CA1119148A - PROCESS FOR POLYMERIZING .alpha.-OLEFINS WITH AT LEAST 3 CARBON ATOMS AND CATALYST FOR USE IN SAID PROCESS - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

Process for preparing a polymer or copolymer having improved high stereeregularity and apparent density of at least 3 carbon atoms in the presence of catalyst compound of an organoaluminum compound component, an electron and a solid titanium componet; characterized in that said catalyst is composed of (1) an organoaluminum compound composition con-sisting of (a) an organoaluminum compound free from halogen atoms directly bound to the alumium atom expressed by the following formula R'3Al???d(b) an organoaluminum com-pound having halogen atoms directly bound to the alumium atom expressed by the formula R1nA1X?R23-m-m' (2) an electron donor, and (3) a halogen-containing solid titanium component having specific characteristics which is the reaction product of a magnesium compound, an electron donor and tetravalent titanium compound ; and catalyst for use in said process,

Description

'--'' 119148 This invention relates to a process for prepar-ing a polymer or copolymer of an olefin having at least 3 carbon atoms by polymerizing an olefin containing at - least 3 carbon atoms, or copolymerizing olefins contain-- ing at least 3 carbon atoms with each other or with not more than 10 mole% of ethylene or a diolefin. Particularly, it relates to an improved process for preparing a polymer or copolymer of an olefin having at least 3 carbon atoms which has an improved apparent density, especially poly-propylene having high stereoregularity, in a high yield while maintaining a prolonged active lifetime of catalyst.
It also relates to a process and a catalyst used for it, which can afford a polymer having a high apparent density and high stereoregularity even by polymerization at as high as 80 to 90C.
A process has previously been known for preparing a polymer or copolymer of an olefin having at least 3 carbon atoms which comprises polymerizing or copolymerizing an olefin with at least 3 carbon atoms and containing O to 10 mole% of ethylene or a diolefin in the presence of a cata-lyst composed of (i) an organoaluminum compound component, (ii) an electron donor and (iii) a solid titanium com-position.
One example of the catalyst suggested for use in such a process is composed of the reaction product obtained by contacting the following starting components:
(i) an organoaluminum compound free from halogen atoms directly bonded to the aluminum atom;
; (ii) an electron-donor compound (such as a

- 2 -`` 1119148 base) in such an amount that 15% to 100% of the organoaluminum compound (i) is combined with the electron-donor compound; and (iii) a solid component comprising, at least on the surface, the reaction product of a halo-genated magnesium compound with a tetravalent titanium compound and with an electron donor compound, the molar ratio of the electron donor to titanium atom in the product being higher than 0.2 and the molar ratio of the halogen atoms to titanium atom being higher than 4, component (iii) being further characteri~ed in that at least 80% by weight of the tetravalent titanium compound contained in it is insoluble in boiling n-heptane, that at least 50% by weight of the titanium com-pound insoluble in n-heptane is insoluble in TiC14 at 80C., and that the surface area of the portion insoluble in TiC14 at 80C., and the surface area of component (iii) itself are higher than 40 m2/g.
(Japanease Laid-Open Patent Publication No. 151691/77 laid-open on December 16, 1977).
This Japanese Publication gives no description about the use of an organoaluminum compound having halogen atoms directly bound to the aluminum atom, and as shown in (i) above, the description of this Publication is : limited to an organoaluminum compound free from halogen atoms directly bound to the aluminum atom, for example a trialkyl aluminum, a dialkyl aluminum hydride, dialkyl aluminum alkoxide, and an alkyl aluminum sesquialkoxide.

.

`` 11~5'148 In all of the Examples in this suggestion, the isotacticity ~boiling n-heptane-insoluble matter) of polypropylene obtained is 9~.5% at the highest. The apparent density of the polypropylene in these examples is 0.5 (kg/Q) at the highest and 0.4 (kg/Q) at the lowest. According to the measuring method of JIS K-6721 employed by the present application, these values correspond to about 0.~0 g/mQ
at the highest and about 0.25 g/mQ at the lowest. As will be shown in Comparative Examples, these are consider-ably low apparent densities.
The present inventors worked extensively in an attempt to eliminate the defect of low stereoregularity and low apparent density in the above suggested process. Con-sequently, we have found that a good quality polymer or copolymer of an olefin having at least 3 carbon atoms which has a high isotacticity and an apparent density, as measured by the method of JIS K-6721, of at least about 0.35 can be produced by using an organoaluminum compound composition composed of an organoaluminum compound having halogen atoms directly bound to the aluminum atom (the use of which is avoided in the above-cited prior art technique) and an organoaluminum compound free from hydrogen atoms directly bound to the aluminum atom, in which the ratio (X/A1) of the halogen atoms (X) to the aluminum atom (Al) is O<X/Al<l.
Furthermore, it has been found that the above-mentioned improvement can be achieved with the accompany-ing advantages of a prolonged life of the catalyst and a high yield of the product. It is noteworthy that a polymer having a high apparent density and high stereo-,~.

~19148 regularity can be obtained even when polymerization is carried out at a temperature of as high as 80 to 90C.
It is an object of this invention therefore to provide an improved process for producing a polymer or co-polymer of an olefin having at least 3 carbon atoms with 0 to 10 mole~ of ethylene or a diolefin which has an im-proved apparent density and high stereoregularity in a high yield while maintaining a prolonged catalyst life.
Another object of this invention is to provide a catalyst for use in this process.
Other objects and advantages of the invention will become apparent from the following description.
The present invention specifically provides a process for preparing a polymer or copolymer of an olefin having at least 3 carbon atoms which comprises polymerizing or copolymerizing an olefin having at least 3 carbon atoms and containing 0 to 10 mole% of ethylene or a diolefin in the presence of a catalyst composed of an organoaluminum compound component, an electron donor and a solid titanium component;
characterized in that said catalyst is composed of (1) an organoaluminum compound composition consisting of (a) an organoaluminum compound free from halogen atom directly bound to the Al atom expressed by the following formula R 3Al wherein Rl represents a group selected from the class consisting of a hydrogen atom, alkyl groups with 1 to 2 carbon atoms, cycloalkyl groups with ' ' !, '` ' ~ ' .

`~ 1119148 5 to 12 carbon atoms, aryl groups with 6 to 12 carbon atoms, alkoxy groups with 1 to 12 carbon atoms, cycloalkoxy groups with 5 to 12 carbon atoms and aryloxy groups with 6 to 12 carbon atoms, and the three Rl groups are identi-cal or different, and (b) an organoaluminum compound having halogen atoms directly bound to the aluminum atom expressed by the formula R AlX R
n m 3-n-m wherein Rl is as defined above, R represents a group selected from the class consisting of a hydrogen atom, alkoxy groups with 1 to 12 carbon atoms and aryloxy groups with 6 to 12 carbon atoms, X represents a halogen atom, O<nc3, O<m<3, and O<n + m<3, the ratio (X/Al) of the halogen atoms (X) to the aluminum atom (Al) being O<X/Al~l, (2) an electron donor, and (3) a halogen-containing solid titanium component which is the reaction product of a magnesium compound, and electron donor and a tetravalent titanium compound and in which the ratio of the electron donor ~moles)/titanium atom is not less than 0.2, the ratio of magnesium ~moles)/titanium atom is from about 3 to 40 and the ratio of the halogen atoms/titanium atom is not less than 4, the component ~3) being further characterized in that at least 80% by weight of the tetravalent titanium compound contained in it is insoluble in boiling n-heptane, that at least 50% by weight of the tetravalent titanium compound is insoluble in TiC14 at ~ - 6 -;~

~19~48 80C., and that the surface area of the product insoluble in TiC14 at 80C., and the surface area of component (3) as such, is higher than 40 m2/g.
The present invention further provides a catalyst for the poly-merization or copolymerization of an olefin having at least 3 carbon atoms and containing 0 to 10 mole% of ethylene or a diolefin, said catalyst being composed of (1) an organoaluminum compound composition consisting of ~ a) an organoaluminum compound free from halogen atom expressed by the following formula R 3Al wherein Rl represents a group selected from the class consisting of a hydro-gen atom, alkyl groups with 1 to 12 carbon atoms, cycloalkyl groups with 5 to 12 carbon atoms, aryl groups with 6 to 12 carbon atoms, alkoxy groups with 1 to 12 carbon atoms, cycloalkoxy groups with 5 to 12 carbon atoms and aryloxy groups with 6 to 12 carbon atoms, and the three Rl groups are iden-tical or different, and (b) an organoaluminum compound having halogen atoms directly bound to the aluminum atom expressed by the formula R AlX R
n m 3-n-m wherein Rl is as defined above, R represents a group selected from the class consisting of a hydrogen atom, alkoxy groups with 1 to 12 carbon atoms and aryloxy groups with 6 to 12 carbon atoms, X represents a halogen atom, O<n~3, O<m<3, and O<n + m<3, the ratio (X/Al) of the halogen atoms (X) to the aluminum atom (Al) being O<X/Al<l, (2~ an electron donor, and (3~ a halogen-containing solid titanium component which is the reac-tion product of a magnesium compound, an electron donor and a tetravalent titanium compound and in which the ratio of the electron donor (moles)/
titanium atom is not less than 0.2 and the ratio of the halogen atoms/

