanium tetrachloride (specification 27 of Japanese Patent Application Laid-open SHO 55[1980]-94,909) are 28 known to the art. These catalyst components, however, can hardly be 29 called satisfactory in terms of activity and stereoregularity.
Further, a catalyst component obtained by causing a 31 hydrocarbyloxysilane to react with a reaction product of a porous 32 carrier such as silica and an alkyl magnesium compound and subse-33 quently causing a titanium halide compound to react upon the resultant 34 reaction product (specification of Japanese Patent Application Laid-open SHO 57[1982]-153,006) and a catalyst component obtained by 36 causing an organic metal compound to react with a porous carrier,

5;~1 1 causing a hydrocarbyl alcohol to react with the resultant reaction 2 product, and then causing a titanium halide compound to react with the 3 reaction product (specification of Japanese Patent Application 4 Laid-open SHO 57[1982]-200,408) have been proposedO These catalyst components are intended for homopolymerization of ethylene or for

6 copolymerization of ethylene with other olefins. They are not

7 suitable for polymerization of alpha-olefins such as propylene.

8 DISCLOSURE OF THE INVENTION

9 Object of the Invention It is an object of this invention to provide a catalyst 11 component which uses a metal oxide as a carrier and which is used for 12 homopolymerization of an olefin exhibiting high activity and high 13 stereoregularity, particularly an alpha-olefin such as propylene, and 14 for copolymerization of the aforementioned olçfin with other olefins.
More particularly, in accordance with an object of this invention 16 there is provided a catalyst component which is prepared by contact-17 ing a contact reaction product of a metal oxide, a dihydrocarbyl 18 magnesium, and a halogen-containing alcohol held in contact with an 19 electron- donating compound and a titanium compound fulfills the object of this invention. This discovery has led to perfection of 21 this invention.
22 _MMARY OF THE INVENTIO
23 To be specific, this invention essentially concerns a 24 catalyst component for the polymerization of olefins which is prepared by contacting a contact reaction product of (1) (a) a metal oxide, (b) 26 a dihydrocarbyl magnesium, and (c) a halogen-containing alcohol held 27 with (2) (d) an electron-donating compound and (e) a titanium 28 compound.
29 Raw materials for preparation of catalyst component (A) Metal Oxide 31 The metal oxide to be used in this invention is the oxide of 32 an element selected from the class of elements belonging to Groups II
33 through IV in the Periodic Table of Elements. Examples of the oxide 34 are B203, MgO, A1203, SiO2, CaO, TiO2, ZnO, ZrO2, SnO2, BaO, and ThO2. Among other oxides enumerated above, B203, MgO, A1203, SiO2, 36 TiO2, and ZrO2 are more desirable selections, and SiO2 is the most 37 desirable selection. Further, composite oxides including these metal 38 oxides are also usable. Examples of these composite oxides are ~8Sl~

1 SiO MgO SiO2-A1203, Si2-Ti2~ Si2-V2S~ SiO2 C 2 3' 2 SiO2-TiO2-MgO-3 The aforementioned metal oxides or composite oxides described above are fundamental1y desired to be an anhydride. It, however, tolerates inclusion of a hydroxide in a very small amount normally 6 entrained in the metal oxide of the class under discussion. It also 7 tolerates inclusion therein of impurities to an extent incapable of 8 appreciably impairing the nature of metal oxide. Examples of the 9 impurities so tolerated are oxides, carbonates, sulfates, and nitrates such as sodium oxide, potassium oxide, lithium oxide, sodium carbon-11 ate, potassium carbonate, calcium carbonate, magnesium carbonate, 12 sodiurn sulfate, aluminum sulfate, barium sulfate, potassium nitrate, 13 magnesium nitrate, and aluminum nitrate.
14 Generally, the metal oxide of the foregoing description is used in the form of powder. The size and shape of the individual-16 particles of this powder are desired to be suitably adjusted because 17 they often have bearing on the shape of the olefin polymer to be 18 produced. Prior to use, this metal oxide is fired at as high a 19 temperature as permissible as for the purpose of expelling poisoned substance and then held so as not to be exposed directly to the 21 atmosphere.
22 (B) Dihydrocarbyl Magnesium 23 The dihydrocarbyl magnesium to be used in the present inven-24 tion (hereinafter referred to as "organic Mg") is represented by the general formula, RMgR'. In this formula, R and R', which can be the 26 same or different, denote an alkyl, cycloalkyl, ary1, or aralkyl group 27 of 1 to 20 carbon atoms.
28 Examples of the organic Mg are dimethyl magnesium (herein-29 after "magnesium" will be abbreviated "Mg"), diethyl Mg, ethylmethyl Mg, dipropyl Mg, diisopropyl Mg, ethylpropyl Mg, dibutyl Mg, diiso-31 butyl Mg, di-sec-butyl Mg, di-tert-butyl Mg, butylethyl Mg, butyl-32 propyl Mg, sec-butylethyl Mg, tert-butylisopropyl Mg, sec-butyl-tert-33 butyl Mg, dipentyl Mg, diisopentyl Mg, ethylpentyl Mg, isopropylpentyl 34 Mg, sec-butylpentyl Mg, dihexyl Mg, ethylhexyl Mg, butylhexyl Mg, tert-butylhexyl Mg, (2-ethylbutyl)ethyl Mg, (2,2-diethylbutyl)ethyl 36 Mg, diheptyl Mg, dioctyl Mg, di-2-ethylhexyl Mg, didecyl Mg, dicyclo-37 hexyl Mg, cyclohexylethyl Mg, butylcyclohexyl Mg, di(methylcyclohexyl) 38 Mg, diphenyl Mg, ethylphenyl Mg, butylphenyl Mg, sec-butylphenyl Mg, 12~8511 ditolyl Mg, ethyltolyl Mg, dixylyl Mg, dibenzyl Mg, benzyl-tert-butyl 2 Mg, diphenethyl Mg, and ethylphenethyl Mg.
3 The organic Mg may be a mixture or complex compound with an 4 organic compound of other metal. The organic compound of other metal is represented by the general formula MRn (wherein M denotes boron, 6 beryllium, aluminum, or zinc, R denotes an alkyl, cycloalkyl, aryl, or 7 aralkyl group of 1 to 20 carbon atoms, and n denotes the valency of 8 the metal M). Concrete examples of the organic compound of other 9 metals are triethyl aluminum, tributyl aluminum, triisobutyl aluminum, triphenyl aluminum, triethyl boron, tributyl boron, diethyl beryllium, 11 diisobutyl beryllium, diethyl zinc, and dibutyl zinc.
12 In the aforementioned mixture or complex compound, the ratio 13 of the organic Mg to the organic compound of other metal generally is 14 such that the amount of the other metal is not more than 5 gram atoms, preferably not more than 2 gram atoms, per gram atom of magnesium.
16 (C) Halogen-containing Alcohol 17 The term "halogen-containing alcohol" as used in this 18 invention means a monohydric or polyhydric alcohol possessing one or 19 more hydroxyl groups in the molecule thereof and having one or more hydrogen atoms thereof other than the aforementioned hydroxyl group 21 substituted with a halogen atom. Concrete examples of the halogen 22 atom are chlorine, bromine, iodine, and fluorine atom. Among the 23 halogen atoms cited above, the chlorine atom is particularly desirable.
24 Examples of the halogen-containing alcohol are 2-chloro-ethanol, 1-chloro-2-propanol, 3-chloro-1-propanol, 1-chloro-2-methyl-26 2-propanol, 4-chloro-1-butanol, 5-chloro-1-pentanol, 6-chloro-1-27 hexanol, 3-chloro-1,2-propane diol, 2-chlorocyclohexanol, 4-chloro-28 benzhydrol, (m,o,p)-chlorobenzyl alcohol, 4-chlorocatechol, 4-chloro-29 (m,o)-cresol, 6-chloro-(m,o)-cresol, 4-chloro-3,5-dimethylphenol, chlorohydroquinone, 2-benzyl-4-chlorophenol, 4-chloro-1-naphthol, 31 (m,o,p)-chlorophenol, p-chloro-alpha-methylbenzyl alcohol, 2-chloro-32 4-phenylphenol, 6-chlorothimol, 4-chlororesorcin, 2-bromoethanol, 33 3-bromo-1-propanol, 1-bromo-2-propanol, 1-bromo-2-butanol, 2-bromo-34 p-cresol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, (m,o,p)-bromo-phenol, 4-bromoresorcin, (m,o,p)-fluorophenol, p-iodophenol:
36 2,2-dichloroethanol, 2,3-dichloro-1-propanol, 1,3-dichloro-2-propanol, 37 3-chloro-1-(alpha-chloromethyl)-1-propanol, 2,3-dibromo-1-propanol, 38 1,3-dibromomono-2-propanol, 2,4-dibromophenol, 2,4-dibromo-1-naphthol:

