GB1576642A - Process and catalyst for polymerisation of alpha-olefins - Google Patents

Description

(54) PROCESS AND CATALYST FOR POLYMERISATION OF ALPHA-OLEFINS (71) We, MITSUI PETROCHEMICAL INDUSTRIES LTD, a Japanese Body Corporate of 2-5, 3-chome, Kasumigaseki, Chiyoda-ku, Tokyo, Japan, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: This invention relates to a catalyst and process for preparing a polymer or copolymer of an olefin having at least 3 carbon atoms. Particularly, it relates to an improved catalyst and process for preparing an olefin polymer or copolymer which has an improved apparent density, especially polypropylene having high stereoregularity, in a high yield, the catalyst having a proglonged active life. It also relates to a process and a catalyst used for it, which can afford an olefin polymer having a high apparent density and high stereoregularity even by polymerization at as high a temperature as 80 to 900C.

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 with 0 to 10 mole % of ethylene or a diolefin in the presence of a catalyst composed of (i) an organoaluminum compound component, (ii) an electron donor and (iii) a solid titanium composition.

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 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 halogenated 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 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 titanium compound insoluble in n-heptane is insoluble in TiCI4 at 80"C., and that the surface area of the portion insoluble in TiCl4 at 80"C., and the surface area of component (iii) itself are higher than 40 m2/g.

(Japanese Laid-Open Patent Publication No. 151691/77 laid-open on December 1977).

This Japanese Publication gives no description of the use of an organoaluminum compound having halogen atoms directly bound to the aluminum atom, and as shown in (i) above, íe 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. In all of the Examples of the Japanese Publication, the isotacticity (boiling nheptane-insoluble matter) of polypropylene obtained is 94.5% at the highest. The apparent density of the polypropylene in these examples is 0.5 (kg/e) at the highest and 0.4 (kg/e) at the lowest. According to the measuring methods of JIS K-6721, employed in the present specification, these values correspond to about 0.40 g/me at the highest and about 0.25 g/me at the lowest. As will be shown in Comparative Examples, these are low apparent densities.

The present invention provides a catalyst for use in the polymerization or copolymerization of an olefin having at least 3 carbon atoms with 0 to 10 mole% of ethylene or a diolefin, the catalyst being composed of (1) an organoaluminum compound composition consisting of (a) an organoaluminum compound having no halogen directly bound to the aluminum atom of the formula R l3Al wherein each R l, which may be the same or different represents hydrogen, alkyl of 1 to 12 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, aryl of 6 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, cycloalkoxy of 5 to 12 carbon atoms or aryloxy of 6 to 12 carbon atoms, subject to the proviso that at least one Rl represents alkyl, cycloalkyl or aryl, and (b) an organoaluminum compound having halogen directly bound to the aluminum atom of the formula Rn1AlXmR3-n-m2 wherein R1 is as defined above such that the compound contains carbon directly bound to the aluminium atom, R2 represents hydrogen, alkoxy of 1 to 12 carbonatoms or aryloxy of 6 to 12 carbon atoms, X represents ahalogen atom, 0 < n < 3, 0 < m < 3, and 0 < n + m < 3 the atomic ratio (X/AI) of halogen (X) to aluminum (Al) in the organoaluminum compound composition (1) being 0 < X/Al < l, 2 an organic electron donor, and 3 a halogen-containing solid titanium component which is the reaction product of a magnesium compound, an organic electron donor and a tetravalent titanium compound and in which the ratio of the electron donor (moles)/titanium atom is not less than 0.2:1 and the ratio of the halogen atoms/titanium atom is now less than 4:1, 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 TiCI4 at 800C., and that the surface area of the product insoluble in TiCl4 at 80"C., and the surface area of component (3) as such, is higher than 40 m2/g.

In another aspect the invention 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 with 0 to 10 mole% of ethylene or a diolefin in the presence of a catalyst of the invention. 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 g/me can be produced by using a catalyst of the invention, the catalyst containing, as ingredient (1)(b), an organoaluminum compound having halogen directly bound to the aluminum atom, the use of which is avoided in the above-cited prior art technique.

This improvement in product quality can be achieved with the accompanying 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 stereoregularity can be obtained even when polymerization is carried out at a temperature as high as 80 to 90"C.

In the polymerization or copolymerization of olefins having at least 3 carbon atoms, the sequence of adding the catalyst ingredients (a), (b), (2) and (3) is optional. For example, the four ingredients (a), (b), (2) and (3) can be mixed simultaneously. Or ingredients (a), (b) and (2) can first be mixed simultaneously, and then ingredient (3) mixed with the first mixture. Or ingredients (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 ingredients (a) and (2) are first mixed, then ingredient (3) is mixed, and finally ingredient (b) is mixed.

Examples of the organoaluminum compound (a) having no halogen directly bound to the aluminum atom expressed by the formula R l3Al are triethyl aluminum, triisopropyl aluminum, triiso-butyl aluminium, trihexyl 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 dioctvl aluminum hydride.

