CA1121326A - Catalyst for producing polyolefins - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
A catalyst suitable for polymerizing an .alpha.-olefin, comprising a solid catalyst component [A] and an organometal compound [B], the solid catalyst component [A] being prepared by reacting an organomsgnesium com-pound (1) soluble in a hydrocarbon medium and represented by the general formula, MgR1pR2qXr?Zs wherein R1 is a hydrocarbon group having 2 to 3 carbon atoms;
R2 is a hydrocarbon group having 4 to 20 carbon atoms and the difference in number of carbon atoms between R1 and R2 is at least 2;
X is an electronegative group having an oxygen atom, a nitrogen atom or a sulfur atom;
Z is an organometal compound of aluminum, boron, beryllium, zinc, silicon or lithium;
p and q each is a number above 0 to 1 r is a number from 0 to 1;
p + q + r = 2; and s is a number above 0 to below 0.1, with a titanium and/or vanadium compound (2) having at least one halogen atom; and a process for polymerizin?; .alpha.-olefin employing the same catalyst.

Description

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BACKGROU~D OF TH~ INVENTION
This invention relates to a catalyst suitable for polymerizing an a-olefin and hàving a high activity and to a polymeri~ation process employing such a catalyst.
Description of the Prior Art It is known in Japanese Patent No. 233,148 to K. Ziegler that polyethylene can be produced under a low pressure using a catalyst comprising an organomagnesium compound and a transition metal compound.
The organomagnesium compound as such, however, is disadvantageously insoluble in an inert hydrocarbon medium employed for the preparation of the catalyst and the polymerization of ethylene and as a result, the catalysts having a high activity have not been obtained.
It is also known in Japanese Patent Publication No. 40959/1972 ;`
and Japanese Patent Application (OPI) No. 439211971 that when the organo-magnesium compound is used in a speci-fic form there can be obtained catalysts having increased activity. Such organomagnesium compounds include, for example, complexes of an organomagnesium halide, i.e. a so-called Grignard reagent with an ether, and organomagnesium alkoxides.
The catalysts comprising these organomagnesium compounds have a compara-tively high activity per transltion metal atom but as for the catalysts capable of completely omitting the catalyst removal step in a process of producing polyethylene, the amount of halogen atoms remaining in the polymers obtained is still large.
Some of the co-inventors of this invention proposed in U.S.
Patent Nos. 3,989,878, 4,004,071 and 4,027,087 a series of complex compounds soluble in an invert hydrocarbon medium and comprising an organomagnesium compound and one of an organo~inc compound, an organoboron compound and an organoberyllium compound in a specific ratio which have a much higher activity than the conventional catalysts and enable complete omission of the catalyst removal step.

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As a result of intensified studies on the catalyst system comprising an organomagnesium compound, the inventors have discovered that without using the above described complex compounds having a specific composition, catalysts havirlg a very high activity and suitable for polymerizing an ~-olefin can be obtained by reacting a solid catalyst component with an organometal compound, the solid catalyst component being prepared by reacting an organomagnesium compound soluble in an inert hydrocarbon medium with a titanium and/or vanadium compound.
According to this invention there is provided a catalyst suitable for polymerizing an ~-olefin, comprising [Al a solid catalyst component and [B] an organometal compound, wherein the solid catalyst component [A] is prepared by reacting (1) an organomagnesium compound soluble in a hydrocarbon medium and represented by the general formula, r~. MgRlpR2qXr Zs wherein Rl is a hydrocarbon group having 2 to 3 carbon atoms;
R2 is a hydrocarbon group having 4 to 20 carbon atoms and the difference in number of carbon atoms between Rl and R2 is at least 2;
X is an electronegative group having an oxygen atom, a nitrogen atom or a ~ulfur atom;
Z is an organometal compound of aluminum, boron, ~: beryllium, zinc, silicon or lithium, p and q each is a number above 0 to 1, : r is a number from 0 to 1, p + q ~ r = 2, and s is a number above 0 to below 0.1 with (2) a titanium and/or vanadium compound having at least one halogen atom.

