CA1187866A - High efficiency catalyst for polymerizing olefins prepared from organotitanium and magnesium components - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Compositions exhibiting high catalytic activity in the polymerization of .alpha.-olefins are prepared by reacting a mixture of a tetrahydrocarbyloxy titanium compound such as tetraisopropyl titanate and a hydrocarbyloxy titanium oxide such as di(isopropoxy) titanium oxide, an organomagnesium component such as a hydrocarbon soluble complex of dialkyl magnesium and an organoaluminum compound such as triethyl aluminum and a halide source such as ethyl aluminum dichloride.
Polymerization processes employing this catalyst compo-sition do not require conventional catalyst removal steps in order to provide polymers having suitable color and other physical characteristics and these catalysts provide higher efficiencies than those catalysts employing either of the titanium compounds alone.

Description

6~i HIGH EFFICIENCY CATALYST FOR POLYMERIZING OLEFINS

This invention relates to a new catalyst composition useful for polymerization of ~-olefins and to a polymerization process employing such a catalyst composition.

It is well known that olefins such as ethylene, propylene and l-butene in the presence of certain metallic catalysts can be polymerized to form sub-stantially unbranched polymers of relative]y high molecular weight. Among the methods for producing such linear olefin polymers, some of the most widely utilized are those described by Professor Karl Ziegler in U.S.
Patents 3,113,115 and 3,257,332. In these methods, the catalyst employed is obtained by admixing a compound of a transition metal of Groups IVB, V, VIB and VIII of Mendeleev's Period Table of Elements with an organo-metallic compound. Generally, the halides, oxyhalides and alkoxides or esters of titanium, vanadium and zirconium are the most widely used transition metal compounds. Common examples of the organometallic compounds include the hydrides, alkyls and haloalkyls of aluminum, alkylaluminum halides, Grignard reagen-ts, alkali metal aluminum hydrides, alkali metal 27,760A-F

'7~i6 borohydrides, alkali metal hydrides, alkaline earth metal hydrides and the like. Usually, polymerization is car~ied out in a reaction medium comprising an inert organic liquid, e.y., an aliphatic hydrocarbon and the aforementioned catalyst. One or more olefins may be brought in-to contact with the reaction medium in any suitable manner. A molecular weight regulator, which is normally hydrogen, is usually present in the reaction vessel in order to suppress the formation of undesirably high molecular weight polymers.

Most of the aforementioned known catalyst systems are more efficient in preparing polyolefins in slurry (i.e., wherein the polymer is not dissolved in the carrier) than in solution (i.e., wherein the temperature is high enough to solubilize the polymer in the carrier). The lower efficiencies oF such catalysts in solution polymerization is generally believed to be caused by deactivation of such catalysts by the higher temperatures employed in solution processes. In addition, processes involving the copolymerization of ethylene with higher ~-olefins exhibit catalyst efflciencies significantly lower than ethylene homopolymerization processes.

Recently, catalysts having higher efflcien-cies have been disclosed, e.g., U.S. Patent 3,392,159;U.S. Patent 3,737,393; West German Patent Application

2,231,982 and ~ritish Patents 1,305,610 and 1,358,437.
While the increased efficiencies achieved by using these recent catalysts are significant, even higher efficiencies are desirable, particularly in copolymer-ization processes. These high efficiency catalysts generally produce polymers of relatively narrow molec-27,760A~F -2-~'7~

ular weigh-t distribution. But for certain uses, a wider molecular weight range is desirable.

The present invention, in one aspect, is an improvement in the cataly-tic reaction produc-t of (A) a tetravalent titanium compound, (B) an organomagnesium component, (C~ a halide source, and, if either components (B) or (C) does no-t contain sufficient quantities of aluminum, then (D) an alumlnum compound is also present;
the improvement being the use of, as the titanium compound, a mixture containing a tetrahydrocarbylo~y titanium compound and a dihydrocarbyloxy titanium oxide. The molar ratio of the tetraalkoxy titanium compound to dialkoxy titanium o~ide is 0.1.1 to 10:1, preferably 0.2:1 to 5:1 and most preferably 0.33:1 to 1~ 3:1.