Examples of the organoaluminum compound (b) having halogen directly bound to the aluminum atom expressed by the formula RlnAlXmR23nm include alkyl aluminum halides such as diethyl aluminum chloride, di-n-butyl aluminum chloride, diiso-butyl aluminum chloride, didecenyl aluminum chloride, diethyl aluminum fluoride, diethyl aluminum bromide, diethyl aluminum iodide, diethyl aluminum sesquichloride, diiso-butyl aluminum sesquichioride and ethyl aluminum difluoride; alkyl aluminum alkoxy halides such as ethyl aluminum ethoxy chloride, butyl aluminum butyoxy 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 organoaluminum compound (b) need not be pure and can be contained in the product of a reaction in which it is formed. Thus, there can be used, without purification, a reaction mixture containing a halogen-containing aluminum compound (b) and an organometallic compound of a metal of Groups I or II of the periodic table such as a Grignard reagent, a reaction mixture containing an organoaluminum compound (b) and a halogen compound of silicon or tin, or a reaction mixture containing an organoaluminum compound (b) 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. Such reaction mixtures may be prepared by the following processes: (a) RMgX + R',AIX',, (b) RSnX + R'3AI (c) RSiX + R'3Al (d) ZrCl2 + R3A1 (e) RX + R'3Al (f) HX + R2A1R'

R8,nAIX"3m + R"'pMgX '2-p R"A1X + R"'SnX R"A1X + R"'SiX R2AICI + ZnR2 R2AIX + R-R' R2AIX + R'H In the above formulae, the organoaluminum compounds produced by the reactions are compounds satisfying the definition of the halogen-containing compound (b) and the symbols R, R', R" and R' " represent groups satisfying the definitions of the symbols R1 and R2; X, X', X" and X'" are the same as X defined hereinabove; n and m are the same as defined hereinabove; and 0 < p < 2.

The organic electron donor (2) used in this invention can be, for example, selected from 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 carboxylic 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, orgaic 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 coordination 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 containing 2 to 18 carbon atoms such as acetic anhydride, propionic anhydride, n-butyric anhydride, iso-butyric anhydride, monochloroacetic anhydride, trifluoroacetic anhydride, caproic anhydride, lauric anhydride and stearic anhydride; (i-b) aliphatic polycarboxylic acid anhydrides containing 4 to 22 carbon atoms such as succinic anhydride, maleic anhydride, glutaric anhydride, citraconic anhydride, itaconic anhydride, methylsuccinic anhydride, dimethylsuccinic anhydride, ethylsuccinic anhydride, butylsuccinic anhydride, octylsuccinic anhydride, stearylsuccinic anhydride, and methylglutaric anhydride; (i-c) alicyclic carboxylic acid anhydrides containing 8 to 10 carbon atoms such as bicyclo[2.2.1]heptene-2, 3-dicarboxylic anhydride or methylbicyclo[2.2]heptene-2, 3-dicarboxylic anhydride; and (i-d) anhydrides of aromatic carboxylic acids containing 9 to 15 carbon atoms such as acetobenzoic anhydride, benzoic anhydride, p-toluic anhydride, phthalic anhydride, and trimellitic anhydnde.

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-hydroxy-benzoic 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 acids esters (ii-a), alicyclic acid esters (ii-b), and aromatic 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 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 5 to 6 carbon atoms, phenols containing 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, and C1-C4 saturated or unsaturated aliphatic primary alcohols bonded to the ring carbonatom of a C3-Cl0 aliphatic or aromatic ring; and lactones containing 3 to 10 carbonatoms.

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 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 5-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 containing 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples 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 C1-C4 saturated or unsaturated aliphatic primary alcohols bonded to the ring carbon atom of a C3-CIo aliphatic or aromatic ring; and aromatic lactones containing 8 to 10 carbon atoms.