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Also~ according to this invention there is provided a process for the production of polyolefins by using the same catalyst.
One of the characteristic features of this invention is a very high catalystic efficiency. Owing to this feature, the amount of catalyst resid~e such as transition metals and halogen atoms remaining in the polymers produced is small. Accordingly, the catalyst of this invention is suitable for a polymerization process which does not require any catalyst removal step.
Another characteristic feature of this invention is that as excellent particle properties, the polymers produced have a uniform particle size and do not contain large coarse particles which cause trouble in a continuous polymerization, and further they have a high bulk density.
Stlll another characteristic feature of this invention is that the molecular weight distribution of polymers can be easily controlled within wide limits.
The polymers obtained by using the above described catalyst of this invention have high molecular weight, high rigidity, narrow molecular weight distribution and high impact strength.
~ ~ Furthermore, in order to broaden the molecular weight distri--~ bution of polymers with a high catalytic activity, the solid catalyst component [A] before being reacted with the organometal compound [B] is additionally reacted with an inorganic or organic compound (3) of aluminum, silicon, tin or antimony or a titanium or vanadium compound (4) to give a solid type catalyst component [A']. This solid type catalyst component [A'~ is employed together with the organometal compound [B] as the catalyst of this invention. Or the solid catalyst component [A] or the solid type catalyst component [A'] together with the organometal compound [B] is further combined with a halogenated hydrocarbon [C].
By employing the solid type catalyst component [A'] together with the 1~.2~6 organometal compound [B] or the solid catalyst com~onent ~A] or the solid type catalyst component [~'] together with the organometal compound [R] in combination with the halogenated hydrocarbon [C], there can be obtained polymers having a broader molecular weight distribution suitable for blow-molding or film- or sheet- molding.
Detailed Desc~ption of the Preferred Embodiments Each of the component materials and reaction conditions employed for the preparation of the catalyst of this invention will be described hereinafter in detail.
The organomagnesium compound (1) which can be employed for preparing the solid catalyst component [A] of this invention is repre-sented by the general formula, gRlpR2qXr- Zs wherein Rl, R2, X, Z, p, q, r and s are the same as defined above.
In this formula, Rl is a hydrocarbon group having 2 to 3 carbon atoms. Exemplary hydrocarbon groups include an ethyl group, a propyl group and an isopropyl. Of these groups, an ethyl group is preferred. In the above describe formula, R2 is a hydrocarbon group having 4 to 20 carbon atoms. Exemplary hydrocarbon groups include a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl and a hexadecyl group.
Of these groups, a butyl group, a pentyl group and a hexyl group are preferred. The difference in number of carbon atom between Rl and R2 of at least 2 is an important factor for rendering the organomagnesium compound (1) soluble in an inert hydrocarbon medium at high concent~
rations. Suitable examples of the electronegative group having an oxygen atom, a nitrogen atom or a sulfur atom include an alkoxy group having 1 to 20 carbon atoms, a siloxy group, a phenoxy group, a sub-stituted phenoxy group, an amino group, an amide group, a -N=C~R4 group l~.Z~I 3~6 wherein R3 and R4 may be the same or different and each is a hydrocarbon group having 1 to 20 carbon atoms, a -SRS group wherein RS is a hydro-carbon group having 1 to 20 carbon atoms, and ~-ketoacid group.
Of these groups, an alkoxy group having 1 to 20 carbon atoms and a siloxy group are preferred.
Exe~plary organometal compounds of aluminum, boron, beryllium, zinc, silicon or lithium represented by Z include a trialkylaluminum, an alkylaluminum alkoxide, a trialkoxyaluminum, a dialkylberyllium, a trialkylboron, a dialkylzinc, a tetralkylsilane, a trialkylhydroxysilane and an alkyllithium. Of these organometal comPounds, an organoaluminum compound of the general formula, AQR6(0R7)3 wherein R6 and R7 may be the same or different and each is a hydrocarbon group having 1 to 20 carbon atoms, and n is a number from 0 to 3 is preferred. ~ trialkylaluminum, an alkylaluminum alkoxide and a trialkoxyaluminum are more prefeTred. p and q are numbers above zero to 1 and r is a number from zero to 1 and p + q + r = 2. When r ranges from zero to 0.6, the catalytic activity is increased. r is an important factor for rendering the molecular weight distribution of a polymer narrow, and when r ranges from 0.2 to 0.6, the effect of imparting a narrow molecular weight distribu~ion to the polymer produced with a high catalytic activity can be achieved. s is a number above 0 below 0.1 and a preferred range is 0.09 to 0.02 in order to render the solution viscosity of the organomagnesium compound (1) decreased, resulting in ease in handling, and to obtain a high activity.
These organomagnesium compounds can be prepared by reacting a reaction product between an organohalide of the formula RlW wherein ~.Z~3~6 Rl is the same as defined above and ~ is a halogen atom and magnesium metal, i.e., a so-called Grignard reagent with an organolithium compound of the formula R2Li wherein R2 is the same as defined above or by reacting an equimolar mixture of an organohalide of the formula RlW and an organohalide oE the formula R2W wherein ~1 and R2 are the same as defined above and W is a halogen atom with magnesium metal in the method as described in U.S. Patent No. 4,127,507.
The introduction of an electronegative group oE X: is conducted by reacting an organomagnesium compound of the formula, MgRlpR2q wherein Rl, R2, p and q are the same as defined above, with a reagent selected from the group consisting of oxygen, an alcohol, an organic acid, an ester of an organic acid, an aldehyde, a ketone, a silanol, a siloxane, an amine, a nitrile and a mercaptan. Exemplary reagents include, in addition to oxygen, ethanol, propanol, butanol, hexanol, octanol, acetic acid, propionic acid, butanoic acid, benzoic acid, methyl acetate, butyl propionate, acetaldehyde, acetone, methyl ethyl ketone, acetylacetone, trimethylsllanol, triphenylsilanol, dimethyldihydrodisiloxane, cyclic methylhydrotetrasiloxane, methyl~
hydropolysiloxane, phenylhydropolysiloxane, acetonitrile, ben~onitrile, methylam me, dimethylamine, ethylamine, diethylamine, phenylamine, methyl mercaptan, propyl merçaptan and butyl mercaptan.
The method of introducing the e]ectronegative group of:X which can be employed is descrlbed in G.E. Coats and K. Wade, Organometal Com-pounds, Vol. 1, published by Methuen & Co., Ltd.
~ xemplary titanlum and/or vanadium compounds (2) having at least one halogen atom which can be employed for preparing the solid catalyst component [~] of this invention include the halides, the oxyhalides and the alkoxyhalides of titanium or vanadium such as titanium ~\ ~