X

` ~119148 titanium atom is not less than 4, the component (3) being further charac-terized in that at least 80% by weight of the tetravalent titanium compound contained in it is insoluble in boiling n-heptane, that at least 50% by weight of the tetravalent titanium compound is insoluble in TiC14 at 80C., and that the surface area of the product insoluble in TiC14 at 80C., and the surface area of component (3) as such, is higher than 40 m2/g.
In the polymerization or copolymerization of olefins having at least 3 carbon atoms, the sequence of adding the catalyst ingredients (a), Ib), (2) and ~3) is optional. For example, the four ingredients (a), (b), (2) and (3) are mixed simultaneously. Or ingredients (a), (b) and (2) are first mixed simultaneously, and then ingredient (3) is mixed. Or ingred-ients (a) and (b) are first mixed, then ingredient (2) is mixed, and finally ingredient (3) is mixed. Or ingredients (a) and (2) are first mixed, then ingredient (b) is mixed, and finally ingredient (3) is mixed. Or ingred-ients (a) and (2) are first mixed, then ingredient (3) is mixed, and finally ingredient (b) is mixed.
Examples of the organoaluminum compound (a) free from halogen atoms directly bound to the aluminum atom expressed by the formula R13Al are triethyl aluminum, triisopropyl aluminum, triiso-butyl aluminum, tri-hexyl aluminum, triiso-prenyl aluminum, trioctyl aluminum, diethyl aluminum ethoxide, dibutyl aluminum butoxide, ethyl aluminum sesquiethoxide, butyl aluminum sesquibutoxide, diethyl cyclopentyl aluminum, diethyl cyclohexyl aluminum, dimethyl cyclohexyl aluminum, diethyl phenyl aluminum, diethyl p-ethyl phenyl aluminum, dibutyl phenyl aluminum, diethyl aluminum hydride, ; dibutyl aluminum hydride and dioctyl aluminum hydride.
The compound R13Al may be reacted before use with water, ammonia, alcohol or a primary amine by a method known per se.
!' Examples of the organoaluminum compound (b) having halogen atoms ; directly bound to the aluminum atom expressed by the formula RlnAlX R23 n m ; 30 include alkyl aluminum halides such as diethyl aluminum chloride, di-n-butyl '~, :: ~
. .

` 11~9148 aluminum chloride, diiso-butyl aluminum chloride, didecenyl aluminum chlor-ide, diethyl aluminum fluoride, diethyl aluminum bromide, diethyl aluminum iodide, diethyl aluminum sesquichloride, diiso-butyl aluminum sesquichloride and ethyl aluminum difluoride; alkyl aluminum alkoxy halides such as ethyl aluminum ethoxy chloride, butyl aluminum butoxy chloride, octyl aluminum octoxy chloride, ethyl aluminum decenoxy chloride, ethyl aluminum 4-butyl-2,6-di-methyl phenoxy chloride; and aryl aluminum halides such as diphenyl aluminum chloride or p-ethyl phenyl aluminum dichloride.
The alkyl aluminum halide may be reacted prior to use with water, ammonia, alcohol, or a primary amine by a method known per se.
A mixture of a halogen-containing aluminum compound and an organo-metallic compound of a metal of Groups I or II of the periodic table such as a Grignard reagent, a mixture of an organoaluminum compound and a halogen compound of silicon or tin, and a mixture of an organoaluminum compound and an alkyl halide, an alkenyl halide, a halide of a metal of Group I or II of the periodic table or a hydrogen halide can also be used as the organoalum-inum compound (b) of the formula Rl AlXmR 3 n m. They are, for example, organoaluminum compounds having a halogen atom directly bound to the alum-inum atom prepared by the following processes.
(a) RMgX + R'nAlX 3-n ~~~ R"mAlX"3 m + R pMgx 2-p (b) RSnX + R'3Al ~ R"~lX + R"'SnX
(c) RSiX + R'3Al ~ R"AlX + R"'SiX
(d~ ZrC12 + R3Al > R2AlCl + ZnR2 (e~ RX + R'3Al ~ R2AlX + R-R' (f) HX + R2AlR' ~ R2AlX * R'H
In the above formula, R, R', R" and R"' are the same as R given hereinabove; X ls the same as X defined hereinabove; n and m are the same as defined hereinabove; and O<p<2.
In the organoaluminum compound composition (1) composed of the organoaluminum compounds (a) and (b), the ratio (X/Al) of the halogen atom '~, ' ' ' .
, : , ., :
' 119~48 to the aluminum atom (Al) is 0<X/Al<l.
The electron donor (2) used in this invention includes, for ex-ample, amines, amides, ethers, ketones, nitriles, phosphines, stibines, arsines, phosphoramides, esters, thioethers, thioesters, acid halides, aldehydes, alcoholates, organic carboxylic anhydrides, organic carboxylic acids, and amides and salts of metals of Groups I to IV of the periodic table. The salts can be prepared in situ by the reaction of organic car-boxylic acids with ingredient (a) or (b).
Preferred electron donors (2) are selected from organic carboxylic acids having 1 to 22 carbon atoms, organic carboxylic anhydrides having 2 to 22 carbon atoms, organic esters having 2 to 18 carbon atoms, organic acid halides having 2 to 15 carbon atoms, ethers having 2 to 20 carbon atoms, ketones having 3 to 15 carbon atoms, aldehydes having 2 to 15 carbon atoms, organic acid amides having 2 to 8 carbon atoms, amines and nitriles. Of these, organic carboxylic anhydrides, organic carboxylic acids, esters, organic acid halides and esters are especially preferred. They can be used either alone or as mixtures. Or they may be used in the form of coordina-tion compounds with compounds of metals such as aluminum or silicon.
Specific examples of the organic carboxylic anhydride having 2 to 22 carbon atoms (i-a) include aliphatic monocarboxylic acid anhydrides con-taining 2 to 18 carbon atoms such as acetic anhydride, propionic anhydride, n-butyric anhydride, iso-butyric anhydride, monochloroacetic anhydride, tri-fluoroacetic anhydride, caproic anhydride, lauric anhydride and stearic an-hydride; (i-b) aliphatic polycarboxylic acid anhydrides containing 4 to 22 carbon atoms such as succinic anhydride, maleic anhydride, glutaric anhyd-ride, citraconic anhydride, itaconic anhydride, methylsuccinic anhydride, dimethylsuccinic anhydride, ethylsuccinic anhydride, butylsuccinic anhydride, octylsuccinic anhydride, stearylsuccinic anhydridej and methylglutaric an-hydride; (i-c) alicyclic carboxylic acid anhydrides containing 8 to 10 car-bon atoms such as bicyclo[2,2,1]heptene-2,3-dicarboxylic anhydride or methyl-1~19148 bicyclo[2.2.]heptene-2,3-dicarboxylic anhydride; and (i-d) anhydrides of aromatic carboxylic acids containing 9 to 15 carbon atoms such as aceto-benzoic anhydride, benzoic anhydride, p-toluic anhydride, phthalic anhyd-ride, and trimellitic anhydride.
Of these, the aromatic carboxylic acid anhydrides are preferred.
The aliphatic monocarboxylic acid anhydrides are next preferred although they tend to give somewhat low polymerization activity.
Examples of the organic carboxylic acids as the electron donor (2) are the carboxylic acids exemplified hereinabove with regard to the organic carboxylic anhydrides. Especially preferred carboxylic acids are aliphatic carboxylic acids such as formic acid, acetic acid, iso-butyric acid, caprylic acid, oxalic acid, lactic acid, acrylic acid, chloroacetic acid, stearic acid, behenic acid; and aromatic carboxylic acid such as benzoic acid, p-hydroxybenzoic acid, anisic acid, t-butylbenzoic acid, terephthalic acid, acetoxyacetic acid, and toluic acid.
Examples of the organic acid esters having 2 to 18 carbon atoms include aliphatic acid esters (ii-a), alicyclic acid esters (ii-b), and aro-matic acid esters (ii-c).
Examples of the aliphatic esters (ii-a) are esters formed between carboxylic acids or halogen-substitution products selected from the group consisting of saturated or unsaturated aliphatic carboxylic acids containing 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and their halogen-substitution products, and alcohols or phenols selected from the group consisting of saturated or unsaturated ali-phatic primary alcohols containing 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, saturated or unsaturated alicyclic alcohols containing 3 to 8 carbon atoms, preferably 5 to 6 carbon atoms, phenols containing 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, and Cl-C4 saturated or unsaturated aliphatic primary alcohols bonded to the ring carbon atom of a C3-C10 aliphatic or aromatic ring; and lactones ~!