Specific examples of the aromatic ester (ii-c) are alkyl or alkenyl esters, preferably Cl-C8, more preferably C1-C4, alkyl esters or 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 benzoate, n-octyl benzoate, 2-ethylhexyl benzoate, vinyl benzoate, and allyl benzoate; cycloalkyl or cycloalkenyl esters of benzoic acid, preferably C3-C8, 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-C3, aryl or aralkyl esters optionally containing a substituent such as a halogen atom or a C1-C4 lower alkyl group of benzoic acid such as phenyl benzoate, 4-tolyl benzoate, 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 aromatic monocarboxylic acid esters containing the electron donating substituent includes esters of hydroxybenoic acid, preferably Cl-C8, more preferably C1-C4, alkyl esters, preferably C2-C8, 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 salicylate, 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 salicylate, 2-tolyl salicylate, benzyl salicylate, phenyl p-hydroxybenozate, 3-tolyl p-hydroxybenzoate, benzyl p-hydroxybenzoate and ethyl a-resorcylate; esters of alkoxy benzoic acids, preferably esters of lower alkoxy benzoic acids containing 1 to 4 carbon atoms, preferably containing a C1-C2 alkoxy group, and preferably C1-C8, more preferably C1-C4, alkyl esters, or preferably C6-Cl0, more preferably C8-ClO, aryl or aralkyl esters of lower alkoxy benzoic acids, such as methyl anisate, ethyl anisate, iso-propyl anisate, iso-butyl anisate, phenyl anisate, benzyl anisate, ethyl o-methoxybenzoate, methyl p-ethoxybenzoate, ethyl p-ethoxybenzoate, n-butyl p-ethoxybenzoate, 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 benzoic acids containing preferably C,-C8, more preferably C1-C4, alkyl group or C2-C8, more preferably C2-C4, alkenyl group, and preferably C1-C8, more preferably C1-C4, alkyl esters and preferably C6-C10, more preferably C8-Cl0, aryl or aralkyl esters of alkyl or alkenyl benzoic acids, 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-ethylbenzoate, iso-propyl o-ethylbenzoate, n-butyl m-ethylbenzoate, ethyl 3,5-cylenecarboxylate, and ethyl p-styrenecarboxylate; and aminobenzoic acid esters, preferably C1-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 C1-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 benozic acid, alkyl or alkenyl benozic acids, and alkoxy benzoic acids are preferred. Especially preferred species are C1-C4 alkyl esters, for example, methyl or ethyl esters, or benzoic acids, 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 exampls of the acid halides are acetyl chloride, benzyl chloride, toluoyl chloride, anisoyl chloride, stearoyl chloride, isobutyryl chloride, n-caproyl chloride, and benzoyl chloride.

Examples of the ethers having 2 to 20 carbon atoms include alkyl 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, propioal dehyde, octyladehyde, benzaldehyde, hydroxy benzaldehyde, tolualdehyde and naphthal dehyde.

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 ethylenediamine.

Examples of the nitriles are acetonitrile, benzonitrile, and tolunitrile.

The proportion of the electron donor (2) used is preferably 0.01 to 1 mole, especially preferably 0.1 to 0.5 mole, per aluminum atom of the organoaluminum compound composi tion (l) composed of the organoaluminum compounds (a) and (b). The ratio between ingredients (a) and (b) 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 proportion of (a) and (b) should be determined such that the atomic ratio (X/AI) of halogen (X) to aluminum (Al) for the organoaluminum compound composition (1) is 0 < X/Al < 1.

The halogen-containing solid titanium catalyst component (3) used together with ingre dients (a), (b) and (2) is a complex consisting essentially of magnesium, halogen, tetravalent titanium and an electron donor, 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 preferably from 3:1 to 40:1, especially from 10:1 to 30:1. The ratio of the halogen atom/titanium atom is at least 4:1, preferably from 10:1 to 90:1, more preferably from 20:1 to 80:1. The ratio of the electron donor (moles)/titanium atom is at least 0.2:1, preferably from 0.4:1 to 6:1, more preferably from 0.4:1 to 3:1.

In the halogen-containing solid titanium component, at least 80% by weight, preferably at least 90% by weight, of the tetravalent titanium compound is insoluble in boiling n-heptane, and at least 50% by weight, preferably at least 70% by weight, of the tetravalent titanium compound is insoluble in TiCl4 at 800C.

The surface area of the portion insoluble in TiC4 at 80"c. and that of the ingredient (3) itself are at least 40 m2/g, preferably at least 100 m2/g, especially preferably 100 to 300 m2/g.

A particularly suitable ingredient (3) is characterized in that in its X-ray spectrum, the most intense line appearing in the spectrum of magnesium 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 interplanar distance d of the maximum intensity line, or the spectrum is characterized 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 distance d of the aforesaid line. With regard to MgCl2, the halo intensity peak is between d = 2.44 A and 2.97 A.

Generally, the composition of ingredient (3) may be expressed as consisting of 70 to 80% by weight of magnesium dichloride or magnesium dibromide, and the difference from 100% consisting of the titanium compound and the electron donor.

The ingredient (3) may contain, in addition to the above compounds, an inert solid filler in an amount of 80U/o or more based on the weight of the ingredient (3).

Examples of such a filler are LiCI, CaCO3, Cacti2, Na2SO4, Na2CO3, Na2B407, CaSO4, AIC13, B203, Awl203, 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 particular, when ingredient (3) is homogeneously mixed with an agglomerating substance, especially B203 or Ail3, 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 Al203 having a high porosity. In this case, the titanium and magnesium halogenated compounds and the electron donor make up a reduced proportion with respect to the total amount, thus permitting the preparation of catalysts in which the amount of unwanted materials such as halogen is minimal.

While the Mg/Ti ratio is generally higher than 1, it is lower than l 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 prepared 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 heptane, hexane, or kerosene.