tetrachloride, titanium tetrabromide, titanium tetraiodide, ethoxy-titanium trichloride, propoxytitanium trichloride, butoxytitanium trichloride, dibutoxytitanium dichloride, tributoxytitanium monochloride, vanadium tetrachloride, vanadyl trichloride, monobutoxyvanadyl dichloride, dibutoxyvanadyl dichloride, and mixtures thereof. Of these compounds, the compounds of titanium and/or vanadium having at least 3 carbon atoms are preferred. More preerred compounds are titanium tetrachloride and vanadium tetrachloride.
The reaction between the organomagnesium compound (1) and the titanium and/or vanadium compound (2) is conducted in an inert reaction medlum including an aliphatic hydrocarbon such as hexane or heptane, an aromatic hydrocarbon such as benzene, toluene or xylene, and an alicyclic hydrocarbon such as cyclohexane or methylcyclohexane at a h temperature of from about -30C to about 100C, preferably from about -20C to about 50C. In order to achieve high activity it is recommended that the reaction ratio of the two components ranges from 0.05 mole to 50 moles, especially from 0 2 mole to 10 moles of the organomagnesium compound (1) per mole of the ti-tanium and/or vanadium compound (2).
The composition and the structure of the solid catalyst com-ponent [A~ obtained ln the above described reaction may be varied within wide limits depending upon factors such as the starting materials selected and the reaction conditions employed. Typlcally the mole ratio of Mg/(Ti and/or V~ of the solid catalyst component [A3 in the range of from 0.2 to 10. A preferred mole ratio of Mg/(Ti and/or V) is in the range of 0.5 to S. The solid catalyst component [A] thus obtained has a very large specific surface area. In accordance with the measurement by the B.E.T. method, the speclfic surface area ranges from about 50 m2¦g to about 400 m2/g.
The inorganic or organic compound (3) of aluminum, silicon, tin or antimony which is additionally reacted with the solid catalyst component [A] before being reacted ~ith the organometal component [B]
is a compound having a halogen atom, a hydrogen atom, a hydrocarbon group, an alkoxy group or an aryloxy group. Suitable examples of such compounds include an alkoxyaluminum dihalide, an allcylaluminum dihalide, a monoalkoxysilicon halide, a monoalkylsilicon halide, a silicon tetrahalide, a monoalkoxytin halide, a monoalkyltinhalide, a tin tetrahalide, antimony pentachloride and a monoalkylantimony halide.
Of these compounds, an alkylaluminum dihalide~ silicon tetrachloride and tin tetrachloride are preferred.
The titanium or vanadium compound (4) which is additionally reacted with the solid catalyst component [A] before being reacted with the organometal component [B] may be the same as the titanium and/or vanadium compound (2). It is preferred that the titanium or vanadium si compound (4) has at least 3 halogen atoms. Titanium tetrachloride and vanadium tetrachloride are more preferred.
The reaction between the solid catalyst [A] and the inorganic or organic compound (3) or the titanium or vanadium compound (4) is conducted in a ratio of 1 g of ~A] to 1 mmole to 100 mmoles of the compound (3) or the compound (4), preferably 1 g of [A] to 2 mmoles to 50 mmoles of the compound (3) or the compound (4) in the presence or absence of an inert hydrocarbon medium at a temperature of from about 10C to about 150C for about 1 to about 50 hours. After completion of the reaction, it is preferred that the solid type catalyst component [A']
formed is isolated and washed with the inert hydrocarbon medium. The above described reaction can be conducted multi-step-wise, i.e.~ in two or three steps by using the same or different compound (3) or compound (4).
~xemplary inert hydrocarbon media include an aliphatic hydrocarbon such as hexane or heptane, an aromatic hydrocarbon such as benzene or toluene and an alicyclic hydrocarbon such as cyclohexane or methlcyclohexane.