The magnesium component is (1) a complex of an organomagnesium compound and an organometallic compound which solubilizes the organomagnesium compound in a hydrocarbon solvent or (2) an organomagnesium compound. The proportions of the foregoing components of said catalytic reaction produc-ts are such that the atomic ratios of the elements are:

Mg:Ti is 1:1 to 200:1;
preferably 2:1 to 100:1;
most preferably 5:1 to 75:1;

Al:Ti is 0.1:1 to 1000:1;
preferably 0.5:1 to 200:1;
most preferably 1:1 to 75:1;

27,760~-F -3-7~
~ .

excess X:AI is 0.0005:1 to 5:1;
preferably 0.001:1 to 2:1;
most preferably 0.01:1 to 1.4:1.

The X is excess halide above that which would be theoretically re~uired to convert the magnesium compound to the dihalide.

In a second aspect, the invention is a process for polymerizing at least one ~-olefin or diolefin under conditions characteristic of Ziegler polymeriza tion wherein the aforementioned reaction product is employed as the catalyst.

The present invention is most advantageously practiced in a polymerization process wherein an ~-olefin or diolefin is polymerized, generally in the presence of hydrogen as a molecular weight control agent, in a polymerization zone containing an inert diluent and the catalytic reaction product. Especially advantageous is the copolymerization of ethylene and higher ~-olefins or diolefins using the cataly-tic reaction product of this invention. The process is most beneficially carried out under inert atmosphere and relatively low temperature and pressure, although very high pressures are optionally employed.

Olefins which are suitably homopolymerized or ~5 copolymeriæed in the practice of this invention are generally the aliphatic ~-monoolefins or ~-diolefins having from 2 to 1~ carbon atoms. Illustratively~ such ~-olefins can include ethylene, propylene, butene-1, pentene-1, 3-methylbutene-1, 4-methylpentene-1, hexene-1, octene-1, dodecene-l, octadecene-1, and 1,7-octadiene.

27,760A-F -4-7~

It is understood that ~olefins may be copolymerized with other ~-olefins and/or with small amounts, i.e. up to about 25 weight percent based on the copolymer, of other ethylenically unsaturated monomers such as styrene, 5 u-methylstyrene and similar ethylenically unsaturated monomers which do not destroy conventional Ziegler catalysts. Most benefits are realized in the polymer-ization of aliphatic ~-monoolefins, particularly ethylene and mixtures of ethylene and up to 50, especially from about 0.1 to 40, weight percent of propylene, butene-1, hexene-l, octene-1, 4-methyl-pentene-l, 1,7-octadiene or similar ~-olefin or diolefin based on total monomer.

Advantageously, the titanium tetraalkoxide is represented by the empirical formula Ti(OR)~I wherein each R is independently an alkyl or an aryl group having from 1 to 12, preferably from 2 to 10, carbon atoms. Exemplary of such compounds include tetra-n--butoxytitanium, tetra(isopropoxy)titanium, and tetraphenoxytitanium.

Advantageously, the dialkoxy titanium oxide is represented by the empirical formula (Ro)~Tio wherein each R is independently an alkyl or an aryl group having 1 to 12, preferably 2 to 10, carbon atoms.
Exemplary of such compounds are diethyoxy titanium oxide, diisopropoxy titanium oxide, di-n-butoxy titanium oxide, diphenoxy titanium oxide, mixtures thereof and the like.

The dihydrocarbyloxy titanium oxides employed in the present invention can be prepared according to the procedure described in THE O~GANIC C~E~ISTRY OF

27,760A-F -5-TITANIUM, Raoul Feld & P. 0. Cowe, Butterwor-th & Co.
(Publishers) Ltd., 1965, page 141.

The preferred organomagnesium component is a hydrocarbon soluble complex illustrated by the empir-ical formula MgR"2-xMR"y wherein each R" is indepen-dently hydrocarbyl or hydrocarbyloxy; M is aluminum, zinc or mixtures -thereof; x is zero to 10, especially zero to 2.5, and y denotes the number of hydrocarbyl groups which corresponds to the ~alence of M. As used herein, hydrocarbyl and hydrocarbyloxy are monovalent hydrocarbon radicals. Preferably, hydrocarbyl is alkyl, cycloalkyl, ar~l, aralkyl, alkenyl and similar hydrocarbon radicals having 1 to 20 carbon atoms, with alkyl having 1 to 10 car~on atoms being especially preferred. Likewise, preferably, hydrocarbyloxy is alkoxy, cycloalkyloxy, aryloxy, aralkyloxy, alkenyloxy and similar oxyhydrocarhon radicals having 1 to 20 carbon atoms, with alkyloxy having 1 -to 10 carbon atoms being preferred. Hydrocarbyl is preferred over hydrocarbyloxy.