Examples of useful magnesium compounds are those of the formulae MgX2, R,MgX2,, Mg(OR)2.cXe, and MgMe(OR)X, in which X represents a halogen atom such as chlorine or bromine or iodine, preferably chloride, R represents 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 e represents a positive number of 0 < e < 2.

Furthermore, in the preparation of ingredient (3), a hydrated magnesium halide containing generally 0.1 to 6 moles of H20 per mole of the halide can be used as a starting material.

MgO, Mg(OH)2, Mg(OH)Cl, magnesium carbonate, a magnesium salt of an organic acid, magnesium silicate, magnesium aluminate, a magnesium alcoholate, and the halogenated derivatives of these 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 compounds are Grignard reagents, and compounds of the formula MgR2 in which R is an alkyl, cycloalkyl or aryl group containing the spectrum of the corresponding magnesium halide of normal type exhibits a decreased relatively intensity and appears asymmetrically broadened so as to form a halo in which the intensity 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 obtained 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 halo 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 TiCl4, if desired in the presence of an electron donor, at such temperatures (generally between room temperature and 200"C.) and for such time periods as are sufficient to fix a proper amount of the titanium compound.

The solid product of the reaction is then separated from the liquid phase, for example by means of filtration, sedimentatidn, etc., under such temperature conditions that in the solid product, after extraction with boiling n-heptane and with TiC14 at 800 C., amounts of extractable titanium compounds exceeding 20% and 50% by weight respectively are no longer present.

In this method, magnesium alkoxy halides, magnesium aryloxy halides, 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.

(1-b) A method according to method (1-a) except that the starting product 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)2eXe, R,MgX2.e or MgMe(OR)X is contacted with 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 (1-a) in the presence or absence of the reaction medium.

(1-c) A method which comprises treating a magnesium compound with a halogenating agent such as chlorine, hydrogen chloride, thionyl chloride, silicon tetrachloride, a silicon alkyl chloride, hydrogen bromide or an aluminum halogen compound, reacting the product with an electron donor, and then treating 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 absence of a reaction medium.

The magnesium compound treated with the halogenating agent in the above manner is then subjected to copulverization treatment by method (1-a), or to treatment in solution by method (1-b), and then treated with the titanium halide by method (1-a).

(1-d) A method which comprises treating the magnesium compound and the electron donor in solution by method (1-b), subjecting the product to halogenation treatment in the same manner as in method (l-c), and then treating the resulting product with the titanium halide in the same way as in method (1-a).

(1-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 (1-a) or (1-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 donor with the organoaluminum compound or the halogenating agent, and treat the resulting product with the electron donor by method (1-a) or (1-b).

Preferably, the treatment of the magnesium compound with the organoaluminum compound, silicon halide or tin halide is performed by suspending the magnesium compound in an inert solvent such as a 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 temperature, 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 (1-a), and separating the solid reaction product so that substantially no titanium compound extractable with boiling n-heptane and with TiCI4 at 80"C. remains on the solid component.

The details of these methods are shown in Japanese Laid-Open Patent 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 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 preparing ingredient (3).

(1-f) When a magnesium compound of the formula MgR2 is used, it is reacted 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, ketone, aldehyde or with a mixture of such a compound and aluminium, etc. Then, the reaction product is reacted with an excess of TiCl4 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 hydrocarbon is treated with 1 to 20 moles, per titanium atom contained in the carrier, of an electron donor, especially an organic acid ester such as an aromatic carboxylic acid ester, at room temperature to 200"C.

The solid reaction product treated by this method is accurately separated from the unreacted electron donor, and then reacted with a halogenated titanium compound, after which the reaction product is separated from the liquid phase by method (1-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 insoluble in boiling n-heptane, and not more than 50% of the titanium compound should be extractable with TiCl4 at 800C. In fact, the presence of a soluble titanium compound is disadvantageous both to the activity and stereospecificity 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 polymerized or copolymerized in the presence of a catalyst composed of the ingredients (a), (b), (2) and (3) described hereinabove.

Examples of suitable olefins are a-olefins with 3 to 16 carbon atoms such as propylene, 1 -butene, 4-methyl-i -pentene, 1 -octene, 1 -decene and 1 -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 a-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 polymerize propylene until a homopolymerization in an amount of about 60 to about 90% based on the entire composition is obtained, and subsequently polymerizing a mixture of propylene and ethylene, or ethylene. Alternatively, a mixture of propylene and ethylene may be polymerized so as to obtain a copolymer 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 millimole, calculated as titanium atom, of ingredient (3), 0.001 to 100 millimoles, calculated as aluminum atom, of ingredient (a), 0.001 to 100 millimoles, 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 reaction. An olefin and if desired hydrogen are fed into the polymerization reactor in the form of gases. The proportions of the catalyst ingredients are the same as in the case of the liquid phase polymerization.

The polymerization temperature is generally 20 to 2000C., preferably 50 to 1800C.

Particularly, the highly stereoregular polymerization of propylene is carried out at a temperature of 50 to 1400C. and a pressure of atmospheric pressure to 50kg/cm2, preferably 2 to 20 kg/cm2.