.. , .. ~ , ~:119148 containing 3 to 10 carbon atoms.
Specific examples of the aliphatic esters (ii-a) include primary alkyl esters of saturated fatty acids such as methyl formate, ethyl acetate, n-amyl acetate, 2-ethylhexyl acetate, n-butyl formate, ethyl butyrate, ethyl valerate, methyl acetylacetate, ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate, and octyl acetoacetate; alkenyl esters of saturated fatty acids such as vinyl acetate and allyl acetate; primary alkyl esters of unsaturated fatty acids such as methyl acrylate, methyl methacrylate or n-butyl crotonate; alkyl esters of halogenated aliphatic monocarboxylic acids such as methyl chloroacetate or ethyl dichloroacetate; and lactones such as propiolactone, y-butyrolactone or ~-valerolactone.
Examples of the alicyclic esters ~ii-b) are esters formed between alicyclic carboxylic acids containing 6 to 12 carbon atoms, preferably 6 to 8 carbon atoms, and saturated or unsaturated aliphatic primary alcohols con-taining 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. Specific ex-amples include methyl cyclohexanecarboxylate, ethyl cyclohexanecarboxylate, methyl methylcyclohexanecarboxylate, and ethyl methylcyclohexanecarboxylate.
Examples of the aromatic esters (ii-c) are esters formed between aromatic carboxylic acids containing 7 to 18 carbon atoms, preferably 7 to 12 carbon atoms, and alcohols or phenols selected from the group consisting of saturated or unsaturated aliphatic primary alcohols containing 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, saturated or unsaturated alicyclic alcohols containing 3 to 8 carbon atoms, preferably 3 to 6 carbon atoms, phenol containing 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms and Cl-C4 saturated or unsaturated aliphatic primary alcohols bonded to the ring carbon atom of a C3`C10 ali-phatic or aromatic ring; and aromatic lactones containing 8 to 10 carbon atoms.
Specific examples of the aromatic ester ~ii-c) are alkyl or al-kenyl esters, preferably Cl-C8, more preferably Cl-C4, alkyl esters or .~

~19148 C2-C8, more preferably C2-C4, alkenyl esters, of benzoic acid, such as methyl benzoate, ethyl benzoate, n- and iso-propyl benzoate, n-, iso-, sec-, and tert-butyl benzoates, n- and iso-amyl benzoates, n-hexyl benzo-ate, n-octyl benzoate, 2-ethylhexyl benzoate, vinyl benzoate, and allyl benzoate; cycloalkyl or cycloalkenyl esters of benzoic acid, preferably C3-Cg, more preferably C5-C8, cycloalkyl or cycloalkenyl esters of benzoic acid such as cyclopentyl benzoate, cyclohexyl benzoate or cyclohexenyl benzoate; aryl or aralkyl esters, preferably C6-C10, more preferably C6-C8, aryl or aralkyl esters optionally containing a substituent such as a halo-gen atom or a Cl-C4 lower alkyl group of benzoic acid such as phenyl benzo-ate, 4-tolyl benzoa*e, benzyl benzoate, styryl benzoate, 2-chlorophenyl benzoate or 4-chlorobenzyl benzoate; and aromatic monocarboxylic acid esters in which an electron donating substituent such as a hydroxyl, alkoxy, alkyl or amino group is bonded to the aromatic ring. Examples of the aro-matic monocarboxylic acid esters containing the electron donating substit-uent includes esters of hydroxybenzoic acid, preferably Cl-C8, more prefer-ably Cl-C4, alkyl esters, preferably C2-Cg, more preferably C2-C4, alkenyl esters, preferably C3-C8, more preferably C5-C8 cycloalkyl or cycloalkenyl ~.
esters, and preferably C6-C10, more preferably C8-C10 aryl or aralkyl ..
esters, of hydroxybenzoic acid, typified by methyl salicylate, ethyl sal-~icylate, iso-butyl salicylate, iso-amyl salicylate, allyl salicylate, methyl ; p-hydroxybenzoate, n-propyl p-hydroxybenzoate, sec-butyl p-hydroxybenzoate, 2-ethylhexyl p-hydroxybenzoate, cyclohexyl p-hydroxybenzoate, phenyl sal-icylate, 2-tolyl salicylate, benzyl salicylate, phenyl p-hydroxybenzoate,

3-tolyl p-hydroxybenzoate, benzyl p-hydroxybenzoate and ethyl ~-resorcylate;
esters of alkoxy benzoic acids, preferably esters of lower alkoxy benzoic acids containing 1 to 4 carbon atoms, preferably containing a Cl-C2 alkoxy group, and preferably Cl-C8, more preferably Cl-C4, alkyl esters, or pref-erably C6-C10, more preferably C8-C10, aryl or aralkyl esters of lower alkoxy benzoic acids, such as methyl anisate, ethyl anisate, iso-propyl ~119148 anisate, iso-butyl anisate, phenyl anisate, benzyl anisate, ethyl o-methoxy-benzoate, methyl p-ethoxybenzoate, ethyl p-ethoxybenzoate, n-butyl p-ethoxy-benzoate, ethyl p-allyloxybenzoate, phenyl p-ethoxybenzoate, methyl o-ethoxybenzoate, ethyl veratrate and ethyl asymguacolcarboxylate; esters of alkyl or alkenyl benzoic acids, preferably alkyl or alkenyl benzoatic acids containing preferably Cl-C8, more preferably Cl-C4, alkyl group or C2-C8, more preferably C2-C4, alkenyl group, and preferably Cl-C8, more preferably Cl-C4, alkyl esters and preferably C6-C10, more preferably C8-C10, aryl or aralkyl esters of alkyl or alkenyl benzoic acid, such as methyl p-toluate, ethyl p-toluate, iso-propyl p-toluate, n-and iso-amyl toluates, allyl p-toluate, phenyl p-toluate, 2-tolyl p-toluate, ethyl o-toluate, ethyl m-toluate, methyl p-ethylbenzoate, ethyl p-ethylbenzoate, sec-butyl p-ethyl-benzoate, isopropyl o-ethylbenzoate, n-butyl m-ethylbenzoate, ethyl 3,5-cylenecarboxylate, and ethyl p-styrenecarboxylate; and aminobenzoic acid esters, preferably Cl-C4 alkyl esters of aminobenzoic acid, such as methyl p-aminobenzoate and ethyl p-aminobenzoate. Other examples of the aromatic esters (ii-c) include naphthoic acid esters, preferably Cl-C4 alkyl esters thereof, such as methyl naphthoate, ethyl naphthoate, propyl naphthoate or butyl naphthoate, and aromatic lactones such as coumarine and phthalide.
Of the aromatic esters (ii-c) exemplified above, esters of benzoic acid, alkyl or alkenyl benzoic acids, and alkoxy benzoic acids are preferred.
specially preferred species are Cl-C4 alkyl es~ters, for example, methyl or ethyl esters, or benzoic acid, o- or p-toluic acid, and p-anisic acid.
Examples of the organic acid halides having 2 to 15 carbon atoms as the electron donor (2) are halides of the carboxylic acid exemplified hereinabove with regard to the organic carboxylic anhydrides with 2 to 22 carbon atoms. Specific examples of the acid halides are acetyl chloride, benzyl chloride, toluoyl chloride, anisoyl chloride, stearoyl chloride, iso-butyryl chloride, n-caproyl chloride, and benzoyl chloride.
Examples of the ethers having 2 to 20 carbon atoms include alkyl 1~19148 ethers containing 2 to 20 carbon atoms, preferably 6 to 20 carbon atoms, such as methyl ether, ethyl ether, iso-propyl ether, butyl ether, iso-amyl ether, octyl ether, ethylene glycol butyl ether, and anisole; cyclic ethers containing 2 to 10 carbon atoms such as tetrahydrofuran and tetrahydropyran;
and aromatic ethers containing 7 to 18 carbon atoms such as diphenyl ether.
Examples of the ketones having 3 to 15 carbon atoms are acetone, methyl ethyl ketone, methyl iso-butyl ketone, acetophenone, benzophenone, cyclohexanone, and benzoquinone.
Examples of the aldehydes having 2 to 15 carbon atoms include acetaldehyde, propioaldehyde, octylaldehyde, benzaldehyde, hydroxy benzalde-hyde, tolualdehyde and naphthaldehyde.
Examples of the organic acid amides having 2 to 8 carbon atoms are acetamide, benzamide and toluamide.
Examples of the amines are tributylamine, N,N'-dimethylpiperazine, tribenzylamine, aniline, pyridine, picoline, and tetramethyl ethylene-diamine.
Examples of the nitriles are acetonitrile, benzonitrile, and tolu-nitrile.
The proportion of the electron donor (2) used is preferably about 0.01 to about 1 mole, especially preferably about 0.1 to about 0.5 mole, per aluminum atom of the organoaluminum compound composition (1) composed of the organoaluminum compounds (a) and (b). The ratio between ingredients (a) and (bJ is optional. For example, ingredient (b) is used in an amount of 0.1 to 5 moles per mole of ingredient (a). Depending upon the types of ingredients (a) and (b) (each of which may consist of at least one compound), the prop-ortion of (a) and (b) should be determined such that the ratio (X/Al) of the halogen atom (X) to the aluminum atom (Al) becomes O<X/Al<l.
The halogen-containing solid titanium catalyst component (3) used together with ingredients (a), (b) and ~2) is a complex consisting essen-tially of magnesium, halogen, tetravalent titanium and an electron donor, ,,4'~