This complex is prepared by reacting particulate magnesium, such as magnesium turnings, or magnesium particles with about a stoichiometric amount of hydro-carbyl or hydrocarbyloxy halide, illustrated as R'X.
The resulting MgR"2, if it is hydrocarbon insoluble, can be solubilized by adding the organometallic compound such as AlR"3 or mixtures thereof with ZnR"2.
The amount of organometallic compounds which is added to the MgR"2 to form the organomagnesium complex should be enough to solubilize a significant amount of MgR"2, e.g., at least 5 weight percent of MgR"2. It is preferred to solubilize at least 50 weight percent of 27,760A-F -~-the MgR"2 and especially preferred to solubilize all the MgR" 2 -To obtain maximum catalyst efficiency atpolymerization temperatures above 180~C, it is desirable to minimize the amount of aluminum in the complex as well as in the total catalyst. Accordingly, for catalysts having Al:Ti atomic ratios less than 120:1 it is desirable to have a Mg:Al atomic ratio more than 0.3:1, preferably 0.5:1 to 10:1. In suitable complexes, organometallic compounds (other than AlR"3 , ZnR"2 or mixtures thereof) which also solubilize the organomagnesium compound in hydrocarbon are employed in beneficial amounts, usually an amount sufficient to produce an a-tomic ratio of 0.01:1 to 10:1 of metal of the organometallic compounds to magnesium. Examples of such other organometallic compounds include boron krialkyls such as boron triethyl, alkyl silanes such as dimethyl silane and tetraethyl silane, alkyl tin and alkyl phosphorous compounds.

Alternately to such solubilized magnesium complexes, other organomagnesium compounds although insoluble i~ hydrocarbons, are often suitably employed.
These compounds can be rendered soluble in hydrocarbon by addition of ether, amine, etc., although such solubilizing ayents often reduce the activity of the catalyst. Recently, such compounds have been made hydrocarbon soluble without such additives, e.g., as taught in U.S. 3,646,231. Such hydrocarbon soluble organomagnesium compounds are -the mos-t desirable if an organomagnesium compound is to be used as the organo-magnesium component.

27,76OA-F 7-ki Preferably the organomagnesium compound is a hydrocarbon soluble dihydrocarbylmagnesium such as -the magnesium dialkyls and the magnesium diaryls. Exemplary suitable magnesium dialkyls include particularly n-butyl-sec-butyl magnesium, diisopropyl magnesium, di-n hexyl magnesium, isopropyl-n-butyl magnesium, ethyl-n-hexyl magnesium, ethyl-n-butyl magnesium, di-n-octyl magnesium and others wherein alkyl is from 1 -to 20 carbon atoms. Exemplary suitable magnesium diaryls include diphenylmagnesium, dibenzylmagnesium, and ditolylmagnesium, being especially preferred.
Suitable organomagnesium compounds include alkyl and aryl magnesium alkoxides and aryloxides and aryl and alkyl magnesium halides with the halogen-free organo-magnesium compounds being more desirable.

Suitable organoaluminum compounds includethose represented by the empirical formula AlR3 aXa wherein R is hydrocarbyl, hydrocarbyloxy or as herein-before defined such as alkyl; X is a halogen and a is a number from zero to 3. Most preferred are the aluminum alkyls such as, for example, triethyl aluminum, triiso-butyl aluminum, diethylaluminum chloride, diethyl-aluminum bromide, mixtures thereof and the like.

It is understood tha-t the organic moieties of 2~ the aforementioned organomagnesium, e.g., R", and the organic moieties of the halide source, e.g., R and R', are suitably any other organic radical provided that they do not contain functional groups that poison conventional Ziegler catalysts. Preferably such organic moieties do not contain active hydrogen, i.e.
those sufficiently active to react with the Zerewitinoff reagent.