3~6 The solid catalyst component ~A] or the solid type catalyst component ~ of this invention as such is useful as a catalyst for polymerizing ~-olefins. ~lowever, the solid catalyst component [A] or the solid type catalyst component [~'] of this invention in combination with an organometal compound [B] becomes a more improved catalyst.
The organometal compound [B] which can be employed in this invention is a compound of a metal of Groups I to III of the Periodic Table, and especially an organoaluminum compound and an organomagnesium complex are preferred. ~s the organoaluminum compounds, those repre-sented by the general formula, ~QRamY3-m wherein R8 is a hydrocarbon group having 1 to 20 carbon atoms, Y is a member selected from a hydrogen atom, a halogen atom, an alkoxy group having 1 to 20 carbon atoms, a phenoxy group, a substituted phenoxy group, and a siloxy group, and m is a number from 2 to 3, can be employed individually or as a mixture. In the above formula, the hydrocarbon groups having 1 to 20 carbon atoms represented by R8 include aliphatic hydrocarbons, aromatic hydrocarbons~and alicyclic hydrocarbons.
Exemplary organoaluminum compounds include triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trihexylaluminum,trioctylalumlnum, tridecylaluminum, tridodecylaluminum, trihexadecylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, diethylaluminum ethoxide, diisobutylaluminum ethoxide, dioctylaluminum butoxide, diisobutylaluminum octyloxide, diethylaluminum chloride, diisobutylaluminum chloride, dimethylhydro-siloxyaluminum dimethyl, ethymethylhydrosi]oxyaluminum diethyl and ethyldimethylsiloxyaluminum diethyl and mixtures thereof.