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2,2,2-trichloroethanol, 1,1,1-trichloro-2-propanol, 13,13,1!3-trichloro-2 tert-butanol, 2,3,4-trichlorophenol, 2,4,5-trichlorophenol, 2,4,6-3 trichlorophenol, 2,4,6-tribrornophenol, 2,3,5-tribromo-2-hydroxy 4 toluene, 2,3,5-tribromo-4-hydroxy toluene, 2,2,2-trifluoroethanol, alpha,alpha,alpha-trifluoro-m-cresol, 2,4,6-triiodophenol: 2,3,4,6-6 tetrachlorophenol, tetrachlorohydroquinone, tetrachloro-bis-phenol A, 7 tetrabromo-bis-phenol A, 2,2,3,3-tetrafluoro-1-propanol, 2,3,5,6-8 tetrafluorophenol, and tetrafluororesorcin.
9 (D) Electron-donating Compound Examples of the electron-donating compound are carboxylic 11 acids, carboxylic anhydrides, carboxylic esters, carboxylic halides, 12 alcohols, ethers, ketones, amines, amides, nitriles, aldehydes, 13 alcoholates, phosphorus, bismuth, and antimony compounds linked with 14 organic groups through the medium of carbon or oxygen atom, phos-phamides, thioethers, thioesters, and carbonic esters. Among other 16 electron-donating compounds cited above, carboxylic acids, carboxylic 17 anhydrides, carboxylic esters, carboxylic halides, alcohols and ethers 18 are particularly desirable.
19 Concrete examples of the carboxylic acids are aliphatic mono-carboxylic acids such as formic acid, acetic acid, propionic acid, 21 butyric acid, isobutyric acid, valeric acid, caproic acid, pivalic 22 acid, acrylic acid, methacrylic acid, and crotonic acid, aliphatic 23 dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, 24 adipic acid, sebacic acid, maleic acid, and fumaric acid, aliphatic oxycarboxylic acids such as tartaric acid, alicyclic carboxylic acids 26 such as cyclohexane monocarboxylic acids, cyclohexene monocarboxylic 27 acids, cis-1,2-cyclohexane dicarboxylic acids, and cis-4-methylcyclo-28 hexane-1,2-dicarboxylic acids, aromatic monocarboxylic acids such as 29 benzoic acid, toluic acid, anisic acid, p tert-butyl-benzoic acid, naphtholic acid, and cinnamic acid, and aromatic poly carboxylic acids 31 such as phthalic acid, isophthalic acid, terephthalic acid, naphthalic 32 acid, trimellitic acid, hemimellitic acid, trimestic acid, 33 pyromellitic acid, and mellitic acid.
34 Concrete examples of carboxylic anhydrides are the anhydrides of the carboxylic acids enumerated above.
36 Carboxylic esters are monoesters and polyesters of the car-37 boxylic acids enumerated above. Concrete examples of such monoesters 38 and polyesters are butyl formate, ethyl acetate, butyl acetate, iso-12~8~11 1 butyl isobutyrate, propyl pivalate, isobutyl pivalate, ethyl acrylate, 2 methyl methacrylate, ethyl methacrylate, isobutyl methacry1ate, 3 diethyl malonate, diisobutyl malonate, diethyl succinate, dibutyl 4 succinate, diisobutyl succinate, diethyl glutarate, dibutyl glutarate, diisobutyl glutarate, diisobutyl adipate, dibutyl sebacate, diisobutyl 6 sebacate, diethyl maleate, dibutyl maleate, diisobutyl maleate, 7 monornethyl fumarate, diethyl fumarate, diisobutyl fumarate , diethyl 8 tartrate, dibutyl tartrate, diisobutyl tartrate, ethyl cyclohexane-9 carboxylates, methyl benzoate, ethyl benzoate, methyl p-to1uate, ethyl p-tert butylbenzoate, ethyl p-anisate, ethyl alpha-naphthoate, iso-11 butyl alpha-naphthoate, ethyl cinnamate, monomethyl phthalate, 12 monobutyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl 13 phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, diallyl 14 phthalate, diphenyl phthalate, diethyl isophthalate, diisobutyl isophthalate, diethyl terephthalate, dibutyl terephthalate, diethyl 16 naphthalate, dibutyl naphthalate, triethyl trimellate, tributyl 17 trimellate, tetramethyl pyromellate, tetraethyl pyromellate, and 18 tetrabutyl pyromellate.
19 Carboxylic halides are halides of the carboxylic acids enumerated above. Concrete examples of such halides are acetic acid 21 chloride, acetic acid bromide, acetic acid iodide, propionic acid 22 chloride, butyric acid chloride, butyric acid bromide, butyric acid 23 iodide, pivalic acid chloride, pivalic acid bromide, acrylic acid 24 chloride, acrylic acid bromide, acrylic acid iodide, methacrylic acid chloride, methacrylic acid bromide, methacrylic acid iodide, crotonic 26 acid chloride, maloic acid chloride, maloic acid bromide, succinic 27 acid chloride, succinic acid bromide, glutaric acid chloride, glutaric 28 acid bromide, adipic acid chloride, adipic acid bromide, sebacic acid 29 chloride, sebacic acid bromide, maleic acid chloride, maleic acid bromide, fumaric acid chloride, fumaric acid bromide, tartaric acid 31 chloride, tartaric acid bromide, cyclohexane-carboxylic acid chloride, 32 cyclohexane-carboxylic acid bromides, l-cyclohexene-carboxylic acid 33 chloride, cis-4-methylcyclohexene-carboxylic acid chloride, cis-4-34 methylcyclohexene-carboxylic acid bromide, benzoyl chloride, benzoyl bromide, p-toluic acid chloride, p-toluic acid bromide, p-anisic acid 36 chloride, p-anisic acid bromide, alpha-naphthoic acid chloride, 37 cinnamic acid chloride, cinnamic acid bromide, phthalic acid 38 dichloride, phthalic acid dibromide, isophthalic acid dichloride, 124~35~ ~.