27,760A-F -8-,_g._ The halide source is suitably a nonmetallic halide corresponding to the empirical formula R'X
wherein R' is hydrogen or an active monovalent organic radical and X is halogen. Alternatively, the halide source is a metallic halide corresponding to the empirical Eormula MRy aXa wherein M is a metal of Group IIIA or IVA of Mendeleev's Periodic Table of the Elements, R is a monovalen~ organic radical, usually hydrocarbyl or hydrocarbyloxy, X is halogen, y is a number corresponding to valence of M and a is a number from 1 to y.

The preferred halide sources are the active non-metallic halides of the formula set forth above including hydrogen halides and active organic halides such as t-alkyl halides, allyl halides, benzyl halides and other active hydrocarbyl halides wherein hydro-carbyl is as defined hereinbefore. By an active organic halide it is meant a hydrocarbyl halide that contains a halide atom at least as active, i.e., as easily los-t to another compound, as the halogen of sec-butyl chloride, and preferably as active as -t-butyl chloride. In addition to the organic monohalides, it is understood that organic dihalides, trihalides and other polyhalides that are active as defined hereinbefore are also suitably employed. Examples of preferred active non-metallic halides include hydrogen chloride, hydrogen bromide, t-butyl chloride, t-amyl bromide, allyl chloride, benzyl chloride, crotyl chloride, methylvinyl carbinyl chloride, ~-phenylethyl bromide, diphenyl methyl chloride, t-butyl chloride, allyl chloride and benzyl chloride.

Suitable metallic halides as set forth by formula hereinbefore are organometallic halides and metal halides wherein the metal is in Group III~ or 27,760A-F -9-IVA, of Mendeleev's Periodic Table of Rlements. Pre-ferred metallic halides are aluminum halides of the empiri~al formula AlR3 aXa wherein each R is indepen-dently hydrocarbyl as hereinbefore defined such as alkyl; X is a halogen and a is a number from 1 to 3.
Most preferred are alkylaluminum halides such as ethyl-aluminum ses~uichloride, diethylaluminum chloride, ethylaluminum dichloride and diethylaluminum bromide, with ethylaluminum dichloride being especially preferred.
Alternatively, a metal halide such as aluminum tri-chloride or a combination of aluminum trichloride with an alkyl aluminum halide or a trialkyl aluminum compound may be suitably employed.

In order to maximize catalyst efficiency, the ca-talyst is prepared by mixing the components of the catalyst in an inert liquid diluent in one of the following especially preferred orders;
(1) A, D (if necessary), C and R;
(2) B, C, D (if necessary) and A;

(3) ~, C, A and D (if necessary and if C is not a tin chloride);

(4) C, D (if necessary), A and B
with methods 2 and 3 being especially preferred. The foregoing catalyst components are combined in propor-tions sufficient to provide molar and atomic ratios as previously mentioned.

The foregoing catalytic reaction is prefer-ably carried out in the presence of an inert diluent.
The concentrations of catalyst componen-ts are prefer-ably such that when the essential components of thecatalytic reaction product are combined, the resultant slurry is 0.005 to 1.0 molar (moles/liter) with 27,760A-F -10-respect to magnesium. By way of an example of suitable inert organic diluents can be men-tioned liquefied ethane~ propane, isobutane, n-butane, n-hexane, the various isomeric hexanes, isooctane, paraffinic mixtures of alkanes haviny from 8 to 12 carbon atoms, cyclohexane, methylcyclopentane, dimethylcyclohexane, dodecane, 2,2,4-trimethylpentane industrial solvents composed of saturated or aroma-tic hydrocarbons such as kerosene, naphthas, etc., especially when freed of any olefin compounds and other impurities, and especially those having boiling points in the range from 50C to 200C. Also included as suitable inert diluents are benzene, toluene, ethylbenzene, cumene, decalin and the like.

Mixing of the catalyst components to provide the desired catalytic reaction product is advanta~
geously carried out under an inert atmosphere such as nitrogen, argon or other inert gas at temperatures in the range from ~100C to 200C, preferably 0C to 100C. The period of mixing is not considered to be critical as it is found that a sufficient catalyst composltion most often occurs within 1 minute or less. In the preparation of the catalytic reaction product, it is not necessary to separa-te hydrocarbon soluble components from hydrocarbon insoluble com-ponents of the reaction product.