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As the organomagnesium complexes, those represented by the general formula, MgdMeR9fRl0h wherein M is a metal atom selected from the group consisting of aluminum, boron, beryllium and zinc;
R9 and Rl may be the same or difEerent and each is a hydrocarbon group having 1 to 10 carbon atoms;
d7 e, f and h, each is zero or a number above zero;
d/e = 1 to 8; and 2d ~ ~e = f ~ h, wherein ~ is the valence of M, can be employed individually or as a mixture.
Of these groups, preferred hydrocarbon groups represented by R9 and Rl are alkyl groups, cycloalkyl groups and aryl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, an amyl groups, a hexyl group, a decyl group, a cyclohexyl group and a phenyl group. An alkyl group is especially preferred as R9. Of the metal atomsS aluminum and zinc are preferred.
These organomagnesium complexes are easily prepared by using the method disclosed in patents such as U.S. Patents 4,004,071, 4,027,089, 3,989,878 and 4,120,883, and the documents such as Annalen der Chemie, 605, 93 - 97 ~1957), J. Chem. Soc., 1964, 2483 - 85, Chemical Communi-cation, 1966, 559, and J. Org. Chem., 34, 1116 (1969).
A combination of these organometal compounds [B] with the above mentioned solid catalyst component [A] or solid type catalyst component [A'] provides a highly active catalyst, and especially a trialkylaluminum and a dialkylaluminum hydride as the organometal compound [B] are pre-ferred because they show the highest activity. The activity tends to decrease upon introduction oE an electronegative group represented by Y
into the trialkylaluminum or the dialkylaluminum hydride. However, such 3~;

organoaluminum compounds containing the Y group show unique polymeri-zatlon behaviors, respectively, to produce useful polymers with a high activity. For example, introduction of an alkoxy group render control of the molecular weight of polymers easy. Since the presence of halogen atoms in the polymeri~ation system and in the polymers produced is not desirable, an alkoxy group and an siloxy group is preferred as the Y
group.
The solid catalyst component [A] and the organometal component [B] may be added under the polymerization conditions to the polymerization system or may be combined prior to the polymerization.
It is preferred that the ratio of these two components ranges from 1 mmole to 3000 mmoles of the organometal compound [B] per gram of the solid catalyst component [A].
The halogenated hydrocarbons which can be employed in combi-nation with the solid catalyst component [A] or the solid type catalyst component [A'] together with the organometal compound [B] in order to give polymers having a broad molecular weight distribution with high catalytic activity are saturated or unsaturated halogenated hydrocarbons having 1 to 15 carbon atoms. It is preferred that the number of halogen atom of the halogenated hydrocarbons is at most twice that of carbon atom of the halogenated hydrocarbons. Exemplary halogenated hydrocarbons include dichloromethane, 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,2,2-tetrachloroethane, 1,2-dichloropropane, 1,3-dichloropropane, 15 2,3-trichloropropane, n-butyl chloride, isobutyl chloride, l,~-dichloro-butane, 2,3-dichlorobutane, 1,2,3,~-tetrachlorobutane, n-hexyl chloride, 1,6-dichlorohexane, 1,2-dichlorooctane, dibromomethane, 1,2-dibromoethane, n-butyl bromide, chloroben~ene, phenethyl chloride, allyl chloride~
bromoben~ene and ethyl iodide.
The combination of these halogenated hydrocarbons [C] with the above described solid catalyst component [A] or solid type catalyst component ~A'] and the organometal compound ~] may be conducted under the reaction conditions with the passage of the polymerization or may be conducted prior to the polymerization. Also, the polymerization can be carried out by USillg the reaction product obtained by reacting the solid catalyst component [A] or solid type catalyst component [A'] with the halogenated hydrocarbon [C] and isolating the solid formed, and the organometal compound with or without further addition of the same or different halogenated hydrocarbon. It is preferred that the ratio of these catalyst components ranges from 1 mmole to 3000 mmoles of the organometal compound [B] per gram of the solid catalyst component [A]
and 1 mmole to 3000 mmoles of the halogenated hydrocarbon per gram of the solid catalyst component [A] and the mole ratio of the halogenated hydrocarbon [C] to the organoaluminum compound 1A] ranges 0.01 to 100, especially 0.1 to 20.
Detailed Description of the Polymerization The olefins polymerized by using the present catalyst may be ~-olefins, especially ethylene. Further, the present catalysts may be employed for copolymerlzing ethylene and other monoolefins such as propylene, butene-l and hexene-l and dienes such as butadiene and isoprene. Also propylene may be polymerized with good efEiciency by employing the present catalysts.
As for the polymerization method, there may be employed the usual suspension-, solution- and gas phase-polymerizations. In the cases of suspension- and solution-polymerizations, the catalyst is introduced into a reactor to~ether with a polymerizat;on medium including an aliphatic hydrocarbon such as hexane or heptane; an aromatic hydrocarbon such as benzene, toluene or xylene; or an alicyclic hydrocarbon such as cyclohexane or methylcyclohexane, and, an ~-olefin is added under a pressure of about l to about 200 Kg/cm2 in an inert atmosphere and allowed to polymerize at a temperature from about 10C to about 300C.