1 isophthalic acid dibromide, terephthalic acid dichloride, and 2 naphthalic acid dichloride. Further monoalkylhalides of dicarboxylic 3 acids such as adipic acid monomethyl chloride, maleic acid monoethyl 4 chloride and maleic acid monomethyl chloride and phthalic acid butyl chloride are also usable.
6 Alcohols are represented by the general formula ROH. In the 7 formula, R denotes an alkyl, alkenyl, cycloalkyl, aryl, or aralkyl 8 group of 1 to 12 carbon atoms. Concrete examples of such alcohols are 9 methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, octanol, 2-ethylhexanol, cyclohexanol, benzyl 11 alcohol, allyl alcohol, phenol, cresol, xylenol, ethyl phenol, 12 isopropyl phenol, p-tertiary butyl phenol, and n-octyl phenol. Ethers 13 are represented by the general formula ROR'. In the formula, R and R' 14 each denote an alkyl, alkenyl, cycloalkyl, aryl, or aralkyl group of 1 to 12 carbon atoms, providing that R and R' may be equal to or 16 different from each other. Concrete examples of such ethers are 17 diethyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, 18 diisoamyl ether, di-2-ethylhexyl ether, diallyl ether, ethylallyl 19 ether, butylallyl ether, diphenyl ether, anisol, and ethylphenyl ether. Any of the compounds cited above as examples of halogen-21 containing alcohols is also usable.
22 (E) Titanium Compound 23 Titanium compounds are divalent, trivalent, and tetravalent 24 titanium compounds. Concrete examples of such titanium compounds are titanium tetrachloride, titanium tetrabromide, trichlorethoxy 26 titanium, trichlorobutoxy titanium, dichlorodiethoxy titanium, 27 dichlorodibutoxy titanium, dichlorodiphenoxy titanium, chlorotriethoxy 28 titanium, chlorotributoxy titanium, tetrabutoxy titanium, and titanium 29 trichloride. Among other titanium compounds enumerated above, such tetravalent titanium halides such as titanium tetrachloride, 31 trichloroethoxy titanium, dichlorodibutoxy titanium, and dichloro-32 diphenoxy titanium prove desirable and titanium tetrachloride proves 33 particularly desirable.
34 Method for Preparation of Catalyst Component The catalyst component of the present invention is obtained 36 by contacting a reaction product comprising (a) a metal oxide 37 (hereinafter referred to as "A component"), the organic Mg 38 (hereinafter referred to as "B component"), and the halogen-containing ~2~8511 1 alcohol (hereinafter referred to as "C component") (b) with an 2 electron-donating compound (hereinafter referred to as "D component") 3 and a titanium compound (hereinafter referred to as "E component").
4 Contact of A Component, B Component, and C Component S The contact of A component, 8 component and C component is 6 effected by (1) a procedure of first establishing contact between A
7 component and B component and then introducing C component into 8 contact therewith, (2) a procedure of first establishing contact 9 between A component and C component and then introducing B component into contact thereof, (3) a procedure of first establishing contact 11 between B component and C component and then introducing A component 12 into contact therewith, or (4) a procedure of establishing contact 13 among A component, B component and C component all at once.
14 The contact mentioned above, for example, is effected by stirring the relevant components in the presence or absence of an 16 inactive medium or by mechanically comminuting the relevant components 17 jointly.
18 Examples of the inactive medium usable in the contact are 19 hydrocarbons such as pentane, hexane, heptane, octane, decane, cyclo-hexane, benzene, toluene, and xylene and halides of hydrocarbons such 21 as 1,2-dichloroethane, 1,2-dichloropropane, carbon tetrachloride, 22 butyl chloride, isoamyl chloride, bromobenzene, and chlorotoluene.
23 The contact of A component, B component and C component is 24 generally carried out at a temperature of -20C to +150C for a period of 0.1 to 100 hours. Where the contact entails evolution of heat, 26 there may be adopted a procedure of first mixing the components 27 gradually at a low temperature and, after all the components have been 28 wholly mixed, elevating the temperature and continuing the contact.
29 Further during the course of the contact of the components, the individual components may be washed with the aforementioned inactive 31 medium. The proportions in which A component, B component, and C
32 component are used in the contact are such that the mol ratio B/A
33 falls in the range of 0.01 to 10, that of C/A in the range of 0.01 to 34 10, and that of C/B in the range of 0.1 to 20.
The solid product obtained by the contact of A component, B
36 component and C component (hereinafter referred to as "reaction 37 product I") is subjected to the subsequent contact. Optionally, the ~Z~3511 1 reaction product I may be cleaned with a suitable cleaning agent such 2 as, for example, the aforementioned inactive medium.
3 Contact with D Component and E Component 4 The contact of the reaction product I with an e1ectron-donating (D component) and a titanium compound (E component) is 6 effected by (1) a procedure of first establishing contact between the 7 reaction product I and D component and then introducing E component 8 into contact therewith, (2) a procedure of first establishing contact 9 between the reaction product I and E component and then introducing D
component into contact therewith, or (3) a procedure of establishing 11 contact between D component and E component used jointly on one part 12 and the reaction product I on the other part.
13 The contact mentioned above is accomplished by mechanically 14 comminuting the relevant components jointly or stirring them in the presence or absence of an inactive medium. It is more desirably 16 effected by stirring the relevant components in the presence or 17 absence of an inactive medium. As the inactive medium, any of the 18 aforementioned compounds can be used effectively.
19 When the contact of the reaction product I with D component and C component is effected by their mechanical joint comminution, it 21 is effected generally at a temperature in the range of 0C to 200C
22 for a period of 0.1 to 100 hours. When the contact is carried out by 23 stirring, it is effected generally at a temperature of 0C to 200C
24 for a period of 0.5 to 20 hours. The amount of D component used in this contact is in the range of 0.05 to 10 gram mols, preferably 0.01 26 to 1 gram mol, per gram atom of magnesium in the reaction product I.
27 The amount of E component used in the contact is above the level of 28 0.1 gram mol, preferably in the range of 1 to 50 gram mols, per gram 29 atom of magnesium in the reaction product I.
The contact between the reaction product I and E component 31 may be carried out twice or more. This contact can be effected by any 32 of the procedures mentioned above. ln this case, the product from the 33 former contact may be cleaned with an inactive medium and the cleaned 34 product allowed to contact with a freshly added portion of E component (in conjunction with the aforementioned medium).
36 Where the contact with E component is carried out in two or 37 more split steps, the reaction mixture under treatment may be allowed 124~

to contact with an inactive hydrocarbon, halide of hydrocarbon, or 2 metal halide compound between the split steps of contact.
3 Examples of the inactive hydrocarbon usable for the contact 4 are aliphatic, alicyclic, and aromatic hydrocarbons. Concrete examples of such hydrocarbons are n-hexane, methyl hexane, dimethyl 6 hexane, ethyl hexane, ethylmethyl pentane, n-heptane, methyl heptane, 7 trimethyl pentane, dimethyl heptane, ethyl heptane, trimethyl hexane, 8 trimethyl heptane, n-octane, methyl octane, dimethyl octane, 9 n-undecane, n-dodecane, n-tridecane, n-tetradecane, n-pentadecane, n-hexadecane, n-octadecane, n-nonadecane, n-eicosane, cyclopentane, 11 cyclohexane, methyl cyclopentane, cycloheptane, dimethyl cyclopentane, 12 methyl cyclohexane, ethyl cyclopentane, dimethyl cyclohexane, ethyl 13 cyclohexane, cyclooctane, indane, n-butyl cyclohexane, isobutyl 14 cyclohexane, adamantane, benzene, toluene, xylene, ethylbenzene, tetramethylbenzne, n-butylbenzene, isobutylbenzene, propyl toluene, 16 decalin, and tetralin.
17 Examples of the halide of hydrocarbon usable for the contact 18 are mono- and poly-halogen substitution products of saturated or 19 unsaturated aliphatic, alicyclic, and aromatic hydrocarbons. Concrete examples of such compounds are aliphatic compounds such as methyl 21 chloride, methyl bromide, methyl iodide, methylene chloride, methylene 22 bromide, methylene iodide, chloroform, bromoform, iodoform, carbon 23 tetrachloride, carbon tetrabromide, carbon tetraiodide, ethyl 24 chloride, ethyl bromide, ethyl iodide, 1,2-dichloroethane, 1,2-dibromo-ethane, 1,2-diiodo-ethane, methyl chloroform, methyl bromo-26 form, methyl iodoform, 1,1,2-trichloro-ethylene, 1,1,2-tribromo-27 ethylene, 1,1,2,2-tetrachloro-ethylene, pentachloro-ethane, ?8 hexachloro-ethane, hexabromo-ethane, n-propyl chloride, 1,2-dichloro-29 propane, hexachloro-propylene, octachloro-propane, decabromobutane, and chlorinated paraffins, alicyclic compounds such as chlorocyclo-31 propane, tetrachlorocyclo-pentane, hexachloro-pentane, and hexachloro-32 cyclohexane, and aromatic compounds such as chlorobenzene, bromo-33 benzene, o-dichlorobenzene, p-dichlorobenzene, hexachlorobenzene, 34 hexabromobenzene, benzotrichloride, and p-chlorobenzo-trichloride~
These compounds are such that one member of a mixture of two 36 or more members selected from the compounds enumerated above may be 37 advantageously used.

124~35~1 "

The metal halide compound is the halide of one element 2 selected from the class of elements of Group IIIa, Group IVa, and 3 Group Va in the Periodic Table of Elements (hereinafter referred to as 4 "metal halide"). Examples of the metal halide are chlorides, fluorides, bromides, and iodides of B, Al, Ga, In, Tl, Si, Ge, Sn, Pb, 6 As, Sb, and Bi. Among other metal halides enumerated above, BC13, 7 BBr3, BI3, AlC13, AlBr3, AlI3, GaC13, GaBr3, InC13, 8 TlC13, SiC14, SnC14, SbC15, and SbF5 prove particularly 9 desirable.
The contact of the reaction mixture optionally made with the 11 inactive hydrocarbon, halide of hydrocarbon, or metal halide (herein-12 after referred to as "F component") between the two or more split 13 steps of contact made by the E component is carried out at a tempera-14 ture in the range of 0 to 200C for a period of 5 minutes to 20 hours, preferably at 20C to 150C for 10 minutes to 5 hours. When 16 the F component is a liquid substance, it is desired to be used in 17 such an amount that the reaction product I is obtained in an amount in 18 the range of 1 to 1,000 9 per liter of the F component. When the F
19 component is a solid substance, this solid F component is desired to be used as dissolved in another F component capable of dissolving the 21 solid F component. The amount of this solid F component is desired to 22 be such that the reaction product I is obtained in an amount in the 23 range of 0.01 to 100 9 per g of the F component.
24 The mass of contact between the reaction product I with the component E may be allowed to contact with the F component. This 26 contact can be carried out in the same manner as in the contact 27 optionally made by the use of the aforementioned F component.
28 The contact reaction product obtained as described above is 29 cleaned, when necessary, with hydrocarbon such as hexane, heptane, octane, cyclohexane, benzene, toluene, or xylene, and then dried to 31 give birth to the catalyst component of the present invention.
32 The catalyst component of the present invention is formed of 33 particles having a specific surface area in the range of 10 to 1,000 34 m3/g and a pore volume in the range of 0.5 to 5 cm3/g as measured by the BET method at the adsorption temperature of liquefied nitrogen 36 and possessing diameters so uniform as to be distributed in a narrow 37 range. As to percentage composition, this catalyst component 38 comprises 3 to 90% by weight of metal oxide, 1 to 25~o by weight of i~4~Sl~