If desired, the catalytic reaction product of this invention may also contain a dialkyl zinc compo-nent wherein the alkyl groups are the same or different and contain from 1 to 10 carbon atoms. Suitable such dialkyl zinc compounds include, for example, diethyl zinc, diisopropyl zinc, di-n-propyl zinc, di-n butyl 27,760A-F -11-7~
-~2-zinc, di sec-butyl zinc, mix-tures thereof and the like.
Such zinc compounds tend to provide polymers of broadened molecu~ar weight distribution, as taught ln U.S. Patent 4,238,355.

In the polymerization process employing the catalytic reaction product, polymerization is effected by adding a catalytic amount of the above catalyst composition to a polymerization zone containing ~-olefin monomer, or vice versa. The polymerization zone is maintained at temperatures in the range from 0 to 300C, preferably at solution polymerization temperatures, e.g., from 130C to 250C for a residence time of a few seconds to several days, preferably 1~ seconds to 2 hours. It is generally desirable to carry out the polymerization in the absence of moisture and oxygen and a catalytic amount of the catalytic reaction product is generally within the range from about 0.001 to 0.1 millimoles titanium per liter of diluent. It is under-stood, however, that the most advantageous catalyst concentration will depend upon polymerization conditions such as temperature, pressure, solvent and presence of catalyst poisons and that the foregoing range is given to obtain maximum catalyst yields in weight of polymer per unlt weight of titanium. Generally in the poly merization process, a carrier which may be an inert organic diluent or solvent or excess monomer, is generally employed. In order to realize the full benefit of the high efficiency catalyst of the present invention, care must be taken to avoid oversatura-tion of the solvent with polymer. If such saturation occurs before the catalyst becomes depleted, the full efficiency of the catalyst ls not realized. For best results, it is preferred that the amount of polymer in the carrier 27,760A-F -12-7~

not exceed about 50 weight percent based on the total weigh-t of the reaction mixture.

The polymeri2ation pressures preferably employed are relatively low, e.g., from 0.~5 to 7.1 MPa (50 to 1000 psig), especially from 0.8 to 5.0 MPa ~100 to 600 psig). However, polymerization within the scope of the present invention can occur at pressure from atmospheric up -to pressures determined by the capabilities of the polymerization eguipment. During polymerization it is desirable to stir the polymerization recipe to obtain better temperature control and to maintain uniform polymerization mixtures throughout the polymer-ization zone.

In order to optimize catalyst yields in the polymerization of ethylene, it is preferable to main-tain an ethylene concentration in the solvent in the range from about 1 to 10 weight percent, most advan-tageously 1.2 to 2 weight percent. To achieve this, when an excess of ethylene is fed into the system, a portion of the ethylene can be vented.

Hydrogen can be employed in the practice of this invention -to alter the molecular weight of the resultant polymer. For the purpose of this invention, it i5 beneficial to employ hydrogen in concentrations ranging from 0.001 to 1 mole per mole of monomer. The larger amounts of hydrogen within this range are found to pro~uce generally lower molecular weight polymers.
It is understood that hydrogen can be added with a monomer stream to the polymerization vessel or separately added to the vessel before, during or after addition of the monomer to the polymerization vessel, but during or before the addition of the catalyst.

27,760A-F -13-7~

The monomer or mixture of monomers is con-tacted with the catlytic reaction product in any con-ven-tional manner, preferably by bringing the catalytic reaction product and monomer together with intimate agitation provided by suitable stirring or other means.
Agitation can be continued during polymerization, or in some instances, the polymerization can be allowed to reamin unstirred while the polymerization takes place.
In the case of more rapid reactions with more active catalysts, means can be provided for refluxing monomer and solvent, if any of the latter is present and thus removing the heat of reaction. In any event adequate means should be provided for dissipa-ting the exothermic heat of polymerization. If desired, the monomer can be brought in the vapor phase into contact with the catalytic reaction product, in the presence or abs~nce of liquid material. The polymerization can be effected in the batch manner, or in a continuous manner, such as, for example, by passing the reaction mixture through an elongated reaction tube which is contacted externally with suitable cooling medium to maintain the desired reaction temperature, or by passing the reaction mi~ture through an equilibrium overflow reactor or a series of the same.

The polymer is readily recovered from the polymerization mixture by driving off unreac-ted monomer and solvent if any is employed. No further removal of impurities is required. Thus, a significant advantage of the present invention is the elimination of the catalyst residue removal steps. In some instanc~s, however, i-t may be desirable to add a small amount of a catalyst deactivating reagent of the types conven-tion~
ally employed for deactivating Ziegler catalysts. The 27,760A-F -14-'7~

resultant polymer is found to contain insignificant amounts of catalyst residue and to possess a relatively bxoad molecular weight distribution.