1. Preparation of ingredient (3) Anhydrous magnesium chloride (20 g) and each of the electron donors 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 80"C. for 2 hours. The solid product was collected by filtration, and fully washed with purified hexane until no free titanium tetrachloride was detected 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 methods.

The amount of trivalent titanium was measured by the potassium permanganate method, and the amount of tetravalent titanium was calculated by subtracting the amount of trivalent titanium from the total amount of titanium.

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 80"C. 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 800C. 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 800 C. were -measured by the nitrogen adsorption method.

In the following tables Et stands for ethyl, Me, methyl; and Bu, butyl.

Table 1 Tetravalent Ti-in- Surface area (m2/g) of Composition of soluble content (wt.%) ingredient (3) before ingredient (3) of ingredient (3) and after extraction with TiCl4 at 80 C. Electron donor Halogen Ti Catalyst Ti (atomic Component Electron donor Boiling 80 C. TiCl4 Before After (mole ratio) ratio) No. (amount) n-heptane

98 98 203 200 1.5 99 96 96 193 188 1.3 52 97 98 183 170 1.3 50 90 95 191 189 1.8 45 89 96 188 176 1.9 43 94 92 173 160 1.8 45 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..

Table 2 Tetravelent Surface area Composition of Ti-insoluble (m2/g) of in- ingredient (3) content (wt. %) gredient (3) of ingredient before and Electron (3) after extrac- donor Halogen Cat. tion with Ti Ti Com- Boiling 80 C. TiCl4 at 80 C. (mole atomic ponent Ti compound Mg compound (g) n-heptane TiCl4 ratio) ratio) No. Before After 2-1 TiCl4 MgBr0.5Cl1.5 25 97 98 191 187 1.6 54 2-2 TiCl4 Et0.1MgCl1.9 20 98 96 195 190 1.3 50

20 96 93 187 181 1.3 49 22 93 90 200 197 1.3 47 20 92 89 201 195 1.5 45 20 95 90 190 182 1.4 47 23 93 91 173 170 1.3 46 20 96 95 206 197 1.4 58 20 92 88 199 195 1.6 45 20 94 91 210 200 1.7 42 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 butanol, 52.5 millimoles of 2-ethylhexanol and 10.5 millimoles of butyl toluate were added dropwise at room temperature. The mixture was stirred at 1 100C. 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 1000C. for 2 hours. The supernatant liquid was removed, and 100 ml of titanium tetrachloride was added. The mixture was stirred at 100"C. for 1 hour, hotfiltered, and washed with hexane to afford ingredient (3). The product is designated as ingredient (3) catalyst component No. (3-1).

(3-2) The same procedure as in (3-1) 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 600C. for 10 hours. The resulting halogencontaining solid titanium component was designated as ingredient (3) catalyst component 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, anhydrous hydrogen chloride was passed into the suspension at 0 C. for 1 hour, and the suspension was further stirred for 1 hour at 20"C. Ingredient (3) was prepared by operating in the same way as in the preparation of catalyst component 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 tetrachloride was changed to 110 C. The resulting product is designated as ingredient (3) catalyst component No. (3-3).

The catalyst components Nos. (3-1), (3-2) and (3-3) are shown in Table 3.

4. Preparation of ingredient (3) (4-1) Commercially available anhydrous magnesium dichloride (5 g; 52.5 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 0 C., and the mixture was stirred at 800C. for 6 hours. The resulting 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 mixture was stirred at 700 C. for 1 hour. The solid was collected by filtration, washed fully with hexane, and dried. The product was treated with titanium tetrachloride under the same conditions as in the preparation of the catalyst component No. (3-1) to afford ingredient (3). This product is designated as ingredient (3) catalyst component No. (4-1).

(4-2) The procedure of the preparation of the ingredient (3) catalyst component No. (4-1) was repeated except that 630 millimoles of tin tetrachloride was used instead of the trioctyl aluminum. Thus, ingredient (3) catalyst component No. (4-2) was obtained.

The resulting catalyst components 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 70"C. for 18 hours, and 1.3 g of ethyl cyclohexyl carboxylate was added. The mixture was stirred at 700 C. for 1 hour, and filtered. The solid separated was washed to afford a solid reaction product. The solid product was suspended in 300 ml of titanium tetrachloride, and stirred at 1000C. 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 component 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 800 C. for 6 hours. Then, 1.5 g of ethyl benzoate was added, and the mixture was stirred at 70"C. for 1 hour. It was filtered, and washed to afford a solid reaction product. The solid product was treated with titanium tetrachloride in the same way as in the preparation of the catalyst component No.

(5-1). The product is designated as ingredient (3) catalyst component No. (5-2).