magnesium, 0.5 to 10% by weight of titanium, and 4 lo 60% by weight of 2 chlorine.
3 Catalyst for the Polymerization of Olefins 4 The catalyst component of the present invention is used, as combined with an organic compound of a metal selected from the class 6 of metals belonging to Groups I through III in the Periodic Table of 7 Elements, for catalyzing the homopolymerization of an olefin or the 8 copolymerization of the olefin with other olefins.
9 Or anic Compound of Metal of Group I throuqh Group III
Examples of the organic metal compounds usable in combination 11 with the catalyst component are organic compounds of lithium, 12 rnagnesium, calcium, zinc, and aluminum. Among other organic metal 13 compounds just mentioned, organic aluminum compounds prove 14 particularly desirable. The organic aluminum compounds usable herein are represented by the general formula RnAlX3 n (wherein R denotes 16 an alkyl group or an aryl group, X denotes a halogen atom, an alkoxy 17 group or a hydrogen atom, and n denotes a desired number in the range 18 of 1 ' n ~ 3). Particularly desirable examples of the organic 19 aluminum compounds are alkyl aluminum compounds such as trialkyl aluminum, dialkyl aluminum monohalide, monoalkyl aluminum dihalide, 21 alkyl aluminum sesquihalide, dialkyl aluminum monoalkoxide, and 22 dialkyl aluminum monohydride, respectively having 1 to 18 carbon 23 atoms, preferably 2 to 6 carbon atoms, and mixtures and complex 24 compounds thereof. Concrete examples of such organic aluminum compounds are trialkyl aluminums such as trimethyl aluminum, triethyl 26 aluminum, tripropyl alurninum, triisobutyl aluminum, and trihexyl 27 aluminum, dialkyl aluminum monohalides such as dimethyl aluminum 28 chloride, diethyl aluminum chloride, diethyl aluminum bromide, diethyl 29 aluminum iodide, and diisobutyl aluminum chloride, monoalkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum 31 dichloride, methyl aluminum dibromide, ethyl aluminum dibromide, ethyl 32 aluminum diiodide, and isobutyl aluminum dichloride, alkyl aluminum 33 sesquihalides such as ethyl aluminum sesquichloride, dialkyl aluminum 34 monoalkoxides such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, diethyl aluminum phenoxide, dipropyl aluminum ethoxide, 36 diisobutyl aluminum ethoxide, and diisobutyl aluminum phenoxide, and 37 dialkyl aluminum hydrides such as dimethyl aluminum hydride, diethyl 38 aluminum hydride, dipropyl aluminum hydride, and diisobutyl aluminum ~2~85~

hydride. Among other organic aluminum compounds enumerated above, 2 trialkyl aluminums, specifically triethyl aluminum, triisobutyl 3 aluminum, prove particularly desirable. The trialkyl aluminum can be 4 used in combination with other organic aluminum compounds such as diethyl aluminum chloride, ethyl alum,num dichloride, ethyl aluminum 6 sesquichloride, diethyl aluminum ethoxide, or diethyl aluminum hydride 7 which is easily available commercially. These other organic aluminum 8 compounds may be used in the form of a mixture or complex compound.
9 Further, an organic aluminum compound having two or more aluminum atoms linked through the medium of an oxygen atom or nitrogen 11 atom is also usable. Concrete examples of this organic aluminum 12 compound are (c2H5)2AloAl(c2Hs)2~ (C4H9)2A ( 4 9 2 13 (C2H5)2Al IAl(C2H5)2 16 Examples of organic compounds of metals other than aluminum 17 are diethyl magnesium, ethyl magnesium chloride, diethyl zinc and such 18 compounds as LiAl(C2H5)4 and LiAl(C7H15)4.
19 The organic metal compound may be used independently or in combination with an electron-donating compound. This electron-21 donating compound may be any of the electron-donating compounds 22 employed in the preparation of the catalyst component described 23 above. Besides, organic silicon compounds capable of serving as 24 electron-donating compounds and electron-donating compounds containing hetero atoms such as nitrogen, sulfur, oxygen, and phosphorus atoms are 26 also usable.
27 Concrete examples of organic silicon compounds are 28 tetramethoxy silane, tetraethoxy silane, tetrabutoxy silane, tetra-29 isobutoxy silane, tetraphenoxy silane, tetra(p-methylphenoxy) silane, tetrabenzyloxy silane, methyl trimethoxy silane, methyl triethoxy 31 silane, methyl tributoxy silane, methyl triphenoxy silane, ethyl 32 triethoxy silane, ethyl triisobutoxy silane, ethyl triphenoxy silane, 33 butyl trimethoxy silane, butyl triethoxy silane, butyl triphenoxy 34 silane, isobutyl triisobutoxy silane, vinyl triethoxy silane, allyl trimethoxy silane, phenyl trimethoxy silane, phenyl triethoxy silane, 36 benzyl triphenoxy silane, methyl triallyloxy silane, dimethyl 37 dimethoxy silane, dimethyl diethoxy silane, dimethyl diisopropoxy 1248Sll 1 silane, dimethyl dibutoxy silane, dimethyl dihexyloxy silane, dimethyl 2 diphenoxy silane, diethyl diethoxy silane, diethyl diisobutoxy silane, 3 diethyl diphenoxy silane, dibutyl diisopropoxy silane, dibutyl 4 dibutoxy silane, dibutyl diphenoxy silane, diisobutyl diethoxy silane, diisobutyl diisobutoxy silane, diphenyl dimethoxy silane, diphenyl 6 diethoxy silane, diphenyl dibutoxy silane, dibenzyl diethoxy silane, 7 divinyl diphenoxy silane, diallyl dipropoxy silane, diphenyl 8 diallyloxy silane, methylphenyl dimethoxy silane, and chlorophenyl g diethoxy silane.
Concrete examples of the electron-donating compound 11 containing a hetero atom are such nitrogen atom-containing compounds 12 as 2,2,6,6-tetramethyl piperidine, 2,6-dimethyl piperidine, 2,6-13 diethyl piperidine, 2,6-diisopropyl piperidine, 2,2,5,5-tetramethyl 14 pyrrolidine, 2,5-dimethyl pyrrolidine, 2,5-diethyl pyrrolidine, 2,5-diisopropyl pyrrolidine, 2-methyl pyridine, 3-methyl pyridine, .
16 4-methyl pyridine, 1,2,4-trimethyl piperidine, 2,5-dimethyl piper-17 idine, methyl nicotinate, ethyl nicotinate, nicotinic acid amide, 18 benzoic acid amide, 2-methyl pyrrole, 2,5-dimethyl pyrrole, imidazole, 19 toluic acid amide, benzonitrile, acetonitrile, aniline, para-toluidine, ortho-toluidine, meta-toluidine, triethyl amine, diethyl 21 amine, dibutyl amine, tetramethylene diamine, and tributyl amine, such 22 sulfur atom-containing compounds as thiophenol, thiophene, ethyl 23 2-thiophene carboxylate, ethyl 3-thiophene carboxylate, 2-methyl 24 thiophene, methyl mercaptan, ethyl mercaptan, isopropyl mercaptan, butyl mercaptan, diethyl thioether, methyl benzenesulfonate, methyl 26 sulfite, and ethyl sulfite, such oxygen atom-containing compounds as 27 tetrahydrofuran, 2-methyl tetrahydrofuran, 3-methyl tetrahydrofuran, 28 dioxane, dimethyl ether, diethyl ether, dibutyl ether, diisoamyl 29 ether, diphenyl ether, anisole, acetophenone, acetone, methylethyl ketone, acetyl acetone, ethyl 2-furalate, isoamyl 2-furalate, methyl 31 2-furalate, and propyl 2-furalate, and such phosphorus atom-containing 32 compounds as triphenyl phosphine, tributyl phosphine, triphenyl 33 phosphite, tribenzyl phosphite, diethyl phosphate, and diphenyl 34 phosphate.
These electron-donating compounds are such that two or more 36 members selected from the group of compounds enumerated above can be 37 used as a mixture. The electron-donating compound may be used at the ~2~3S~