`~ 1119~48 and is preferably present in the form of a reaction product of a magnesium dihalide, a tetravalent titanium halide and an electron donor. The ratio of magnesium (moles)/titanium atom is from about 3 to about 40, preferably from about 10 to about 30. The ratio of the halogen atom/titanium atom is at least 4, preferably from about 10 to about 90, more preferably from about 20 to about 80. The ratio of the electron donor (moles)/titanium atom is at least 0.2, preferably from about 0.4 to about 6, more preferably from about 0.4 to about 3.
In the halogen-containing solid titanium component, at least 80%
by weight, preferably at least about 90% by weight, of the tetravalent titan-ium compound is insoluble in boiling n-heptane, and at least 50% by weight, preferably at least about 70% by weight, of the tetravalent titanium com-pound is insoluble in TiC14 at 80C.
The surface area of the portion insoluble in TiC14 at 80 C. and that of the ingredient (3) itself are at least 40 m2/g, preferably at least about 100 m2/g, especially preferably about 100 to about 300 m2/g.
A particularly suitable ingredient (3) is chracterized in that in its X-ray spectrum, the most intense line appearing in the spectrum of mag-nesium dichloride and magnesium dibromide of the normal type defined by standards ASTM 3-0854 and 15-836 for the chloride and bromide, respectively, exhibits a reduced relative intensity and appears asymmetrically broadened, thus forming a halo showing an intensity peak shifted with respect to inter-planar distance d of the maximum intensity line, or the spectrum is charac-terized in that the maximum intensity line is no longer present and in its place a halo appears having an intensity peak shifted with respect to dis-tance d of the aforesaid line. With regard to MgC12, the halo intensity peak is between d = 2.44 R and 2.97 R.
Generally, the composition of ingredient (3) may be expressed as consisting of 70 to 80% by weight of magnesium dichloride or magnesium di-bromide, and the difference from 100% consisting of the titanium compound ~119~48 and the electron donor.
The ingredient ~3) may contain, in addition to the above com-pounds, an inert solid filler in an amount of 80% or more based on the weight of the ingredient ~3).
Examples of such a filler are LiCl, CaCO3, CaC12, Na2S04, Na2C03, 2 4 7 4' 13, B203, A12O3, SiO2, TiO2, naphthalene, and durene It is noted that when ingredient ~3) is prepared in the presence of the inert solid filler, the surface area generally decreases. In par-- ticular, when ingredient ~3) is homogeneously mixed with an agglomerating substance, especially B2O3 or AlC13, the resulting product generally has a surface area below 10-20 m2/g. However, the performance of the catalysts obtained from such ingredient ~3) is still acceptable especially in regard to the yield of polymer.
In the preparation of ingredient ~3), it is possible to support the active constituents or an inert carrier such as SiO2 and A1203 having a high porosity. In this case, the titanium and magnesium halogenated com-pounds and the electron donor make up a reduced proportion with respect to the~total amount, thus permitting the preparation of catalysts in which the -i amount of unwanted materials such as halogen is minimal.
While the Mg/Ti ratio is generally higher than 1, it is lower than 1 when TiO2 and similar inert titanium compounds, such as the titanium salts of oxygen-containing inorganic acids, are used as inert fillers.
The halogen-containing solid titanium component ~d) can be pre-pared by various methods. Preferably, it can be prepared by reacting a solid reaction product between the magnesium compound and the electron donor with the tetravalent titanium compound while maintaining the solid reaction product in the suspended state in the tetravalent titanium compound or both ' the tetravalent titanium compound and an inert organic solvent such as hep-tane, hexane or kerosene.
Examples of useful magnesium compounds are those of the formulae 1~;

" 1119148 MgX2, RQMgX2 Q, Mg(OR)2 QXQ, and MgMe~OR)X, in which X rperesents a halogen atom such as chlorine or bromine or iodine, preferably chloride, R, repre-sents a group selected from the class consisting of alkyl groups preferably with 1 to 12 carbon atoms, and aryl group preferably with 6 to 12 carbon atoms, Me represents Al or Si, and Q represents a positive number of O<Qc2.
Furthermore, in the preparation of ingredient ~3), a hydrated mag-nesium halide containing generally 0.1 to 6 moles of H2O per mole of the halide can be used as a starting material. MgO, Mg(OH)2, Mg(OH)Cl, magnes-ium carbonate, a magnesium salt of an organic acid, magnesium silicate, mag-nesium aluminate, a magnesium alcoholate, and the halogenated derivatives ofthese can also be used. An organomagnesium compound at least containing an Mg-C bond can also be used as a starting material. Examples of such com- -pounds are Grignard reagents, and compounds of the formula MgR2 in which R
is an alkyl, cycloalkyl or aryl group containing up to 20 carbon atoms.
- Examples of the electron donor that can be used to prepare ingred-ient (3) are those given hereinabove with regard to ingredient (2). The electron donor used to prepare ingredient (3) may, or may not, be the same as the electron donor (2).
Suitable tetravalent titanium compounds are, for example, compounds of the formula Ti(OR~)gx4-g wherein R' represents an alkyl group containing 1 to 12 carbon atoms, cyclo-alkyl group containing 5 to 12 carbon atoms and aryl group containing 6 to 12 carbon atoms, X represents a halogen atom such as chlorine, bromine or iodine, and g is a number of 0 to 4.
Specific examples of these titanium compounds are titanium tetra-halides such as TiC14, TiBr4 or TiI4; alkoxytitanium trihalides such as Ti(OCH3)C13, Ti(OC2H5)C13, Ti(On-C4Hg)cl3~ Ti~Cl2H2s)cl3~ Titoc2H5)Br3 or Ti~O iso-C4Hg)Br3; alkoxytitanium dihalides such as Ti(OCH3)2C12, Ti(OC2Hs)2C12, Ti(O n-C4Hg)2Cl and Ti(OC2H5)2Br; trialkoxytitanium mono-~ ' , halides such as Ti~OCH3)3Cl, Ti~OC2ll5)3Cl, Ti(O n-C4Hg)3Cl and Ti(OC2ll5?3Br;
tetraalkoxytitaniums such as Ti(OCH3)4, Ti(OC2H5)4 and Ti~O n-C4Hg)4 and aryloxy titanium halide such as Ti~OC6H5)nC14_n, Ti(OC6H4.CH3)nC14_n and Ti[OC6H2~4-t-C4Hg-2~6~(CH3)2]nC14 n. f these, the titanium tetrahalides are especially preferred. Titanium tetrachloride is most preferred. They may be used as mixtures with the electron donor ~2).
Various means such as those described below can be used in prepar-ing ingredient ~3).
(l-a) A general method consists in starting from a particular composi-tion or carrier comprising a magnesium halide and a complex between the mag-nesium halide and an electron donor in which the mole ratio of Mg/the elec-tron donor is higher than 2 and preferably ranges from 2 to 15, treating the composition or carrier with a liquid tetravalent titanium compound under conditions such that a certain amount of the titanium compound is fixed to the carrier, and subsequently separating the solid reaction product from the liquid phase under conditions such that practically no titanium compound soluble in boiling n-heptane and extractable with TiC14 at 80C. remain in the product.
The peculiar feature of the carrier to be treated with the liquid titanium compound is that it provide an X-ray spectrum in which the diffrac-tion line of maximum intensity appearing in the spectrum of the correspond-ing magnesium halide of normal type exhibits a decreased relatively intensity : and appears asymmetrically broadened so as to form a halo in which the in-tensity peak is shifted with respect to the maximum intensity line, or the maximum intensity line is not present in the spectrum and instead of it, a halo appears having an intensity peak shifted with respect to distance d of the maximum intensity line. However, when such a magnesium halide is fixed to another carrier such as magnesia, the spectrum of the magnesium halide sometimes does not appear in the X-ray spectrum. In this case, the presence of amorphous magnesium halide can be confirmed by analyzing the product ob-.X

l48 tained by extracting the supported magnesium halide with an alcohol, for example.
This carrier, i.e. the starting material for the preparation of ingredient (3) of the catalyst of this invention, can be obtained in various ways.
A preferred method comprises grinding a mixture of a magnesium halide, especially magnesium dichloride or magnesium dibromide, with an electron donor, optionally operating in the presence of a titanium compound and/or an inert co-carrier and/or an agent which facilitates the grinding, such as silicone oils, until the above-described hàlo having the intensity peak shifted with respect to the maximum intensity line appear in the X-ray spectrum of the ground product.
The ground product is treated with a halogenated titanium compound, particularly TiC14, if desired in the presence of an electron donor, at such temperatures (generally between room temperature and 200C.) and for such time periods as are sufficient to fix a proper amount of the titanium com-pound.
The solid product of the reaction is then separated from the liq-uid phase, for example by means of filtration, sedimentation, etc., under such temperature conditions that in the solid product, after extraction with boiling n-heptane and with TiC14 at 80C., amounts of extractable titanium compounds exceeding 20% and 50% by weight respectively are no longer present.
In this method, magnesium alkoxy halides, magnesium aryloxy hal-ides, magnesium alkoxides, magnesium aryloxides and magnesium carboxylate can be used instead of the magnesium halides. In this case, halogenating agents may be used at the time of grinding.
tl b) A method according to method (l-a) except that the starting prod-uct composed of the magnesium halide and the electron donor is prepared in solution instead of the grinding treatment. Specifically, the magnesium halide such as MgX2, Mg(OR)2 QXQ, RQMgX2 Q or MgMe(OR)X is contacted with ~i `` ~il9~48 the electron donor in the presence of a solvent inert to the magnesium halide and/or the electron donor, for example hexane, heptane, kerosene, benzene, toluene, xylene or chlorobenzene at a desired temperature, and the product is treated with the same titanium compound as in method (l-a) in the presence or absence-of the reaction medium.
(l-c) A method which comprises treating a magnesium compound with a halo-genating agent such as chlorine, hydrogen chloride, thionyl chloride, sil-icon tetrachloride, a silicon alkyl chloride, hydrogen bromide or an alum-inum halogen compound, reacting the product with an electron donor, and then treat~ng the product further with a titanium halide. The treatment of the ~-magnesium compound with the halogenating agent is preferably carried out in the presence of a reaction medium, but it can also be performed in the ab-sence of a reaction medium.
A magnesium compound treated with the halogenating agent in the above manner is then subjected to copulverization treatment by method ~l-a), -or to treatment in solution by method (l-b), and then treated with the titanium halide by method (l-a).
(l-d) A~method which comprises treating the magnesium compound and the electron donor in solution by method (l b), subjecting the product to halo-genation treatment in the same manner as in method tl-c), and then treating the resulting product with the titanium halide in the same way as in method -(l-a~.
(l-e) Another method for preparing a carrier suitable for the production of ingredient (3) comprises reacting a magnesium compound, an electron donor (preferably an organic acid ester) and another electron donor in any desired sequence by method (l-a) or (l-c), and treating the reaction product with an organoaluminum compound or a halogenating agent such as silicon halides or tin halides.
The order of reaction can be changed. For example, it is possible to treat a complex formed between the magnesium compound and the electron i, ....... .
-~19~48 donor with the organoaluminum com~ound or the halogenating agent, and treat the resulting product with the electron donor by method Cl a) or (l-b).
Preferably, the treatment of the magnesium compound with the organoaluminum compound, silicon halide or tin halide is performed by sus-pending the magnesium compound in an inert solvent such as hydrocarbon, and adding the organoaluminum compound or the halogenating agent (e.g., silicon halide or tin halide), either alone or as a solution in an inert solvent, to the suspension. Generally, the reaction proceeds sufficiently at room tem-perature, and heating is not particularly necessary. Heating, however, is generally advantageous since it promotes the reaction.
The resulting product is washed with an inert hydrocarbon solvent to remove traces of free organoaluminum compound or halogenating agent such as a silicon halide or tin halide, then reacting the product with a titanium compound, especially TiC14 as in method (l-a), and separating the solid reac-tion product so that substantially no titanium compound extractable with boiling n-heptane and with TiC14 at 80C. remains on the solid component.
The details of these methods are shown in Japanese Laid-Oyen Pàtent Publication No. 28189/76 (laid open on March 9, 1976) and Japanese Laid-Open Patent Publication No. 92885/76 ~laid open on August 14, 1976;
West German Laid-Open Patent Publication (OLS) No. 2605922).
When a magnesium halide is used in the methods described above, and especially when the catalyst ingredient is prepared by pulverization, the magnesium halide is preferably as anhydrous as possible (an H2O content of not more than 1% by weight).
When a magnesium aryloxyhalide or aralkoxyhalide is used as the magnesium compound in the preparation of ingredient (3), it is preferred to employ a method which involves reacting it with an organic acid ester as the electron donor, and then reacting the product with a titanium halide in the same way as in the aforesaid methods. The details of this method are shown in Japanese Laid-Open Patent Publication No. 147688/77 (laid open on !L~.