(5-3) Magnesium benzoyloxy chloride (5 g) was suspended in 100 ml of hexane, and hydrogen chloride was added at 0 C. The suspension was stirred at 30"C. for 6 hours. Then, 1.5 g of n-butyl benzoate was added, and the mixture 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 1 100C. for 2 hours. the supernatant liquid was removed, and 100 ml of titanium tetrachloride was added. The mixture was stirred at 1100C. for 1 hour, filtered, washed and dried to afford a product designated as ingredient (3) catalyst component No. (5-3).

The catalyst components Nos. (5-1), (5-2) and (5-3) are shown in Table 3.

Table 3 Tetravelent Ti-in- Surface area (m2/g) of Composition of ingredient (3) soluble content (wt.%) ingredient (3) before of ingredient (3) and after extraction Electron donor Halogen Ingredient (3) with TiCl4 at 80 c. catalyst Boiling 80 C. TiCl4 Ti Ti component No. n-heptane Before After (mole ratio) (atomic ratio) 3-1 97 98 270 250 2.1 23 3-2 96 97 280 270 1.9 35 3-3 98 96 143 125 1.7 24 4-1 97 97 195 194 1.5 26 4-2 98 98 140 135 1.3 24 5-1 96 97 130 100 0.7 24 5-2 96 97 80 75 1.3 24 5-3 97 97 150 130 1.4 25 Examples I 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 organoaluminum 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 1-liter glass flask was used. The amount of ingredient (3), as titanium atom, was 0.015 millimole in Examples 1 to 19; 0.001 millimole in Example 20; 0.002 millimole in Examples 21 to 24; 0.05 millimole in Examples 25 to 31; and 0.015 millimole in Comparative Examples 1 to 3.

Table 4 Comparative Example 1 2 3 Solvent hexane hexane hexane Amount of solvent (ml) 750 750 750 Pressure of propylene (kg/cm2G) 7 7 7 Polymerization temperature ( C.) 70 70 70 Polymerization time (hrs) 4 4 0.5 Presence of hydrogen Yes Yes Yes Ingredient (a) Et3Al - Et3Al Amount (mmoles) 1.5 - 1.5 Ingredient (b) - Et2AlCl Et2AICl Amount (mmoles) - 1.5 1.5 X/AI ratio 0 1 0.5 Electron donor (2)

Amount (mmole) 0.5 0.15 (3)Catalyst Component 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 Table 4 (continued) Example 1 2 3 Solvent Hexane Hexane Hexane Amount of solvent (ml) 750 750 750 Pressure of propylene (kg/cm2G) 7 7 7 Polymerization temperature ( C.) 70 '70 70 Polymerization time (hrs) 4 4 4 Presence of hydrogen Yes Yes Yes Ingredient (a) Et3Al (n-C8Ht,)3AI Me3AI Amount (mmoles) 0.75 0.75 0.75 Ingredient (b) Et2AlCl (n-Bu)2AlCl Et2AlCl Amount (mmoles) 0.75 1.5 2.25 X/AI ratio 0.5 0.67 0.75 Electron donor (2)

Amount (mmoles) 0.375 0.375 0.375 (3) Catalyst Component 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 Example 4 5 6 Solvent Hexane Hexane Hexane Amount of solvent (ml) 750 750 750 Pressure of propylene (kg/cm2G) 7 7 7 Polymerization temperature ( C.) 70 70 70 Polymerization time (hrs) 4 4 4 Presence of hydrogen Yes Yes Yes Ingredient (a) (i-Bu)3Al Et2AlH (i-Bu)2.9Al(OEt)0.1 Amount (mmoles) 1.125 0.75 1.0 Ingredient (b) (i-Bu) 2AlCl Et2AlCl (i-Bu) 2AlCl Amount (moles) 1.125 0.75 1.25 X/Al rstio 0.5 0.5 0.56 Electron donor (2)

Amount (mmole) 0.563 0.428 0.625 (3) Catalyst Component No. 1-4 1-5 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 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 temperature ( C.) 70 60 70 Polymerization time (hrs) 4 1 1 Presence of hydrogen Yes Yes Yes Ingredient (a) Et3AI Et3AI (i-Bu)3A Amount (mmole) 0.75 0.5 0.5 Ingredient (b) Et2AIC1 Et2AlCl (i-Bu)2AlCl Amount (mmole) 0.375 0.25 0.5 Z/Al ratio 0.33 0.33 0.5 Electron donor (2)

Amount (mmole) 0.375 0.25 0.23 (3) Catalyst component No. 2-1 2-2 2-3 Yield (g-pp/mmole Ti) 17,700 18,300 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.