1 same time that the organic metal compound is used in combination with 2 the catalyst component or it may be used after it has been placed in 3 contact with the organic metal compound.
4 The amount of the organic metal compound to be used relative to the catalyst component of the present invention falls generally in 6 the range of 1 to 2000 gram mols, preferably 20 ti 500 gram mols, per 7 gram atom of titanium present in the catalyst component.
8 The proportions of the organic metal compound and the 9 electron-donating compound are such that the amount of the organic metal compound falls in the range of 0.1 to 40 gram atoms, preferably 11 1 to 25 gram atoms, per mol of the electron-donating compound.
12 Polymerizatio of Olefins 13 The catalyst which comprises the catalyst component obtained 14 as described above and the organic metal compound (and the electron-donating compound) is useful for catalyzing homopolymeriza-16 tion of a monoolefin of 2 to 10 carbon atoms or copolymerization of 17 the monoolefin in combination with other monoolefins or diolefins of 3 18 to 10 carbon atoms. The catalyst exhibits an outstanding function, 19 particularly in catalyzing homopolymerization of an alpha-olefin such as5 for example, propylene, l-butene, 4-methyl-l~pentene, or l-hexene, 21 copolymerization of two such alpha-olefins and/or random and block 22 copolymerization of the alpha-olefin with ethylene.
23 The polymerization may be carried out in either the gaseous 24 phase or the liquid phase. When the polymerization is performed in the liquid phase, it can be effected on a liquid monomer in an 26 inactive hydrocarbon such as normal butane, iso-butane, normal pen-27 tane, iso-pentane, hexane, heptane, octane, cyclohexane, benzene, 28 toluene, or xylene. The polymerization temperature falls generally in 29 the range of -80C to +150C, preferably in the range of 40C to 120C. The polymerization pressure is sufficient in the range of 1 to 31 60 atmospheres. Adjustment of the molecular weight of the polymer to 32 be obtained is attained by causing the polymerization to proceed in 33 the presence of hydrogen or other known molecular weight adjusting 34 agents. The amount of the other olefin with which the olefin is copolymerized generally is not allowed to exceed 30% by weight and 36 preferably is selected in the range of 0.3 to 15% by weight. The 37 polymerization by the catalyst system of this invention can be carried lZ485~11 1 out continuously or batchwise under those conditions which are 2 generally adopted for the purpose of polymerization. The copoly-3 merization may be performed in one step or in two or more split 4 steps.
Effect of the Invention 6 The catalyst component of the present invention functions 7 effectively as a catalyst for the production of a polyolefin, 8 particularly isotactic polypropylene, a random copolymer of ethylene 9 and propylene, and a block copolymer of ethylene and propylene.
The polymerization catalyst using the catalyst component of 11 the present invention possesses high polymerization activity and high 12 stereoregularity and permits the high polymerization activity to be 13 retained long during the course of the polymerization. The olefin 14 polymer powder consequently obtained has high bulk density. The polymer powder abounds with fluidity.

17 The present invention will be described more specifically 18 below with reference to working examples and applied examples. The 19 examples are for purposes of illustrating the invention and should not be interpreted as a limitation of the invention. The percents (%) 21 mentioned in the working examples and the applied examples are per-22 cents by weight unless otherwise specified.
23 The heptane insolubles content (hereinafter referred to as 24 "HI") which shows the proportion of crystalline polymer to the whole of a given polymer represents the residue after 6 hours extraction of 26 the polymer with boiling n-heptane in an improved version of Soxhlet 27 extracter. The melt flow rate (MFR) represents the value determined 28 in accordance with ASTM D-1238. The bulk density represents the value 29 determined by the method A defined in ASTM D-1895-69.

31 Contact of Silicon Oxide with n-Butylethyl Magnesium 32 A flask having an inner volume of 200 ml and provided with a 33 dropping funnel and a stirrer has its interior air displaced with 34 nitrogen gas. In the flask, 5 9 of silicon oxide (product of Davison Corp. having a specific surface area of 302 m /9, a pore volume of 36 1.54 cm3/g, and an average pore radius of 204 A and marketed under 37 the trademark designation of G-952)(hereinafter referred to as 38 "SiO2") fired under a flow of nitrogen gas at 200C for two hours lZ~85~1 1 and further at 700C for five hours and 20 ml of n-heptane were 2 placed. The compounds so placed and 20 ml of a 20% n-heptane solution 3 of n-butylethyl magnesium (hereinafter referred to as "BEM") (the 4 solution in the amount of 26.8 mmol as BEM) added thereto were stirred at 90C for two hours. The supernatant consequently formed was 6 removed by decantation and the solid was washed with 50 ml of 7 n-heptane at room temperature and the supernatant formed again was 8 removed by decantation. The washing treatment with n-heptane was 9 repreated four more times.
Contact with 2,2,2-trichloethanol _ 11 The solid product issuing from the last washing treatment was 12 suspended in 20 ml of n-heptane. Into the resultant suspension, a 13 solution of 9.6 g (64 mmols) of 2,2,2-trichloroethanol in 10 ml of 14 n-heptane was added dropwise through the dropping funnel at 0C over a period of 30 minutes. The suspension and the added solution were 16 stirred at 0C for one hour, heated to 80C over a period of one hour 17 and again stirred at 80C for one hour. After the completion of the 18 reaction, the reaction mixture at room temperature was washed twice 19 with 50 ml of n-heptane and three times with 50 ml of toluene. The solid consequently obtained (solid component I), by analysis, was 21 found to contain 49.5% of SiO2, 3.8% of magnesium, and 33.5% of 22 chlorine. This solid was found to have a specific surface area of 255 23 m2/g and a pore volume of 0.79 cm2/g.
24 Contact with d-n-butyl phthalate and titanium tetrachloride The solid component I obtained in the preceding procedure and 26 20 ml of toluene and 0.6 9 of di-n-butyl phthalate added thereto were 27 heated for reaction at 50C for two hours. Then, the reaction mixture 28 and 30 ml of titanium tetrachloride added thereto were heated for 29 reaction at 90C for two hours. The solid substance obtained by this reaction was washed at room temperature eight times with 50 ml of 31 n-hexane. It was then dried under a vacuum at room temperature for 32 one hour. Consequently, 7.5 g of a catalyst component was obtained.
33 This catalyst component was found to have a specific surface area of 34 285 m2/g and a pore volume of 0.87 cm3/g. This catalyst component was found to contain 55.9% of SiO2, 4.3% of magnesium, 16.3% of 36 chlorine, and 3.1% of titanium.

38 The solid substance formed after contact with titanium lZ4851~

1 tetrachloride in the procedure of Example 1 was separated. This solid 2 substance and 30 ml of titanium tetrachloride added thereto were 3 heated for reaction at 90C for two hours. The solid substance 4 consequently formed was treated in the same way as in Example 1, to afford a catalyst component having a titanium content of 2.8%.

7 The reaction mixture formed after contact with titanium 8 tetrachloride in the procedure of Example 1 was decanted to expel the 9 supernatant. The solid substance which remained was cleaned in 50 ml of toluene at 90C for 15 minutes. The washing treatment with toluene 11 was repeated. The washed solid substance and 20 ml of toluene and 30 12 ml of titanium tetrachloride added thereto were heated for reaction at 13 90C for two hours. The resultant reaction mixture was washed with 14 n-hexane and dried in the same way as in Example 1, to afford 7.4 9 of a catalyst component. This catalyst component was found to have a 16 specific surface area of 279 m2/g and a pore volume of 0.90 m3/g.
17 It was found to contain 56.5% of SiO2, 4.4 9 of magnesium, 15.1% of 18 chloride, and 2.4% of titanium.

The procedure of Example 3 was repeated, except that the 21 temperature of contact with titanium tetrachloride was changed from 22 90C to 120C. Consequently, there was prepared a catalyst component 23 having a titanium content of 2.1%.

-The procedure of Example 3 was repeated, except that in the 26 contact of di-n-butyl phthalate and titanium tetrachloride, these two 27 compounds were added at the same time for reaction. Consequently, 28 there was prepared a catalyst component having a titanium content of 29 2.5%.

31 The procedure of Example 3 was repeated, except that in the 32 contact of di-n-butyl phthalate and titanium tetrachloride, 30 ml of 33 titanium chloride was added and abruptly heated to 90C while under 34 stirring, 0.6 9 of di-n-butyl pnthalate was added subsequently and heated for reaction at 90C for two hours. Consequently, there was 36 prepared a catalyst component having a titanium content of 2.4%.

38 The solid component I obtained in the procedure of Example 1 ~24851~

,9 1 and 50 ml of titanium tetrachloride added thereto were stirred and 2 heated suddenly to 90C. The resultant mixture and 0.6 g of di-n-3 butyl phthalate added thereto were heated for reaction at 90C for two 4 hours. After completion of the reaction, the supernatant was removed and the residue and 50 ml of titanium tetrachloride added thereto were 6 heated for reaction at 90C for two hours. The resultant reaction 7 mixture was washed and dried by following the procedure of Example 1, 8 to afford a catalyst component having a titanium content of 3.3%.

In the procedure of Example 7, between the two split steps of 11 contact with titanium tetrachloride, the reaction mixture was washed 12 twice with 50 ml of titanium tetrachloride at 90C for 15 minutes.
13 The reaction mixture was washed and dried by following the procedure 14 of Example 1. Consequently, there was prepared a catalyst component having a titanium content of 3.0%.

17 The procedure of Example 3 was followed, except that in the 18 contact of di-n-butyl phthalate and titanium tetrachloride, xylene 19 (Example 9), n-heptane (Example 10), and 1,2-dichloroethane (Example 11) were severally used as an inactive medium in the place of 21 toluene. Consequently, there were prepared catalyst components having 22 titanium contents of 2.2% (Example 9), 3.5% (Example 10), and 2.8%
23 (Example 11).