December 8, 1977).
When organomagnesium compounds, magnesium alkoxides, magnesium aryloxides, magnesium alkoxyhalides, or magnesium aryloxyhalides are used as the magnesium compound, it is also possible to react a reaction product between the magnesium compound and a halogenating agent and an electron donor (preferably an organic acid ester), with a titanium halide in prepar-ing ingredient ~3).
~l-f) When a magnesium compound of the formula MgR2 is used, it is re-acted with a compound having the ability to destroy the Mg-R bond of MgR2 such as a halogen-containing silicon or tin compound or with an ester, amine, carboxylic acid or its metal salt, keteone, aldehyde or with a mix-ture of such a compound and aluminum, etc. Then, the reaction product is reacted with an excess of TiC14 in the presence of the electron donor (2).
Then, the solid reaction product is separated at an elevated temperature.
The resulting solid product as a suspension in an inert hydrocar-bon is treated with 1 to 20 moles, per titanium atom contained in the car-rier, of an electron donor, especially an organic acid ester such as an aromatic carboxylic acid ester, at room temperature to 200C.
The solid reaction product treated by this method is accurately separated from the unreacted electron donor, and then reacted with a halo-genated titanium compound, after which the reaction product is separated from the liquid phase by method ~l-a).
It is important that in the above-described methods, at least 80%
by weight of the titanium compound contained in ingredient ~3) should be in-soluble in boiling n-heptane, and not more than 50% of the titanium compound should be extractable with TiC14 at 80C. In fact, the presence of a sol-uble titanium compound is disadvantageous both to the activity and stereo-specificity of the catalyst especially when the polymerization is carried out in the presence of hydrogen.
According to this invention, an olefin having at least 3 carbon atoms and containing 0 to 10 mole~ of ethylene or a diolefin is polymer-ized or copolymerized in the presence of a catalyst composed of the ingred-ients ~a), (b), (2) and (3) described hereinabove.
Examples of suitable olefins are ~-olefins with 3 to 16 carbon atoms such as propylene, l-butene, 4-methyl-1-pentene, l-octene, l-decene and l-hexadecene. Examples of the diolefin are butadiene, 1,4-hexadiene, 1,7-octadiene, and ethylidene norbornene.
The process of this invention is especially useful for obtaining highly stereoregular polymers or copolymers of ~-olefins having at least 3 carbon atoms in high yields. The polymerization may be homopolymerization, random copolymerization, or block copolymerization. For example, when propylene is to be copolymerized with ethylene, it is possible to polymer-ize propylene until a homopolymerization in an amount of about 60 to about 90% based on the entire composition is obtained, and subsequently polymer-izing a mixture of propylene and ethylene, or ethylene. Alternatively, a mixture of propylene and ethylene may be polymerized so as to obtain a co-polymer containing ethylene in a proportion of not more than about 10 mole%.
The polymerization can be performed either in the liquid phase or in the vapor phase. When the polymerization is carried out in the liquid phase, an inert solvent such as hexane, heptane or kerosene may be used as a reaction medium. The olefin itself may also be used as a reaction medium.
In the liquid phase polymerization, it is preferred to use 0.0001 to 1 milli-mole, calculated as titanium atom, of ingredient (3), 0.001 to 100 milli-moles, calculated as aluminum atom, of ingredient (a), 0.001 to 100 milli-moles, calculated as aluminum atom, of ingredient (b), and 0.001 to 100 millimoles of ingredient ~2) and adjusting the amount of aluminum in the ingredients (a) and (b) to 1 to 100 moles, preferably 1 to 300 moles, per mole of titanium in ingredient (3), all per liter of the liquid phase.
In the vapor phase polymerization, a fluidized bed or a stirred fluidized bed is usually employed. The ingredient ~3) is used either as a solid or as diluted with hexane or an olefin, and ingredients (a), (b) and (2) are either diluted, or not diluted, with hexane or an olefin prior to feeding into the polymerization reactor. An olefin and if desired hydrogen are fed into the polymerization reactor in the form of gases. The propor-tions of the catalyst ingredients are the same as in the case of the liquid phase polymerization.
The polymerization temperature is generally 20 to 200C., prefer- -ably 50 to 180C. Particularly, the highly stereoregular polymerization of propylene is carried out at a temperature of 50 to 140C., and a pressure of atmospheric pressure to 50 kg/cm2, preferably 2 to 20 kg/cm2.
1. Preparation of ingredient (3) Anhydrous magnesium chloride ~20 g) and each of the electron don-ors indicated in Table 1 were placed in a stainless steel ~SUS-32) ball mill vessel having an inner capacity of 800 ml and inside diameter of 100 mm and containing 2.8 kg of stainless steel ~SUS-32) balls each having a diameter of 15 mm, and were contacted for 24 hours at an impact acceleration of 7G
in an atmosphere of nitrogen. Ten grams of the resulting solid was suspended in 100 ml of titanium tetrachloride, and contacted with stirring at 80C.
for 2 hours. The solid product was collected by filtration, and fully washed with~purified hexane until no free titanium tetrachloride was detec*ed in the wash liquid. Thus, the halogen-containing solid titanium components described in Table 1 for use as ingredient ~3) were prepared.
The titanium-insoluble portion of ingredient ~3) was measured by the following method.
The total amount of titanium in ingredient (3) used as a catalyst ingredient was measured by the hydrogen peroxide chlorimetric method.
The amount of trivalent titanium was measured by the potassium per-manganate method, and the amount of tetravalent titanium was calculated by subtracting the amount of trivalent titanium from the total amount of titan-ium.

. .
,,,~7 -~119148 Five grams of ingredient ~3) used as a catalyst ingredient was mixed and stirred in 100 ml of boiling n-heptane for 1 hour. The n-heptane was separated, and the residue was washed twice with room-temperature n-heptane in an atmosphere of nitrogen and dried under reduced pressure. By the same method, the amount of titanium was measured, and the proportion of the portion insoluble in boiling n-heptane was calculated.
Furthermore, 5 g of ingredient (3) was suspended in 100 ml of titanium tetrachloride, and stirred at 80C. for 1 hour in an atmosphere of nitrogen. The titanium tetrachloride was separated, and in an atmosphere of nitrogen, the residue were washed four times with hexane, and dried at room temperature under reduced pressure. The amount of titanium was measured by the same method, and the proportion of the portion insoluble in titanium tetrachloride at 80C. was calculated.
The specific surface area of the halogen-containing solid titanium component used as ingredient (3), and the specific surface area of the solid titanium component extracted with titanium tetrachloride at 80C. were mea-sured by the nitrogen adsorption method.
In the following tables Et stands for ethyl, Me, methyl; and Bu, butyl.

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2. Preparation of ingredient ~3) Halogen-containing solid titanium components were prepared in the same way as in 1 except that each of`the magnesium compounds and titanium compounds shown in Table 2 was used instead of the magnesium chloride and titanium tetrachloride, and 2 ml of ethyl benzoate was used~as the electron donor. The results are shown in Table 2.