The following examples are given to illus-trate the invention. All parts and percentages are byweight unless otherwise indicated.

The following atomic weight values were employed in the examples to calculate the ratios of the components.

10Al = 26.98Mg = 24.31 C = 12.01 O = 16.00 Cl = 35.45Ti = 47.90 H = 1.01 In the following examples and comparative experiments, the melt index values I2 and I1o were determined by ASTM D 1238-70 and the density values were de-termined by ASTM D 1248.

COMPARATIVE EXPERIMENT A
A. Preparation of the dihydrocarbyl_xytitanium oxide To 14.88 ml of 0.336 M Ti(OiPr)4 are added, with intense stirring, 0.09 ml of deionized and deoxy-genated water. After allowing 1 -to 2 minutes for reaction, 85.03 ml of 2,2,4-trimethylpentane was added to bring the total volume to 100.0 ml. This results in a 0.05 M solution of the diisopropoxytitanium oxide.
The resulting reaction produc-t is a slurry of ra-ther coarse particles. All component mixing was accom-plished at ambient temperature.

27,760A-F -15-~ ~1'7~

B. Preparat.ion of the Catalyst Composition The catalyst composition was prepared by adding,with stirring under a nitrogen atmosphere to a 120-ml serum bottle the following components in the indicated order:

97.98 ml of 2,2,4-trimethylpentane 0.75 ml of 1.00 M ethylaluminum dichloride (EADC) in 2,2,4-trimethylpentane 0.30 ml of 0.050 M diisopropoxytitanium oxide (Ti(OiPr) 2 O) in 2,2,4-trimethylpentane 0.97 ml of 0.62 M butyl ethyl magnesium in 2,2,4-trimethylpentane The temperature of the serum bottl~ was maintained at ambient temperature (22C) and the reaction was observed to be complete within 5 minutes.

The atomic ratios in -the catalyst components were as follows:
Mg/Ti = 40/1 Al/Ti = 50/1 excess Cl/Al = 0.40/1.

C Pu~-r ~ D
Two liters of 2,2,4-trimethylpentane are added to a one-gallon, stirred batch reactor and heated to 150C. To this is added 0.06 MPA (9 psig) of hydrogen, 0.90 MPa (130 psig) of ethylene, and 5 ml (0.00075 mMole Ti) of the above catalyst. The,temperature was controlled at 150C and the ethylene pressure was held constant during the total reaction time of 30 minutes.
The catalyst yielded 135 gms of polymer for an efficiency of 3.76 x 106 wt. of polyethylene per wt. of titanium.

27,760A-F -16-The polyrner has an I2 melt index of 2.22, and I1o melt index of 19.08, an l1o/I2 ratio of 8.59, and a density of 0.9632.

~. Preparation of the Catalyst Composition The catalyst components were added to a 120 ml serum bot-tle in the following order with stirring under a nitrogen atmosphere:

97.91 ml of 2,2,4-trimethylpentane 0.75 ml of 1.00 M E.~DC in 2,2,4-trimethylpentane 0.225 ml of 0.050 M Ti(OiPr)2O in 2,2,4-trimethylpentane 0.97 ml of 0.62 M butyl ethyl magnesium in 2,Z,4-trimethylpentane 0.15 ml of 0.025 M tetraisopropoxy titanium (Ti(OiPr)~) in 2,2,4-trimethylpentane The molar ratio of Ti(OiPr) 2 : Ti(OiPr)~ = 3:1.

The atomic ratios of the catalyst componen-ts were as follows:

Mg/Ti - 40/1 Al/Ti = 50/1 excess Cl/Al = 0.40/1 B. Polymeri~ation Employing the procedure of Comparative Exper-iment A, 5 ml (O.00075 ~Mole Ti) of this catalyst yielded 168 gms of polymer for a catalyst efficiency of 4.68 x 106 wt. of polyethylene per wt. of titanium.
The polymer had an I2 melt index of 1.21, an I1o melt index of 11.73, a I1o/I2 ratio of 9.69 and a density of 0.9622.