During the course of contact with di-n-butyl phthalate and 26 titanium tetrachloride in the procedure of Example 3, the reaction 27 mixture resulting from the first step of contact with titanium tetra-28 ch7Oride was freed of the supernatant. The residue and 50 ml of 29 toluene and 3 9 of silicon tetrachloride (Example 12), 3 9 of aluminum trichloride (Example 13), or 3 9 of hexachloroethane (Example 14) 31 added thereto were heated for reaction at 60C for one hour. The 32 resultant reaction mixture was washed four times with 50 ml of toluene 33 at 60C. The washed reaction mixture was mixed with 20 ml of toluene 34 and 30 ml of titanium tetrachloride to undergo the second reaction with titanium tetrachloride. The reaction mixture consequently 36 obtained was washed and dried in the same way as in Example 1.
37 Consequently, there were produced catalyst components having titanium 38 contents of 2.1% (Example 12), 2.7% (Example 13), and 2.3% (Example lZ485~lî

1 14) respectively.
2 EXAMPLES 15 and 16 3 A solid substance was obtained by effecting the reaction of 4 the solid substance I with titanium tetrachloride and di-n-butyl phthalate in the same way as in Example 3. This solid substance was 6 washed eight times with n-hexane similarly to Example 1. The washed 7 solid substance was converted by addition of n-hexane into a slurry 8 (4.5 9 of solid substance and 6.~ 9 of n-hexane). The slurry was held 9 in contact with 1.1 9 of hexachloroethane and 100 ml of n-hexane (Example 15), 100 ml 1,2-dichloro-ethane (Example 16) at 50C for 30 11 minutes. The solid substance consequently obtained was separated by 12 filtration at 50C, washed with 100 ml of n-hexane at room 13 temperature, dried under a vacuum for one hour. Consequently, there 14 were prepared catalyst components having titanium contents of 1.6%
(Example 15) and 1.4% (Example 16) respectively.

17 Catalyst components having titanium contents shown below in 18 Table I were prepared by following the procedure of Example 3, except 19 that varying metal oxides indicated below were used in the place of 20 SiO2.

22 Firing Titanium 23 Example Metal Oxide Conditions Content (%) -24 17 A1203 2000C/2 hours 3.5 700C/5 hours 26 18 (M9)2(sio2)3 200C/2 hours 2.5 27 500C/5 hours 28 19 Mixture of 1 kg of SiO2 200C/2 hours 2.3 29 and 100 9 of A1203 700C/5 hours Mixture of 1 kg of SiO2 200C/2 hours 1.9 31 and 20 9 of CrO3 700C/5 hours 33 Catalyst components having titanium contents indicated below 34 were prepared by following the procedure of Example 3, except that varying magnesium compounds indicated below in Table II were used in 36 the place of BEM.

~Z48Sll 2 Titanium 3 Example Organic Mg Content (%) 4 21 Di-n-hexyl magnesium (product of Texas Alkyls 2.5 Corp., marketed under trademark designation 6 of MAGALA~ DNHM) 7 22 Di-n-butyl magnesium (0.5 mol)-triethyl 2.4 8 aluminum (1 mol) complex ~product of Texas 9 Alkyls Corp., marketed under trademark designation of MAGAL ~ 0.5E) 11 23 Di-n-butyl magnesium (7.5 mols)-triethyl 2.5 12 aluminum (1 mol) complex product of Texas 13 Alkyls Corp., marketed under trademark 14 designation MAGALA~ 7.5E) 16 Catalyst components having titanium contents indicated below 17 in Table III were prepared by following the procedure of Example 3, 18 except that varying halogen-containing alcohols indicated below in 19 Table III were used in the place of 2,2,2-trichloroethanol.

~2~851~

2 Titanium 3 Example Halogen-Containing Alcohol Content (%) 4 24 1,1,1-Trichloro-2-propanol 2.3 B,~,~-Trichloro-tert-butanol 2.6 6 26 2,2-Dichloroethanol 2.8 7 27 1,3-Dichloro-2-propanol 2.7 8 28 2-Chloroethanol 2.3 9 29 4-Chloro-l-butanol 2.2 6-Chloro-l-hexanol 2.6 11 31 p-Chlorophenol 2.9 12 32 4-Chloro-o-cresol 2.7 13 33 2,4,6-Trichlorophenol 2.4 14 34 Tetrachlorohydroquinone 2.2 --1-Bromo-2-butanol 2.6 16 36 1,3-Dibromo-2-propanol 2.5 17 37 p-Bromophenol 2.3 18 38 2,4,6-Tribromophenol 2.3 19 39 p-Iodophenol 2.7 2,4,6-Triiodophenol 2.5 21 41 2,2,2-Trifluoroethanol 2.9 22 42 p-Fluorophenol 2.2 24 Catalyst components having titanium contents shown below in Table IV were obtained by following the procedure of Example 3, except 26 that varying electron-donating compounds indicated below in Table IV
27 were used in the place of di-n-butyl phthalate during the contact with 28 the solid component I.

12~8S~

2 Titanium 3 Example Electron-Donating Compound Content 4 43 Ethyl benzoate 2.3 44 Diisobutyl phthalate 2.1 6 45 Phthalic anhydride 2.4 7 46 Phthalic acid dichloride 2.7 8 47 Phthalic acid n-butyl chloride 2.5 9 48 Mono-n-butyl phthalate 2.4 49 Benzoic anhydride 2.2 11 50 Benzoyl chloride 2.6 12 51 Ethyl cinnamate 2.4 13 52 Ethyl cyclohexane carboxylate 2.5 14 53 Tartaric acid 2.8 54 Di-n-butyl tartrate 2.4 16 55 Isobutyl methacrylate 2.3 17 56 Phthalic acid 2.1 18 57 Benzoic acid 3.0 19 58 Di-n-butyl maleate 3.2 59 Diisobutyl sebacate 2.8 21 60 Tri-n-butyl trimellitate 2.2 22 61 Ethanol 2.3 23 62 Isobutanol 2.0 24 63 2-Ethylhexanol 2.3 64 p-Cresol 2.1 26 65 Diethyl ether 2.0 27 66 Di-n-butyl ether 2.2 28 67 Diphenyl ether 2.5 lZ~Sll 1 _XAMPLE 68 2 Contact of Silicon Oxide and 2,2,2-Trichloroethanol 3 A flask having an inner volume of 200 ml and provided with a 4 dropping funnel and a stirrer had its interior air displaced with nitrogen gas. In this flask, 5 9 of the same SiO2 as used in 6 Example 1, 40 ml of n-heptane, and 12 9 of 2,2,2-trichloroethanol 7 added thereto were stirred for contact at 90C for two hours. After 8 completion of the reaction, the reaction mixture was washed three 9 times with 50 ml of n-heptane and decanted at room temperature.
Contact with n-butylethyl magnesium 11 The solid substance obtained in the foregoing procedurP was 12 suspended in 20 ml of n-heptane. To the resultant suspension, 11 ml 13 of the same BEM solution as used in Example 1 was added dropwise 14 through the dropping funnel at 0C over a period of 30 minutes. The -resultant mixture was stirred at 0C for one hour, heated to 80C over 16 a period of one hour, and stirred at 80C for one hour. After comple-17 tion of the reaction, the reaction mixture was washed twice with 50 ml 18 of n-heptane and three times with 50 ml of toluene.
19 Contact with di-n-butyl phthalate and titanium tetrachloride By following the procedure of Example 3, except that the 21 solid component obtained in the preceding procedure was used instead 22 in the contact with the di-n-butyl phthalate and titanium 23 tetrachloride, there was obtained 7.8 9 of a catalyst component having 24 a titanium content of 2.5%.

26 Contact of Silicon Oxide and 2,2,2-Trichloroethanol 27 In a mill pot, 10 9 of the same SiO2 as used in Example 1 28 and 4.4 9 of 2,2,2-trichloroethanol were subjected to a crushing 29 treatment for 24 hours.
Contact with n-Butylethyl Magnesium 31 A flask having an inner volume of 200 ml and provided with a 32 dropping funnel and a stirrer had its interior air displaced with 33 nitrogen gas. In the flask, 6 9 of the solid substance obtained in 34 the preceding procedure and comminuted and 40 ml of n-heptane were placed. Then, 9 ml of the same BEM solution as used in Example 1 was 36 added thereto dropwise through the dropping funnel at 0C over a 37 period of 30 minutes. The resultant reaction mixture was thereafter 38 treated in the same way as in Example 68 to obtain a solid component.

lZ48511 1 Contact with di-n-Butyl Phthalate and Titanium Tetrachloride 2 By following the procedure of Examp1e 3, except that the 3 solid component obtained in the preceding procedure was used instead 4 in the contact with di-n-butyl phthalate and titanium tetrachloride, there was obtained 8.1 9 of a catalyst component having a titanium 6 content of 2.3%.