_ 28 -X~

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^ 1119148 3. Preparation of ingredient (3) (3-1) Commercially available magnesium dichloride (5 g; 52.5 millimoles) was suspended in 100 ml of hexane, and 105 millimoles of butanal, 52.5 mil-limoles of 2-ethylhexanol and 10.5 millimoles of butyl toluate were added dropwise at room temperature. The mixture was stirred at 110C. for 1 hour.
To the mixture was added dropwise 79 millimoles of diethylaluminum chloride, and the mixture was stirred for 1 hour. The resulting solid was collected by filtration, and washed fully with hexane. The solid was suspended in 100 ml of titanium tetrachloride, and the suspension was stirred at 100C.
for 2 hours. The supernatant liquid was removed, and 100 ml of titanium tetrachlo~ide was added. The mixture was stirred at 100C. for 1 hour, hot-filtered, and washed with hexane to afford ingredient (3). The product is designated as ingredient (3) catalyst No. (3-1).
(3-2) The same procedure as in (3-l) was repeated except that 157.5 millimoles of silicon tetrachloride was used instead of the diethylaluminum chloride, and after the addition of silicon tetrachloride, the mixture was stirred at 60C. for 10 hours. The resulting halogen-containing solid titan-ium component was designated as ingredient (3) catalyst No. (3-2).
(3-3) Diethoxy magnesium (5 g; 43.7 millimoles) was suspended in 50 ml of kerosene, and 10.9 millimoles of butyl benzoate was added. Then, an-hydrous hydrogen chloride was pas~ed into the suspension at 0C. for 1 hour, and the suspension was further stirred for 1 hour at 20C. Ingredient (3) was prepared by operating in the same way as in the preparation of catalyst No. (3-1) except that the amount of titanium tetrachloride was adjusted to 300 ml and the temperature at which to treat the product with titanium tet-rachloride was changed to 110C. The resulting product is designated as ingredient (3) catalyst No. (3-3).
The catalysts Nos. (3-1), (3-2) and (3-3) are shown in Table 3.

4. Preparation of in~redient (3) (4-1) Commercially available anhydrous magnesium dichloride (5 g; 52.5 -` 1119148 millimoles) was suspended in 200 ml of toluene, and 315 millimoles of ethanol was added dropwise at room temperature. The mixture was stirred at room temperature for 1 hour. Trioctyl aluminum (630 millimoles) was added dropwise at 0C., and the mixture was stirred at 80C. for 6 hours. The re- -sulting solid was separated by filtration, and washed fully with hexane.
The resulting solid was suspended in 100 ml of toluene, and 7.5 millimoles of p-methoxyethyl benzoate was added dropwise at room temperature. The mix-ture was stirred at 70C. for 1 hour. The solid was collected by filtra-tion, washed fully with hexane, and dried. The product was treated with titanium tetrachloride under the same conditions as in the preparation of the catalyst No. (3-1) to afford ingredient (3). This product is designated as ingredient (3) catalyst No. (4-1).
(4-2) The procedure of the preparation of the ingredient (3) catalyst No. (4-1) was repeated except that 630 millimoles of tin tetrachloride was used instead of the trioctyl aluminum. Thus, ingredient (3) catalyst No.
(4-2) was obtained.
The resulting catalysts Nos. (4-1) and ~4-2) are shown in Table 3.

5. Preparation of ingredient ~3) ~5-1) Commercially available magnesia ~5 g) was suspended in 100 ml of kerosene, and 20 g of thionyl chloride was added. The mixture was stirred at 70C. for 18 hours, and 1.3 g of ethyl cyclohexyl carboxylate was added.
The mixture was stirred at 70C. for 1 hour, and filtered. The solid sep-arated was washed to afford a solid reaction product. The solid product was suspended in 300 ml of titanium tetrachloride, and stirred at 100C. for 2 hours. The product was hot-filtered and washed with hexane to afford a solid product. The product is designated as ingredient ~3) catalyst No.
(5-1).
(5-2) Commercially available magnesium hydroxide ~5 g) was suspended in 100 ml of kerosene, and chlorine gas was added. The suspension was stirred at 80C. for 6 hours. Then, 1.5 g of ethyl benzoate was added, and the mix-~7 i~.

-`` 11~9~48 ture was stirred at 70C. for 1 hour. It was filtered, and washed to afford a solid reaction product. The solid product was treated with titanium tet-rachloride in the same way as in the preparation of the catalyst No. (5-1).
The product is designated as ingredient (3) catalyst No. (5-2).
(5-3) Magnesium benzoyl chloride (5 g) was suspended in 100 ml of hex-ane, and hydrogen chloride was added at 0C. The suspension was stirred at 30C. for 6 hours. Then, 1.5 g of n-butyl benzoate was added, and the mix-ture was stirred at room temperature for 1 hour. Hexane was evaporated, and 100 ml of titanium tetrachloride was added to the resulting solid. The mixture was stirred at 110C. for 2 hours. The supernatant liquid was re-moved, and 100 ml of titanium tetrachloride was added. The mixture was stirred at 110C. for 1 hour, filtered, washed and dried to afford a product designated as ingredient (3) catalyst No. (5-3).
The catalysts Nos. (5-1), (5-2) and (5-3) are shown in Table 3.

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" , Examples 1 to 31 and Comparative Examples 1 to 3 Propylene was polymerized using each of the halogen-containing solid titanium components prepared by methods 1 to 5 above, and the organo-aluminum components (a) and (b) and the electron donors (2) shown in Table 4. The results are shown in Table 4.
In Examples 1 to 24 and Comparative Examples 1 to 3, a 2-liter autoclave was used, and in Examples 25 to 31, a l-liter glass flask was used. The amount of ingredient 13), as titanium atom, was 0.015 millimole in Examples 1 to 19; 0.001 millimole in Example 20; 0.002 millimole in Ex-amples 21 to 24; 0.05 millimole in Examples 25 to 31; and 0.015 millimole in Comparative Examples 1 to 3.

" ~

~ 1119148 Table 4 ~ .
Comparative Example 1 2 3 .
Solvent hexane hexane hexane Amount of solvent ~ml~ 750 750 750 Pressure of propylene ~ ~:
~kg/cm2Gj 7 7 7 Polymerization tempera-ture (C.) 70 70 70 Polym~rization time ~hrs) 4 4 0.5 Presence of hydrogen Yes Yes Yes Ingredient ~a) t3Al _ Et3Al Amount ~mmoles) 1.5 _ 1.5 Ingredient ~b) _ Et2AlCl Et2AlCl :
Amount ~mmoles) _ 1.5 1.5 X/Al ratio 0 1 0.5 Electron donor ~2) Me ~G2Me Me~O2M~ _ Amount (mmole) 0.5 0.15 _ (3) Catalyst No. 1-1 1-1 1-1 = ~ = = = _ = = = . ~ = _ ~
Yield (g-pp/mmole Ti) 15,000 4,500 11,000 : .
Isotacticity (%) 93.2 94.3 65.2 Apparent density (g/ml) 0.39 0.38 0.24 Melt index 3.9 8.6 35.5 . ,:

,, - - . .- :
.: . . . :
.

` 1119148 Table 4 (continued) .....
Example 2 3 .
Solvent Hexane Hexane Hexane Amount of solvent ~mll 750 750 750 Pressure of propylene (kg/cm2G) 7 7 7 Polymerization tempera-ture (C.) 70 70 70 Polymerization time (hrs) 4 4 4 Presence of hydrogen Yes Yes Yes Ingredient (a) 3 1 ( 8 17)3 3 .
Amount (mmoles)0.75 0.75 0.75 Ingredient (b)Et3AlCl (n-BU)2AlCl Et2AlCl Amount (mmoles)0.75 1.5 2.25 X/Al ratio 0.5 0.67 0.75 Electron donor (2) e ~ o2Me Me ~ 02Et Me ~ 02Et Amount (mmoles) 0.375 0.375 0.375 (3) Catalyst No. 1-1 1-2 1-3 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ = _ ~ ~
_______ ____ ______ _ __ Yield (g-pp/mmole Ti) 21,400 17,300 15,200 Isotacticity (%) 96.0 95.2 94.8 Apparent density (g/ml) 0.45 0.41 0.39 Melt index 2.4 2.1 2.8 -` 1119148 Table 4 (continued) Example 45 6 Solvent Hexane Hexane Hexane Amount of solvent (ml) 750 750 750 Pressure of propylene (kg/cm2G) 7 7 7 Polymerization tempera-ture (C.) 70 70 70 Polymerization time (hrc ) 4 4 4 Presence of hydrogenYes Yes Yes Ingredient (a)(i-Bu)3Al Et2AlH~i-Bu)2 gAl~OEt~o 1 Amount ~mmoles)1.125 0.75 1.0 Ingredient ~b) ~i-Bu)2Alcl Et2AlCl~i-BU)2AlC
Amount ~mmoles) 1.125 0.75 1.25 X/Al ratio 0.5 0.5 0.56 Electron donor ~2) e ~ O2Me ~ C2Et Me ~ O2Me Amount (mmole) 0.563 0.428 0.625 (3~ Catalyst No. 1-4 1~S5 1-6 _ _ _ _ .
_ = = = = = = = = _ -- = . _ _ _ _ ; =~
Yield (g-pp/mmole Ti) 12,000 12,800 13,100 Isotacticity (%) 94.0 93.8 92.9 Apparent density (g/ml) 0.42 0.40 0.41 Melt index 3.0 4.1 4.3 .~."i " 1119148 Table 4 (continued) _ Example 7 8 9 Solvent Hexane Propylene Propylene Amount of solvent ~ml) 750 500 g 500 g Pressure of propylene (kg/cm2g) 7 25 30 Polymerization tempera- ~.
ture (C.) 70 60 70 Polymerization time ~hrs) 4 1 1 Presence of hydrogen Yes Yes Yes Ingredient (a) Et3Al t3 (i-Bu)3A
Amount (mmoles)O.75 O.5 O.5 Ingredient ~b)Et2AlCl Et2AlCl ~i-BU)2AlC
Amount (mmoles)0.375 0.25 0.5 X/Al ratio 0.33 0.33 0.5 Electron donor (2) Me 0 ~ 02Et Me ~ 02Bu ~ 2BU
Amount (mmoles) 0.375 0.25 0.23 (3) Catalyst No. 2-1 2-2 2-3 _ _ _ _ _ _ _ _ _ _ _ _ _ _ ~ _ _ _ ._ _ Yield (g-pp/mmole Ti) 7,700 8,300 17,000 Isotacticity (%) 96.0 94.4 93.2 Apparent density (g/ml) 0.40 0.42 0.43 Melt index 2.0 1.8 1.5 _ ., .