3~
For gas phase-plymerization, it is possible to carry out poly-merization under an ~-olefin pressure of about 1 to about 50 Kg/cm2 and a temperature from about 10C to about 120C, using a fluidized bed, moving bed or mixing with a stirrer to provide better contact between the ~-olefin and the catalyst.
There may be employed single stage polymerization having one polymerization zone or multistage polymerization having a plurality of polymerization zones.
When multiple stage polymerization is effected in at least two polymerization zones having different polymerization conditions, by using the present catalyst it is possible to produce a polymer whose molecular weight distribution is much broader.
In order to control the molecular weight of the polymer, it is also possible to add hydrogen, a halogenated hydrocarbon or an organo-metalic compound which can cause chain transfer.
The following examples of preferred embodiments further illustrate the principle and practice of ~he invention.
In the following e~ample Mw is the weight average molecular weight determined according to the following equation;
[~] = 6.8 x lo-4Mwo. 6 7 [see Journal of Polymer Science, 36, 91 ~1957)], ~w/Mn is the index of molecular weight distribution measured by gel permeation chromatography, and the term "catalytic efficiency" shows the amount of polymer formed per gram of catalyst per hour of reaction time per Kg/cm2 of ~-olefin pressure.

3~
Example 1 (I) Synthesis of Organomagnesium Compound (1) In a 1 Q flask purged with nitrogen were charged 6.1 g (250 mmoles) oE magnesium powder, and then 1/10 of 300 mQ of a n-heptane solution containing 250 mmoles of C2H5Br was added thereto. On stirring at an internal temperature of the flask o 90C~ the reaction was started after about 10 minutes. To the reaction mixture solution was added the rest of the n-heptane solution over 2 hours with stirring while keeping the inter-nal temperature of the flask at 90C, and further the reaction was con-tinued at 90C for one hour. Then 200 mQ of a heptane solution containing 1 mole/Q of n-butyllithium to the reaction solution and the mixture was refluxed under heating for 6 hours. After completion of the reaction, the reaction solution was left to stand and the supernatant liquid was r collected. On analysis of Mg and Br, this liquid contained 0.37 mole/Q
of Mg and less thon 0.01 mole/Q of Br. Also, the liquid was reacted with iodine in two equivalent amount of iodine to magnesium atom and the alkyl iodide formed had a C2H5I to n-C4HgI mole ratio of 1.05 according to the analysis~by gas chromatography. The organomagnesium compound obtained was C2HsMgn-C4H9.
(II) Synthesis of Solid Catalyst Component [A]
The oxygen and moisture present inside a 500 mQ flask equipped with two dropping funnels were purged with dry nitrogen, and to the flask were charged 160 mQ of n-heptane and cooled to -5C. Then 80 mQ of a heptane solution containing 40 mmoles of the above-obtained C2HsMgn-C~Hg and 80 mQ of a n-heptane solution containing 60 mmoles of titanium tetrachloride were accurately measured and separately charged in the dropping funnels, respectively. Both components were simultaneously added to the flask at -5C with stirring over two hours, and further the aging reaction was continued at 5C. The solid catalyst component [A]

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formed which was insoluble in the hydrocarbon medium was isolated, washed with n-heptane and dried.
(III) Polymerization In a 1.5 Q autoclave evacuated and purged with nitrogen were charged 5 mg of the solid catalyst component ~A] and 0.4 mmole of triisobutylaluminum with 0.8 Q of dehydrated and deaerated n-heptane.
While keeping the internal temperature of the autoclave at 85C, hydrogen was added up to a gauge pressure of 1.6 Kg/cm2. Then ethylene was added up to a total gauge pressure of 4.0 Kg/cm2. While maintai-ning the total gauge pressure of 4.0 Kg/cm2 by adding additional ethylene~ the polymeri-zation was carried out for one hour to give 134 g of a polymer. The polymer had Mw of 125000, Mw/Mn of 10.3, a catalytic efficiency of 11200 and a bulk density of 0.39 g!c.c.