8 Contact of 2,2,2-trichloroethanol and n-butylethyl magnesium 9 A flask having an inner volume of 200 ml and provided with a dropping funnel and a stirrer had the interior air displaced with 11 nitrogen gas. In the flask, 5 9 of 2,2,2-trichloroethanol and 40 ml 12 of n-heptanol were kept at 0C. Then, 12.5 ml of the same BEM
13 solution as used in Example 1 was added dropwise at 0C over a period 14 of 30 minutes. The contents of the flask were stirred at 0C for one hour, then heated to 80C over a period of one hour, and then stirred 16 at 80C for one hour. After completion of the reaction, the reaction 17 mixture was washed three times with 50 ml of n-heptane at room 18 temperature and then dried under a vacuum at room temperature for one 19 hour. Consequently, there was obtained a solid reaction product.
Contact with silicon oxide 21 In a mill pot, 5 9 of the solid reaction product obtained in 22 the preceding procedure and 8 g of the same SiO2 as used in Example 23 1 were subjected to a comminution treatment for 24 hours.
24 Contact with di-n-butyl phthalate and titanium tetrachloride By following the procedure of Example 3, except that 6 9 of 26 the comminuted solid substance obtained in the preceding procedure was 27 used instead in the contact with di-n-butyl pthalate and titanium 28 tetrachloride, there was obtained 6.8 9 of a catalyst component having 29 a titanium content of 2.5%.

31 Contact of Silicon Oxide, n-Butylethyl Magnesium, and 32 2,2,2-Trichloroethanol 33 A flask having an inner volume of 200 ml and provided with a 34 dropping funnel and a stirrer had its interior air displaced with nitrogen gas. In the flask, 5 9 of the same SiO2 as used in Example 36 1 and 20 ml of n-heptane were placed. Then 30 ml of the same BEM
37 solution as used in Example 1 was added and subsequently 12 9 of 38 2,2,2-trichloroethanol was added dropwise thereto at 0C over a period lZ4851~

1 of 30 minutes. The resultant mixture was stirred at 0C for one hour, 2 heated to 80C over a period of one hour, and stirred at 80C for one 3 hour. After completion of the reaction, the reaction mixture was 4 washed twice with 50 ml of n-heptane and three times with 50 ml of tolùene at room temperature, to obtain a solid component.
6 Contact with di-n-butyl phthalate and titanium tetrachloride 7 By following the procedure of Example 3, except that the 8 solid component obtained in the preceding procedure was used instead 9 in the contact of di-n-butyl phthalate and titanium tetrachloride, there was obtained 7.5 9 of catalyst component having a titanium 11 content of 2.6%.

13 In a stainless steel autoclave having an inner volume of 1.5 14 liters and provided with a stirrer, a reaction mixture obtained by mixing 30.3 mg of the catalyst component prepared by the procedure of 16 Example 1, 0.97 ml of a solution containing 1 mol of triethyl aluminum 17 (hereinafter referred to as "TEAL") per liter of n-heptane, and 0.97 18 ml of a solution containing 0.1 mol of phenyl triethoxy silane 19 (hereinafter referred to as "PES") per liter of n-heptane and allowing the resultant mixture to stand for five minutes was placed under a 21 blanket of nitrogen gas. Then, 0.1 liter of hydrogen gas as a 22 molecular weight regulator and 1 liter of liquefied propylene were 23 introduced therein under pressure. The reaction system was heated to 24 70C to effect polymerization of propylene for one hour. After completion of the polymerization, the unaltered propylene was purged 26 to produce 105 9 of white polypropylene powder having 97.6% of HI, 4.7 27 of MFR, and 0.42 g/cm3 of bulk density [Kc (amount of produced 28 polymer in 9 per 9 of catalyst component) = 3,500 and Kt (amount of 29 produced polymer in kg per 9 of titanium in catalyst component) = 113].

31 Polymerization of propylene was carried out by following the 32 procedure of Applied Example 1, except that the catalyst components 33 obtained in Examples 2-71 were severally used. The results are shown 34 in Table VI. The polypropylene powder obtained in Applied Example 3 was tested for particle diameter distribution. The results are shown 36 in Table V below.

124~351:1 2 Particle diameter (~m) Proportion of distribution (%) _ _ 3 Less than 149 o 250 - 350 2.3 6 350 - 420 5.9 7 420 - 590 24.9 8 590 - 840 42.3 9 840 - 1,000 12.8 1,000 - 1,680 11.6 11 Exceeding 1,680 0.1 13 Bulk 14 Applied Catalyst Kc Kt HI MFR Density Example Component (9/9 Cat) (kg/g Ti) (~) (9/lO min) (glcm3 16 2 Example 2 3,200 114 97.5 4.5 0.42 17 3 " 3 4,300 179 98.1 4.7 0.44 18 4 " 4 3,900 186 98.0 5.1 0.43 lg 5 " 5 3,900 156 97.9 4.0 0.43 6 " 6 4,300 179 98.4 3.9 0.45 21 7 " 7 3,100 94 97.7 5.5 0.43 22 8 " 8 3,600 120 98.0 5.0 0.44 23 9 " 9 4,000 182 98.0 4.2 0.43 24 10 " 10 3,600 103 97.9 6.2 0.40 11 " 11 3,700 132 97.5 5.8 0.42 26 12 " 12 3,600 171 97.8 4.9 0.41 27 13 " 13 3,900 144 98.2 6.0 0.43 28 14 " 14 3,700 161 98.0 4.9 0.42 29 15 " 15 3,200 200 98.2 5.4 0.44 16 " 16 3,400 243 98.3 5.9 0.45 31 17 " 17 3,100 89 97.8 4.5 0.43 32 18 " 18 2,800 112 97.3 4.8 0.41 33 19 " 19 2,600 113 97.2 5.3 0.40 34 20 " 20 2,900 153 97.6 5.8 0.41 21 " 21 3,900 156 97.8 4.3 0.44 36 22 " 22 3,600 150 97.6 6.2 0.42 37 23 " 23 3,500 140 97.5 5.8 0.43 38 24 " 24 3,900 170 97.9 4.3 0.44 1 TABLE VI, (cont.) 2 Bulk 3 Applied Catalyst Kc Kt HI MFR Density 4 Example Component (y/g Cat) _kg/g Ti) (%) (9/10 min) (g/c ~_ Example 25 4,100 158 98.0 4.9 0.43 6 26 " 26 3,600 129 97.7 5.6 0.43 7 27 " 27 2,900 107 97.5 5.3 0.43 8 28 " 28 3~200 139 97.6 6.1 0.43 9 29 " 29 3,200 145 97.4 5.6 0.42 " 30 2,900 112 97.3 6.7 0.43 1l 31 " 31 3,600 124 97.7 5.4 0.43 12 32 " 32 3,300 122 97.8 4.8 0.41 13 33 " 33 3,700 154 97.6 6.2 0.42 14 34 " 34 2,700 123 97.6 6.3 0.43 -" 35 2,500 96 97.4 7.1 0.42 16 36 " 36 2,800 112 97.2 5.8 0.41 17 37 ~ 37 3,100 135 97.1 6.6 0.43 18 38 " 38 2,900 126 97.3 5.5 0.43 19 39 " 39 2,600 96 97.0 4.6 0.42 " 40 2,500 100 97.4 7.2 0.41 21 41 " 41 3,100 107 97.3 6.8 0.43 22 42 " 42 2,600 118 97.3 6.3 0.42 23 43 " 43 3,000 130 97.9 3.8 0.43 24 44 " 44 3,800 181 98.2 4.0 0.43 " 45 3,200 133 98.0 4.6 0.40 26 46 " 46 3,500 130 98.1 4.2 0.40 27 47 " 47 3,100 124 98.0 4.0 0.42 28 48 " 48 3,300 138 97.9 5.1 0.41 29 49 " 49 2,900 132 97.9 5.8 0.40 " 50 2,900 112 97.8 4.0 0.40 31 51 " 51 2,700 113 97.6 4.6 0.38 32 52 " 52 2,900 116 97.8 4.7 0.39 33 53 " 53 2,800 100 97.5 6.1 0.40 34 54 " 54 2,900 121 97.6 4.0 0.40 " 55 3,100 135 97.6 6.8 0.41 36 56 " 56 3,000 143 97.8 4.2 0.40 37 57 " 57 3,000 100 97.5 4.0 0.40 38 58 " 58 2,900 91 97.6 5.8 0.41 ~24~351~