Table 4 (continued) . , Example 10 11 12 Solvent PropylenePropylene Propylene Amount of solvent (g) 500 500 500 Pressure of propylene (kg/cm2G) 30 25 30 ; Polymerization tempera-ture (C.) 70 60 70 Polymerization time (hr 1 1 1 -Presence of hydrogen Yes Yes Yes Ingredient (a) Et3Al Et3Al (i-Bu)3A
Amount (mmoles) 0.5 0.5 0.5 Ingredient (b) Et2AlClEt2AlCl Et2AlCl Amount (mmoles) 0.75 0.25 0.25 X/Al ratio 0.6 0.33 0.33 Electron donor (2) e ~ 02Me Me ~ 02Me Et ~ 02Et Amount (mmoles) 0.25 0.25 0.33 (3) Catalyst No. 2-4 2-5 2-6 === = ===-- . ~ = = = = = = =_ .
Yield (g-pp/mmole Ti) 15,700 3,gO0 3,200 Isotacticity (%) 93.6 94.6 94.8 Apparent denstiy (g/ml) 0.42 0.41 0.42 Melt index 1.3 1.7 1.0 :

~ - 39 -.- , Tab].e 4 (continued) _ _ _ Example 13 14 15 _ Solvent Propylene Propylene Propylene Amount of solvent (g) 500 500 500 Pressure of propylene (kg/cm2G) 25 30 30 Polymerization tempera ture (C.) ¦60 70 70 Polymerization time (hr) 1 1 1 Presence of hydrogen Yes Yes Yes Ingredient (a) 3 Et3Al Et3 1 Amount (mmoles) 0.5 0.5 0.5 Ingredient (b) Et2AlCl Et2AlCl Et2AlCl Amount (mmoles) 0.25 0.25 0.5 X/Al ratio0.33 0.33 0.5 Electron donor (2) Me ~ C2Me MeO ~ O2Me Me ~ C2Me Amount (mmolé) 0.33 0.33 0.33 (3) Catalyst No. _2-7 2-8 _ _ _ _ _ _ _ _ _ ~_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ . _ _ _ _ _ _ _ _ _ _ _ _ _ __ Yield (g-pp/mmole Ti) 15,100 17,800 14,900 Isotacticity (%) 94.1 93.8 93.1 Apparent density (g/ml 0.41 0.42 0.40 Melt index 1.4 3.0 1.2 ,7 , ~", --" 1119148 : `

Table 4 (continued) Example ~ 17 18 Solvent Propylene Hexane Kerosene Amount of solvent (ml) 500 g 750 750 Pressure of propylene (kg/cm2G) 25 7 7 Polymerization tempera ture ( C.) 60 70 60 Polymerization time (hrs) 1 4 4 Presence of hydrogen Yes Yes Yes Ingredient (a) (i-Bu)3Al ( 8 17)3 (i-Bu)2AlH
Amount (mmoles) 0.5 0.75 0.75 Ingredient (b) Et2AlCl C8H17AlC12 Et2AlCl Amount (mmoles)0.25 0.3 0.9 X/Al ratio 0.33 0.57 0.55 Electron donor (2) Me ~ 02Me MeO ~ 02Bu Me ~ O2Et Amount (mmoles)0.33 0.375 0.556 -(3) Catalyst No. 2-10 4-1 4-2 ,_-- _ _ _ _ _ _ _ _ _ _ _ _ _ . _ _ _ _ _ . _ _ _ _ _ _ _ Yield (g-pp/mmole Ti) 14,400 13,000 12,600 Isotacticity (%) 94.5 94.3 93.8 Apparent density (g/ml 0.40 0.40 0.40 Melt index 1.4 2.5 4.8 ~ . ..

~119148 Table 4 ~continued) .. . _ .
Example 19 20 21 Solvent Heptane Propylene Propylene Amount of solvent (ml) 750 500 g 500 g Pressure of propylene (kg/cm2G) 9 30 30 Polymerization temper _ ture (C.) ¦ 85 80 70 Polymerization time (hrs) 4 0.5 1 Presence of hydrogenYes Yes Yes Ingredient (a)(n-Bu)3Al Et2Al ~ Me3Al Amount (mmoles) 1.5 0.5 0.5 Ingredient (b)Etl 5AlC11 5 EtAl(OEt)Cl tAl~OBu)Cl Amount (mmoles) 1.5 0.5 0.5 X/Al ratio 0.75 0.5 0.5 ,_~e Electron donor (2) Me ~ O2Me HO ~ OO-C8H 7 ~ CO2Et Amount (mmoles) 0.75 0.33 0.33 (3) Catalyst No.4-3 5-1 5-2 ~ _=_ == _ . ~ == = = == = _ = = .
Yield (g-pp/mmole Ti) 10,600 21,600 15,400 Isotacticity (%)95.0 95.0 94.3 Apparent density (g/ml) 0.41 0.45 0.43 Melt index ¦ 3.5 2.1 1.5 Table 4 ~continued) Example 22 23 24 . . _ _ Solvent Propylene PropylenePropylene Amount of solvent (g) 500 500 500 Pressure of propylene (kg/cm2G) 25 25 30 Polymerization tempera-ture (C.) 60 60 70 Polymerization time (hrs) 1 1 1 Presence of hydrogenYes Yes Yes Ingredient ~a) 3 Et2 gAl(C8H17)01 t3Al Amount (mmoles) 0.5 0.50 5 Me Ingredient (b) Et2AlCl EtAl(OC8H17)ClEtAl(0 ~ u)Cl Amount (mmole) 0.25 0.25 0.25 X/Al ratio 0.33 0.33 0.33 Electron donor (2) Me ~ C2BU (Me)2N ~ CO2Et Et ~ o2Et Amount (mmoles) 0.25 0.2 0.33 (3) Catalyst No 6-1 6-2 6-3 _ _ _ __ _ _ _ _ _ _ _ _ _ ~ . _ _ __ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Yield (g-pp/mmole Ti)10,400 8,700 21,300 ~-Isotacticity (%) 93.9 94.1 96.3 Apparent density (g/ml)~ 0.44 0.38 0.40 Melt index 3.5 1.0 1.9 _ _ :

Table 4 tcontinued) Example 25 26 27 _ _ Solvent Kerosene KerosencKerosene Amount of solvent (ml) 500 500 500 Pressure of propylene (atms) l l Polymerization tempera-ture (C.) 60 60 60 Polymerization time (hr) 1 1 1 Ingredient (a) 3Al Et3Al 3 Amount (mmoles) 1.5 1.5 1.5 Ingredient (b) (i-BU)2AlCl Et2AlCl Et2AlCl Amount (mmoles) l 1.5 1.5 X/Al ratio 0.4 0 5 O.H5 Electron donor (2)(MeC0)2o ( ~ C0)20 ~ CH0 Amount (mmole) 0.83 0.83 0.83 (3) Catalyst No. 1-2 1-2 1-2 Specific activity (g-pp/mmoles Ti-h atm of propylene)507 1,344 2,086 Isotacticity (%) 98.5 97.8 92.1 Apparent density (g/ml) 0.35 0.35 0.35 j 3~1i9~8 Table 4 (continued) _ Example 28 29 30 _ Solvent Kerosene KeroseneKerosene Amount of solvent (ml) 500 500 500 Pressure of propylene (atms) 1 1 1 Polymerization tempera-ture (C.) 60 60 60 Polymerization time (hr) 1 1 1 Ingredient (a) 3 t3Al 3 Amount (mmoles) 1.5 1.5 1.0 Ingredient (b) Et2AlCl Et2AlCl Et2AlCl ~ -Amount (mmoles) 1.5 1.5 1.0 X/Al ratio 0.5 0.5 0.5 Electron donor (2) CH3COOH Bu ~ OOH CH3(CH2)4cooc5 . Amount (mmoles) 0.83 1.5 0.56 : (3) Catalyst No. 1-2 1-2 1 2 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ __ _ _ _ _ _ _ _ _ _ _ ~
Specific activity (g-pp/mmoles Ti h-atm of propylene)1,879 673 954 Isotacticity (%) 88.5 95.1 91.3 . Apparent density 0.35 0.35 0.37 .

~

,, ~

~119148 Table 4 (continued) Example 31 _ .