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Examples 2 to 12 Solid catalyst component [~] were prepared by reacting (1) the organomagnesium compounds as set forth in Table I with (2) the titanium and/or vanadium compounds having at least one halogen atom as set forth in Table I under the reaction conditions as set forth in Table I in the same manner as described in Example 1. Using these solid catalysts (1) and triisobutylaluminum, polymerization of ethylene was carried out under the same polymerization conditions as in Example 1. The results are shown in Table I.

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Examples 13 to 21 Polymerization of ethylene was carried out under the same polymerization conditions as in Example l, except that the organometal compounds [B] and the halogenated hydrocarbons [C] as set forth in Table II were used instead of the triisobutylaluminum. The results are shown in Table II.

1~.2~;~26 Examples 22 to 31 2 g of the same solid catalyst component [A] as prepared in Example 2 were reacted with the component (3) and/or the component (4) as set forth in Table III under the reaction conditions as set forth in Table III to give solid type catalyst component9 [A']. Polymerization of ethylene was carried out under the same polymerization conditions as in Example 1, by using 5 mg of the solid type catalyst as obtained above and the organoaluminum compound [B] and the halogenated hydrocarbon [C] as set forth in Table III. The results are shown in Table III.

Example 32 2 g of the same solid catalyst component [A] as prepared in Example 8 were reacted with 8 mmoles of AQ(C2H5)CQ2 in 100 mQ of n-heptane at 80C for 2 hours. After completion oE the reaction, the supernatant liquid was removed from the reaction mixture solution and the residue was washed twice with n-heptane. Then 10 mmoles of TiCQ4 and 50 mQ of n-heptane were added to the residue, and the reaction was carried out at 80C for one hour and the solid type catalyst component [A'] formed was isolated.
Polymerization of ethylene was carried out under the same polymerization conditions as in Example l, by using the above obtained solid catalyst to give 87 g of a polymer.~ The polymer had a catalytic efficiency of 7250, a Mw of 193000, a Mw/~n of 16.3 and a bulk density of 0.~17 glc-c-It will be appreciated that the instant specification andexamples are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit and scope of the present invention.

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Claims (30)

WHAT IS CLAIMED IS :

1. A catalyst suitable for polymerizing an .alpha.-olefin, comprising a solid catalyst component [A] and an organometal compound [B], the solid catalyst component [A] being prepared by reacting an organomagnesium com-pound (1) soluble in a hydrocarbon medium and represented by the general formula, MgR1pR2qXr?Zs wherein R1 is a hydrocarbon group having 2 to 3 carbon atoms;
R2 is a hydrocarbon group having 4 to 20 carbon atoms and the difference in number of carbon atoms between R1 and R2 is at least 2;
X is an electronegative group having an oxygen atom, a nitrogen atom or a sulfur atom;
Z is an organometal compound of aluminum, boron, beryllium, zinc, silicon or lithium;
p and q each is a number above 0 to 1;
r is a number from 0 to 1;
p + q + r = 2; and s is a number above 0 to below 0.1, with a titanium and/or vanadium compound (2) having at least one halogen atom.

2. The catalyst of claim 1, wherein R1 is a member selected from the group consisting of an ethyl group, a n propyl group and an isopropyl group.

3. The catalyst of claim 1, wherein R2 is a member selected from the group consisting of a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group and a hexadecyl group.

4. The catalyst of claim 1, wherein R1 is an ethyl group and R2 is a butyl group.

5. The catalyst of claim 1, wherein R1 is an ethyl group and R2 is a pentyl group.

6. The catalyst of claim 1, wherein R1 is an ethyl group and R2 is a hexyl group.

7. The catalyst of claim 1, wherein X is a member selected from the group consisting of an alkoxy group having 1 to 20 carbon atoms, a siloxy group, a phenoxy group, a substituted phenoxy group, an amino group, an amido group, an group wherein R3 and R4 may be the same or different and each is a hydrocarbon group having 1 to 20 carbon atoms, an SR5 group wherein R5 is a hydrocarbon group having 1 to 20 carbon atoms, and a .beta.-ketoacid group.