Example 10 11 12 Solvent Propylene Propylene Propylene Amount of solvent (g) 500 500 500 Pressure of ropylene (kg/cm2Gb 30 25 30 Polymerization temperature ( C). 70 60 70 Polymerization time (hr) 1 1 1 Presence of hydrogen Yes Yes Yes Ingredient (a) Et3AI Et3AI (i-Bu)3A1 Amount (mmole) 0.5 0.5 0.5 Ingredient (b) Et2A1CI Et2AICI Et2AICI Amount (mmole) 0.75 0.25 0.25 X/AI ratio - 0.6 0.33 0.33 Electron donor (2)

Amount (mmole) 0.25 0.25 0.33 (3) Catalyst Component No. 2-4 2-5 2-6 Yield (g-pp/mmole Ti) 15,700 13,900 13,200 Isotacticity (%) 93.6 94.6 94.8 Apparent density (g/ml) 0.42 0.41 0.42 Melt index 1.3 1.7 1.0 Table 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 temperature ( C.) 60 70 70 Polymerization time (hr) 1 1 1 Presence of hydrogen Yes Yes Yes Ingredient (a) Et3Al Et3Al Et3Al Amount (mmole) 0.5 X 0.5 0.5 Ingredient (b) Et2AlCl Et2AlCl Et2AlCl Amount (mmole) 0.25 0.25 0.5 X/ Al ratio 0.33 0.33 0.5 Electron donor (2)

Amount (mmole) 0.33 0.33 0.33 (3) Catalyst Component No. 2-7 2-8 2-9 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 Example; 16 17 18 Solvent Propylene Hexane Kerosene Amount of solvent (ml) 500 g 750 750 Pressure of ropylene 25 (kg/ cm2G 7 7 Polymerization temperature ( C.) 60 70 60 Polymerization time (hrs) 1 4 4 Presence of hydrogen Yes Yes Yes Ingredient (a) (i-Bu)3AI (CsHz7)3Al (i-Bu) 2AlH Amount (mmole) 0.5 0.75 0.75 Ingredient (b) Et2AlCl C8H17AlCl2 Et2AlCl Amount (mmole) 0.25 0.3 0.9 X/ Al ratio Electron donor (2)

Amount (mmole) 0.33 0.375 0.556 (3) Catalyst Component No. 2-10 3-1 3-2 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 Table 4 (continued) Example 19 20 21 Solvent Heptane Propylene Propylene Amount of solvent (ml) 750 500 g 500 g Pressure of ropylene (kg/cm2GU 9 30 30 Polymerization temperature ( C.) 85 80 70 Polymerization time (hrs) 4 0.5 1 Presence of hydrogen Yes Yes Yes Ingredient(a) (n-Bu)3Al

Amount (mmoles) 1.5 0.5 0.5 Ingredient (b) Et1.5AlCl1.5 EtAl(OEt)CI EtAl(OBu)CI Amount (mmoles) 1.5 0.5 0.5 X/AI ratio 0.75 0.5 0.5 Electron donor (2)

Amount (mmoles) 0.75 0.33 0.33 (3)Catalyst Component No. 3-3 4-1 4-2 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 Propylene Propylene Amount of solvent (g) 500 500 500 Pressure of propylene (kg/cm2G) 25 25 30 Polymerization temperature (OC.) 60 60 70 Polymerization time (hr) 1 1 1 Presence of hydrogen Yes Yes Yes Ingredient (a) Et3A1 Et2.9Al(OC5H17)0.1 Et3A1 Amount (mmole) Ingredient (b) Amount (mmole) X/ Al ratio Electron donor (2) Amount (mmole)

(3) Catalyst Component No. 5-1 5-2 5-3 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 (continued) Example 25 26 27 Solvent Kerosene Kerosene Kerosene Amount of solvent (ml) 500 500 500 Pressure of propylene (atms) 1 1 1 Polymerization temperature (OC.) 60 60 60 Polymerization time (hr) 1 1 1 Ingredient (a) Et3AI Et3AI Et3AI Amount (mmoles) 1.5 1.5 1.5 Ingredient (b) (i-Bu)2AlCl Et2AlCl Et2A1CI Amount (mmoles) 1 1.5 1.5 X/A1 ratio 0.4 Electron donor (2) (MeCO)2O

Amount (mmole) 0.83 0.83 0.83 (3) Catalyst Component No. 1-2 1-2 1-2 Specific activity (g-pp/mmoles Ti 507 1,344 2,086 h atm of propylene) Isotacticity (%) 98.5 97.8 92.1 Apparent density (g/ml) 0.35 0.35 0.35 Example 28 29 30 Solvent Kerosene Kerosene Kerosene Amount of solvent (ml) 500 500 500 Pressure of propylene (atms) 1 1 1 Polymerization temperature ( C.) 60 60 60 Polymerization time (hr) 1 1 1 Ingredient (a) Et3Al Et3Al Et3AI Amount (mmoles) 1.5 1.5 1.0 Ingredient (b) Et2AICI Et2A1CI Et2AlCI Amount (mmoles) 1.5 1.5 1.0 X/AI ratio 0.5 0.5 0.5 Electron donor (2)