Solvent Kerosene Amount of solvent (ml) 500 Pressure of propylene 1 (atms) Polymerization tempera-ture (C.) 60 Polymerization time (hr) 1 Ingredient (a) 3 Amount (mmole) 1.0 Ingredient (b)Et2AlCl Amount (mmole)1.0 X/Al ratio 0.5 Electron donor (2) 3 0 H2 2 5 Amount (mmole)0.56 ~ = _ = ==~
Specific activity (g-pp/mmoles.Ti.1,014 h-atms of propylene) Isotacticity (%)97.6 Apparent density 0.37 Example 32 Preparation of ingredient (3) Anhydrous magnesium chloride (20 g), 5.0 ml of ethyl benzoate and 3.0 ml of methylpolysiloxane (viscosity 100 centipoises at 25C.) were placed in an atmosphere of nitrogen in a stainless steel (SUS-32) ball mill vessël having an inner capacity of 800 ml and an inside diameter of 100 mm and con-taining 2.8 kg of stainless steel (SUS-32) balls each having a diameter of 15 mm, and were contacted for 24 hours at an impact acceleration of`7G. Ten grams of the resulting solid product was suspended in 100 ml of titanium tet-rachloride. The mixture was stirred at 80C. for 2 hours. The solid was collected by filtration, and fully washed with purified hexane until no free titanium tetrachloride was detected in the wash liquid. It was then dried -` ~119~8 to afford a titanium complex which contained 2.0% by weight of titanium atom, 64.0% by weight of chlorine atom, 23.0% by weight of magnesium atom, and 7.60% by weight of ethyl benzoate and has a surface area of 194 m2/g.
Polymerization A l-liter flask was charged with 500 ml of purified kerosene, and in an atmosphere of propylene, with 1.25 millimoles of triethyl aluminum and 0.83 millimole of methyl p-toluate. They were stirred for 15 minutes, and then 1.25 millimoles of diethylaluminum chloride was added. The mixture was stirred for another 15 minutes. Then, 0.1 millimole, calculated as titanium atom, of ingredient (3) was added. The mixture was heated to 60C., and polymerization was performed for 1 hour with stirring.
The resulting solid was filtered, and dried to afford 73.8 g of polypropylene as a white powder. The polymer had a boiling n-heptane ex-traction residue of 99.1% and an apparent density of 0.40 g/ml. Concentra-tion of the liquid phase afforded 2.0 g of a solvent-soluble polymer. The specific activity of the catalyst was 758 g-pp/mmol.Ti.h.atm.
Example 33 The same polymerization as in Example 32 was performed except that the amount of triethyl aluminum was changed to 0.83 millimole and the amount of diethylaluminum chloride was changed to 2.5 millimoles. There was obtained 53.5 g of a white powdery polymer having a boiling n-heptane extraction res-idue of 99.0% and an apparent density of 0.39 g/ml. The amount of a solvent-soluble polymer was 0.8 g. The specific activity of the catalyst was 543 g-pp/mmol.Ti. h.atm.
Example 34 A 2-liter autoclave was purged with-propylene, and at room tem-perature, with 2.25 millimoles of triethyl aluminum, 1.5 millimoles of di-ethylaluminum chloride, 1.25 millimoles of methyl toluate, and 0.0225 milli-mole of the ingredient (3) catalyst No. (1-1) in this order. Then, hydrogen gas was introduced, and the temperature wasraised. At 55C., a gaseous mix-~19~48 ture consisting of 93.1 mole% of propylene, 2.8 mole% of ethylene and 4.1 mole% of l-butene was fed, and polymerized for 2 hours while maintaining the pressure at 2.5 kg/cm G. Filtration and washing with hexane afforded 199.6 g of a white powdery polymer. Infrared analysis showed that the white pow-dery polymer contained 2.0 mole% of ethylene and 3.4 mole% of butene, and -had an apparent density of 0.30. The amount of a solvent-soluble polymer obtained was as small as 5.4 g. Thus, the yield of the polymer was high.

X

~ . . .

Claims (6)

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

1. A process for preparing a polymer or copolymer of an olefin hav-ing at least 3 carbon atoms which comprises polymerizing or copolymerizing an olefin having at least 3 carbon atoms and containing 0 to 10 mole% of ethylene or a diolefin in the presence of a catalyst composed of an organo-aluminum compound component, an electron donor and a solid titanium com-ponent; characterized in that said catalyst is composed of (1) an organoaluminum compound composition consisting of (a) an organoaluminum compound free from halogen atoms directly bound to the aluminum atom expressed by the following formula wherein R1 represents a group selected from the class consisting of a hydro-gen atom, alkyl groups with 1 to 12 carbon atoms, cycloalkyl groups with 5 to 12 carbon atoms, aryl groups with 6 to 12 carbon atoms, alkoxy groups with 1 to 12 carbon atoms, cycloalkoxy groups with 5 to 12 carbon atoms and aryloxy groups with 6 to 12 carbon atoms and the three R1 groups are identi-cal or different, and (b) an organoaluminum compound having halogen atoms directly bound to the aluminum atom expressed by the formula wherein R1 is as defined above, R2 represents a group selected from the class consisting of a hydrogen atom, alkoxy groups with 1 to 12 carbon atoms and aryloxy groups with 6 to 12 carbon atoms, X represents a halogen atom, 0<n<3, 0<m<3, and 0<n + m?3, the (X/Al) ratio of the halogen atoms (X) to the aluminum atom (A1) being 0<X/A1<1, (2) an electron donor, and (3) a halogen-containing solid titanium component which is the reaction product of a magnesium compound, and electron donor and a tetravalent titanium compound and in which the ratio of the electron donor (moles)/titanium atom is not less than 0.2, the ratio of magnesium (moles)/titanium atom is from about 3 to 40 and the ratio of the halogen atoms/titanium atom is not less than 4, the component (3) being further characterized in that at least 80% by weight of the tetravalent titanium compound contained in it is insoluble in boiling n-heptane, that at least 50% by weight of the tetravalent titanium compound is insoluble in TiC14 at 80°C, and that the surface area of the product insoluble in TiC14 at 80°C, and the surface area of component (3) as such, is higher than 40 m2/g.

2. The process of claim 1 wherein the electron donor (2) is a member selected from the group consisting of organic carboxylic acids with 1 to 22 carbon atoms, organic carboxylic anhydrides with 2 to 22 carbon atoms, esters with 2 to 18 carbon atoms, organic acid halides with 2 to 15 carbon atoms, ethers with 2 to 20 carbon atoms, ketones with 3 to 15 carbon atoms, alde-hydes with 2 to 15 carbon atoms, organic acid amides with 2 to 8 carbon atoms, amines and nitriles.

3. The process of claim 1 wherein per liter of the liquid phase, the amount of ingredient (a) is 0.001 to 100 millimoles calculated as Al atom; the amount of ingredient (b) is 0.001 to 100 millimoles; the amount of ingredient (2) is 0.001 to 100 millimoles; and the amount of ingredient (3) is 0.0001 to 1 millimole calculated as Ti atom.

4. The process of claim 1 wherein the olefin is an .alpha.-olefin having 3 to 16 carbon atoms.

5. A catalyst for polymerization or copolymerization of an olefin having at least 3 carbon atoms and containing 0 to 10 mole% of ethylene or a diolefin, said catalyst being composed of (1) an organoaluminum compound composition consisting of (a) an organoaluminum compound free from halogen atom directly bound to the aluminum atom expressed by the following formula wherein R1 represents a group selected from the class consisting of a hydro-gen atom, alkyl groups with 1 to 12 carbon atoms, cycloalkyl groups with 5 to 12 carbon atoms, aryl groups with 6 to 12 carbon atoms, alkoxy groups with 1 to 12 carbon atoms, cycloalkoxy groups with 5 to 12 carbon atoms and aryloxy groups with 6 to 12 carbon atoms, and the three R1 groups are identical or different, and (b) an organoaluminum compound having halogen atoms directly bound to the aluminum atom expressed by the formula R1nA1XmR 3-n-m wherein R1 is as defined above, R2 represents a group selected from the class consisting of a hydrogen atom, alkoxy groups with 1 to 12 carbon atoms and aryloxy groups with 6 to 12 carbon atoms, X represents a halogen atom, 0<n<3, 0<m<3, and 0<n + m?3, the ratio (X/A1) of the halogen atoms (X) to the aluminum atom (A1) being O<X/A1<1, (2) an electron donor, and (3) a halogen-containing solid titanium component which is the reaction product of a magnesium compound, an electron donor and a tetravalent titanium com-pound and in which the ratio of the electron donor (moles)/titanium atom is not less than 0.2, the ratio of magnesium (moles)/titanium atom is from about 3 to 40 and the ratio of the halogen atoms/titanium atom is not less than 4, the component (3) being further characterized in that at least 80%
by weight of the tetravalent titanium compound contained in it is insoluble in boiling n-heptane, that at least 50% by weight of the tetravalent titanium compound is insoluble in TiC14 at 80°C, and that the surface area of the product insoluble in TiC14 at 80°C, and the surface area of component (3) as such, is higher than 40 m2/g.

6. The catalyst of claim 5 wherein the electron donor (2) is a mem-ber selected from the group consisting of organic carboxylic acids with 1 to 22 carbon atoms, organic carboxylic anhydrides with 2 to 22 carbon atoms, esters with 2 to 18 carbon atoms, organic acid halides with 2 to 15 carbon atoms, others with 2 to 20 carbon atoms, ketones with 3 to 15 carbon atoms, aldehyde with 2 to 15 carbon atoms, organic acid amides with 2 to 8 carbon atoms, amines and nitriles.