8. The catalyst of claim 7, wherein X is an alkoxy group having 1 to 20 carbon atoms.

9. The catalyst of claim 7, wherein X is a siloxy group.

10. The catalyst of claim 1, wherein r is a number from 0 to 0.6.

11. The catalyst of claim 10, wherein r is a number from 0.2 to 0.6.

12. The catalyst of claim 1, wherein Z is an organoaluminum compound of the general formula, A?R6n(OR7)3-n, wherein R6 and R7 may be the same or different and each is a hydro-carbon group having 1 to 20 carbon atoms, and n is a number from 0 to 3.

13. The catalyst of claim 1, wherein s is a number from 0.02 to 0.09.

14. The catalyst of claim 1, wherein the titanium and/or vanadium compound (2) has at least 3 halogen atoms.

15. The catalyst of claim 1, wherein the mole ratio of the organo-magnesium compound (1) to the titanium and/or vanadium compound (2) [Mg/(Ti and/or V)] is 0.2 to 10.

16. The catalyst of claim 15, wherein the mole ratio of the organo-magnesium compound (1) to the titanium and/or vanadium compound (2) [Mg/(Ti and/or V)] is 0.5 to 5.

17. The catalyst of claim 1, wherein the organometal compound [B] is an organoaluminum compound of the general formula, A?R8mY3-m wherein R8 is a hydrocarbon group having 1 to 20 carbon atoms.
Y is a member selected from the group consisting of a hydrogen atom, a halogen atom, an alkoxy group having 1 to 20 carbon atoms, a phenoxy group, a substituted phenoxy group and a siloxy group and m is a number from 2 to 3.

18. The catalyst of claim 17, wherein the organometal compound is a trialkylaluminum.

19. The catalyst of claim 17, wherein the organometal compound is a dialkylaluminum hydride.

20. The catalyst of claim 1, wherein the organometal compound [B] is an organomagnesium complex of the general formula, MgdMeR9fR10h wherein M is a metal atom selected from the group consisting of aluminum, boron, beryllium and zinc;
R9 and R10 may be the same or different and each is a hydrocarbon group having 1 to 10 carbon atoms;
d, e, f and h, each is zero or a number above zero;
d/e = 1 to 8; and 2d + .alpha.e = f + h, wherein .alpha. is the valence of M.

21. The catalyst of claim 20, wherein M is aluminum.

22. The catalyst of claim 20, wherein M is zinc.

23. The catalyst of claim 1, additionally containing [C] a halogenated hydrocarbon having 1 to 15 carbon atoms, the number of halogen atom being at most twice that of carbon atom and the mole ratio of the halogenated hydrocarbon [C] to the organometal compound [B] being 0.01 to 100.

24. The catalyst of claim 1 or 23, wherein the solid catalyst com-ponent [A] before being reacted with the organometal compound [B] is additionally reacted with an inorganic or organic compound (3) of aluminum, silicon, tin or antimony having at least one halogen atom and being soluble in a hydrocarbon medium, in a ratio of 1 g of [A] to 2 mmoles to 10 mmoles of the compound (3) at a temperature of from about 10°C to about 150°C.

25. The catalyst of claim 1 or 23, wherein the solid catalyst com-ponent [A] before being reached with the organometal compound [B] is additionally with a titanium or vanadium compound (4) having at least one halogen atom in a ratio of 1 g of [A] to 2 to 10 mmoles of the compound (4) at a temperature of from about 10°C to about 150°C.

26. A process for polymerizing an .alpha.-olefin which comprises contacting the .alpha.-olefin with the catalyst of claim 1.

27. The process of claim 26, wherein the .alpha.-olefin is ethylene.

28. A process for polymerizing ethylene which comprises contacting the ethylene with the catalyst of claim 23.

29. A process for polymerizing ethylene which comprises contacting the ethylene with the catalyst of claim 24

30. A process for polymerizing ethylene which comprises contacting the ethylene with the catalyst of claim 25.