Amount (mmoles) 0.83 1.5 0.56 (3) Catalyst Component No. 1-2 1-2 1-2 Specific acitivity (g-pp/mmoles Ti 1,879 673 954 h atm of propylene) Isotacticity (%) 88.5 95.1 91.3 Apparent density 0.35 0.35 0.37 Table 4 (continued) Example 31 Solvent Kerosene Amount of solvent (ml) 500 Pressure of propylene (atms) 1 Polymerization tempera ture ("C.) 60 Polymerization time (hr) 1 Ingredient (a) Et3A1 Amount (mmole) 1.0 Ingredient (b) Et2AICl Amount (mmole) 1.0 X/Al ratio 0.5 Electron donor (2) CH3COCH2COOC2H5 Amount (mmole) 0.56 (3) Catalyst Component No. 1-2 Specific activity (g-pp/mmoles.Ti. 1,014 h atms of propylene) Isotacticity (io) 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 250C.) were placed in an atmosphere of nitrogen in a stainless steel (SUS-32) ball mill vessel having an inner capacity of 800 ml and an 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. Ten grams of the resulting solid product was suspended in 100 ml of titanium tetrachloride. The mixture was stirred at 800 C. 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 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 60"C., 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 extraction residue of 99.1% and an apparent density of 0.40 g/ml. Concentration 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 residue 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 temperature, with 2.25 millimoles of triethyl aluminum, 1.5 millimoles of diethylaluminum chloride, 1.25 millimoles of methyl toluate, and 0.0225 millimole of the ingredient (3) catalyst component No. (1-1) in this order. Then hydrogen gas was introduced, and the temperature was raised. At 55"C., a gaseous mixture consisting of 93.1 mole% of propylene, 2.8 mole% of ethylene and 4.1 mole% of 1-butene was fed, and polymerized for 2 hours while maintaining the pressure at 2.5 kg/cm2G. Filtration and washing with hexane afforded 199.6 g of a white powdery polymer. Infrared analysis showed that the white powdery 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.

Claims (8)

WHAT WE CLAIM IS:

1. A catalyst for use in the polymerization or copolymerization of an olefin having at least 3 carbon atoms with 0 to 10 mole % of ethylene or a diolefin, the catalyst being composed of (1) An organoaluminum compound composition consisting of (a) an organoaluminum compound having no halogen directly bound to the aluminum atom of the formula Rl3AI wherein each Rl, which may be the same or different, represents hydrogen, alkyl of 1 to 12 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, arylof6to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, cycloalkoxy of 5 to 12 carbon atoms or aryloxy of 6 to 12 carbon atoms, subject to the proviso that at least one R1represents alkyl, cycloalkyl or aryl, and (b) an organoaluminum compound having halogen directly bound to the aluminum atom of the formula R 'nAlXmR23nn wherein R l is as defined above such that the compound contains carbon directly bound to the aluminium atom. R2 represents hydrogen, alkoxy of 1 to 12 carbon atoms or aryloxy of 6 to 12 carbon atoms, X represents a halogen atom, O < n < 3, O < m < 3, and 0 < n + m < 3, the atomic ratio (X/Al) of halogen (X) to aluminum (Al) in the organoaluminum compound composition (1) being O < X/A1 < 1, 2 an organic electron donor, and 3 a halogen-containing solid titanium component which is the reaction product of a magnesium compound, an organic electron donor and a tetravalent titanium compound and in which the ratio of the electron donor (moles)/titanium atom is not less than 0.2:1 and the ratio of the halogen atoms/titanium atom is not less than 4:1, the component (3) being further characterized in that at least 80% by weight of the tetravalent titanium compound contained in its is insoluble in boiling n-heptane, that at least 50%by weight of the tetravalent titanium compound is insoluble in TiCI4 at 800 C., and that the surface area of the product insoluble in TiCI4 at 800 C., and the surface area of component (3) as such, is higher than 40 m2/g.

2. A catalyst according to claim 1 wherein the electron donor (2) is an organic carboxylic acid of 1 to 22 carbon atoms, organic carboxylic anhydride of 2 to 22 carbon atoms, ester of 2 to 18 carbon atoms, organic acid halide of 2 to 15 carbon atoms, ether of 2 to 20 carbon atoms, ketone of 3 to 15 carbon atoms, aldehyde of 2 to 15 carbon atoms, organic acid amide of 2 to 8 carbon atoms, amine or nitrile.

3. A catalyst according to claim 1 substantially as described with reference to any one of the Examples.

4. A process for preparing a polymer of copolymer of an olefin having at least 3 carbon atoms which comprises polymerizing or copolymerizing an olefin having at least 3 carbona aoms with 0 to 10 mole% of ethylene or a diolefin in the presence of a catalyst as claimed in claim 1, 2 or 3.

5. A process according to claim 4 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 0.001 to 1 millimole calculated as Ti atom.

6. A process according to claim 4 or 5 wherein the olefin is an a-olefin of 3 to 16 carbon atoms.

7. A process according to claim 4 substantially as described by reference to any one of the Examples.

8. An olefin polymer or copolymer when prepared by a process as claimed in any one of claims 4 to 7.