1 TABLE VI, (cont.) 2 Bulk 3 Applied Catalyst Kc Kt HI MFR Density 4 Example Component (g/g Cat) (kg/g Ti) (%) (9/lO min) (g/cm3) 59 Example 59 3,000 107 97.9 5.2 0.40 6 60 " 60 3,200 145 98.1 4.1 0.43 7 61 " 61 3,000 130 98.0 5.2 0.41 8 62 " 62 2,900 145 97.9 4.8 0.39 9 63 " 63 3,000 130 98.0 4.8 0.41 64 " 64 3,100 148 98.0 5.2 0.40 11 65 " 65 2,800 140 97.4 6.8 0.38 12 66 " 66 2,900 132 97.6 6.5 0.39 13 67 " 67 2,900 116 97.6 6.0 0.39 14 68 " 68 4,000 160 98.1 4.1 0.42 69 " 69 3,900 170 98.0 3.8 0.38 16 70 " 70 3,900 156 98.2 4.5 0.38 17 71 " 71 3,800 146 97.9 4.4 0.40 19 Gaseous-phase Polymerization of Propylene In an autoclave having an inner volume of 5 liters and 21 provided with a stirrer, 150 9 of polypropylene powder dried in 22 advance under a flow of nitrogen gas at 90C for four hours was 23 placed. To this autoclave, with the stirrer thereof operated at 150 24 rpm, the same catalyst component as prepared in Example 3 was fed at a rate of 50 mg/hr, TEAL at a rate of 0.7 mmol/hr, PES at a rate of 0.05 26 mmol/hr, propylene at a rate of 130 g/hr, and hydrogen gas at a rate 27 of 15 ml/hr for continuous polymerization of propylene under the 28 conditions of 70C of temperature and 20 kg/cm2 of pressure, with 29 the product of polymerization continuously withdrawn from the autoclave. Consequently, there was obtained polypropylene powder at a 31 rate of 90 g/hr. The polymer so produced was found to have an MFR of 32 5.2 9/10 min and an HI of 96.8%.

34 Block Copolymerization of Propylene In an autoclave having an inner volume of 1.5 liters and 36 provided with a stirrer, a reaction mixture obtained by mixing 30.0 mg 37 of the catalyst component prepared by the procedure of Example 3, 0.75 38 ml of n-heptane solution of TEAL (1 mol/liter), and 0.75 ml of 1;~485~1 1 n-heptane solution of PES (0.1 mol/liter) and allowing the resultant 2 mixture to stand for five minutes was placed under a blanket of 3 nitrogen gas. Then, 100 ml of hydrogen gas and 1 liter of liquefied 4 propylene were introduced therein under pressure. The reaction system consequently formed was heated to 70C to effect homopolymerization of 6 propylene for one hour. In an experiment of polymerization performed 7 parallelly under the same conditions, the polypropylene obtained was 8 found to have a HI of 98.1%. After completion of the polymerization, 9 the unaltered propylene was purged and the interior of the autoclave was displaced with nitrogen gas. Then, a mixed gas of ethylene and 11 propylene [ethylene/propylene = 1.5 (by mol ratio)] was introduced at 12 such a rate as to keep the monomer gas pressure at 1.5 atmospheres.
13 Under these conditions, copolymerization was effected at 70C for 14 three hours. After completion of the polymerization, the unaltered mixed gas was discharged. Consequently, there was obtained 175 9 of 16 block copolymer of propylene.
17 The proportion of the copolymer fraction calculated based on 18 the consumed amount of the mixed gas and the total amount of polymer 19 was found to be 26.3% and the ethylene content in the total polymer was found by infrared spectral analysis to be 12.6%. Thus, the 21 ethylene content in the copolymer fraction is found by calculation to 22 have been 48%. The amount of the homopolymer of propylene per g of 23 the catalyst component found based on the amount of the total polymer 24 and the consumed amount of the mixed gas was found to be 4,300 9 and the amount of the copolymer fraction formed to be 1,530 9. The block 26 copolymer so produced was found to have a MFR of 2.9 9/10 min and a 27 bulk density of 0.44 g/cm3. The polymer particles were free from 28 cohesion and showed absolutely no sign of fouling in the autoclave.

Random Copolymerization of Propylene and Ethylene 31 During the polymerization of propylene in the procedure of 32 Applied Example 1, 0.6 g of ethylene was introduced under pressure 33 into the autoclave six times at intervals of 10 minutes to effect 34 random copolymerization of propylene and ethylene. After completion of the polymerization, the unaltered monomers were discharged from the 36 polymerization system. Consequently, there was obtained 136 9 of a 37 random copolymer of propylene and ethylene. The ethylene content in 38 the produced copolymer was found by infrared spectral analysis to be ~248 1 2.7%. The amount of the copolymer formed per 1 9 of the catalyst 2 component was 4,500 9. The produced copolymer was found to have a MFR
3 of 12.4 9/lO min and a bulk density of 0.43 g/cm .

Polymerization of l-Butene 6 By following the procedure of Applied Example 1, except using 7 205 mg of the catalyst component obtained in Example 3, 400 ml of 8 isobutane as a medium, and 400 ml of l-butene (liquid) in the place of 9 liquefied propylene and carrying out the polymerization under the conditions of 40C of temperature and five hours of duration, l-butene 11 was polymerized. Consequently, there was obtained 307.3 g of powdery 12 poly-l-butene. The value, Kc, was found to be 1,500 9/9 of catalyst 13 component. The produced polymer was found to have a MFR of 4.1 9/10 14 min, a bulk density of 0.41 g/cm3, and an ether insolubles content (residue after five hours' extraction from boiling diethyl ether) of 16 99.3%.

18 Polymerization of 4-methyl-1-pentene 19 By following the procedure of Applied Example 75, except using 230 mg of the catalyst component obtained by Example 3 and 400 21 ml of 4-methyl-1-pentene in the place of l-butene, 4-methyl-1-pentene 22 was polymerized. Consequently, there was obtained 312.5 9 of powdery 23 poly-4-methyl-1-pentene. The value, Kc, was found to be 1,360 9/9 of 24 catalyst component. The produced polymer was found to have a MFR of 3.5 g/10 min, a bulk density of 0.38 g/cm3, and an ether insolubles 26 content of 98.5%.

Claims (14)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A titanium containing supported catalyst component comprising the product obtained by contacting (1) a reaction product comprising (a) a metal oxide or a composite of metal oxides of Group II, III, or IV of the Periodic Table, (b) a dihydrocarbyl magnesium compound, mixtures thereof or a complex with an organic compound of aluminum, boron, beryllium, or zinc, and (c) a halogen-containing alcohol held with (2) (d) an electron-donating compound and (e) a di-, tri-, or tetravalent titanium compound.

2. The titanium containing supported catalyst component of claim 1 wherein the metal oxide is SiO2.

3. The titanium containing supported catalyst component of claim 1 wherein the dihydrocarbyl magnesium compound is represented by the general formula RMgR' wherein R and R', which can be the same or different, can be an alkyl, cycloalkyl, aryl, or aralkyl group having from 1 to 20 carbon atoms.

4. The titanium containing supported catalyst component of claim 1 wherein the titanium compound is selected from the group consisting of titanium tetrachloride, trichloroethoxy titanium, dichlorodibutoxy titanium and dichlorodiphenoxy titanium.

5. The titanium containing supported catalyst component of claim 1 wherein the electron-donating compound is selected from a group consisting of carboxylic acids, carboxylic anhydrides, carboxylic esters, carboxylic halides, alcohols, ethers, ketones, amines, amides, nitriles, aldehydes, alcoholates, phosphorous, bismuth, and antimony compounds bonded to an organic group through carbon or oxygen atoms, phosphamides, thioethers, thioesters, and carbonic esters.

6. The titanium containing supported catalyst component claim 5 wherein the electron-donating compound is selected from the group consisting of carboxylic acids, carboxylic anhydrides, carboxylic esters, carboxylic halides, alcohols, or ethers.

7. The titanium containing supported catalyst component of claim 1 wherein the halogen-containing alcohol is a monohydric or polyhdric alcohol and the halogen atom is chlorine.

8. The titanium containing supported catalyst component of claim 7 wherein the halogen-containing alcohol is a 2,2,2-trichloro-ethanol.

9. The titanium containing supported catalyst component of claim 1 wherein the reaction product is contacted with the titanium compound at least two times.

10. The titanium containing supported catalyst component of claim 9 wherein the reaction product is contacted with an inactive hydrocarbon, a halide of a hydrocarbon or a metal halide between the titanium halide treatments.

11. A titanium containing supported catalyst component comprising the product obtained by contacting (1) a reaction product comprising (a) SiO2, (b) n-butylethyl magnesium, and (c) 2,2,2-trichloroethanol, with (2) (d) di-n-butylphthalate, and (e) titanium tetrachloride.

12. The titanium containing supported catalyst component of claim 11 wherein the product is treated a second time with titanium tetrachloride.

13. A catalyst system for the polymerization of olefins comprising (A) the titanium containing supported catalyst component of and (B) an organo metallic compound of Group I through III.

14. A process for the homopolymerization of an olefin or the copolymerization of an olefin with another olefin, said process comprising polymerizing the olefin(s) in the presence of the catalyst system of claim 13.