27,760A F -1'7-A. Preparation of the catalyst comPosition , The catalyst components were added to a 120-ml serum bottle in the following order wi-th stirring under a nitrogen atmosphere:

97.76 ml of 2,2,4-trimethylpentane 0.75 ml of 1.00 M EADC in 2,2,4-trimethylpentane 0.075 ml of 0.050 M Ti(OiPr)~O in 2,2,4-trimethylpentane 0.97 ml of 0.62 M butyl ethyl magnesium in 2,2,4-trimethylpentane 0.45 ml of 0.025 M Ti(OiPr)4 in 2,2,4-trimethylpentane The molar ratio of Ti(OiPr) 2 : Ti(OiPr) 4 =
15 0.33:1.

The atomic ratios of the catalyst components were as follows:
Mg/Ti = 40/1 Al/Ti = 50/l excess Cl/Al = 0.40/1 B. Polymerization Employing -the procedure of Comparative Exper-iment A, 5 ml (0.00075 mMole Ti) of this catalyst yielded 182 gms of polymer for a catalyst efEiciency of

5.07 x 106 wt. of polyethylene per wt. of titanium.
The polymer had an I2 melt index of 1~20, an I1o melt index of 12.17, a I1o/I2 ratio of 10.14 and a density of 0.9619.

27,760A-F -18-~ ~'7l~ti~

EXAMPLE_ A. Preparation of the catalyst composition , The catalyst components were added to a 120-ml serum bottle in the following order with stirring under a nitrogen a-tmosphere:

97.83 ml of 2/2,4-trimethylpentane O.75 ml of 1.00 M EADC in 2,2,4-trimethylpentane 0.15 ml of 0.050 M Ti(OiPr)2O in 2,2,4-trimethylpentane 0.97 ml of 0.62 M butyl ethyl magnesium in 2,2,4-trimethylpentane 0.30 ml of 0.025 M Ti(OiPr)4 in 2,2,4-trimethylpentane The molar ratio of Ti(OiPr)2O:Ti(OiPr)4 = 1:1.

The atomic ratios of the catalyst componen-ts were as follows:
Mg/Ti = 40/1 Al/Ti = 50/1 excess Cl/Ti = 0.40/1 B. Polymerlzation Employing the procedures of this catalyst, 5 ml (0.00075 mMole Ti) of this catalyst yielded 173.9 gms of polymer for a catalyst efficiency of 4.84 x 106 wt. of polyethylene per wt. of titanium.
The polymer had an I2 melt index of 2.04, an I1o mel-t index of 18.95, a I1o/I2 ratio of 9.29 and a density of 0.9627.

27,760A-F -19-COMPARATIVE EXPERIMENT B
A. Preparation of the catalyst composition , The catalyst components were added to a 120 ml serum bottle in the following order with stirring under a nitrogen atmosphere:

97.68 ml of 2,2,4-trimethylpentane O.75 ml of l.00 M EADC in 2,2,4-trimethylpentane 0.60 ml of 0.025 M Ti(OiPr)4 in 2,2,4-trimethylpentane 0.97 ml of ~.62 M butyl ethyl magnesium in 2,2,4-trimethylpentane The atomic ratios of the catalyst components were as follows:
Mg/Ti = 40/1 Al/Ti = 50/1 excess Cl/Ti = 0.40/1 B. Polymerization Employing the same procedure of Comparative Experiment A, 5 ml (0.00075 mMole Ti) of this catalyst yielded 138.3 gms of polymer for a catalyst efficiency of 3.85 x 106 wt. polymer per wt. of titanium.

These examples and comparative experiments demonstrate that mixtures of Ti(OiPr)~ with the Ti(OiPr) 2 O interact synergistically to produce catalyst efficiencies higher than either component individually.

27,760A-F -20-

Claims (10)

1. A catalytic reaction product of (A) a tetravalent titanium compound, (B) an organomagnesium component, (C) a halide source, and if necessary (D) an organoaluminum compound, is also present, said catalytic reaction product having atomic ratios of the improvement which comprises employing as the tetravalent titanium compound, a mixture of (A-1) a tetrahydrocarbyloxy-titanium compound and (A-2) a dihydrocarbyloxytitanium oxide in a molar ratio of (A-1):(A-2) of 0.1:1 to 10:1 and having atomic ratios of:
Mg:Ti is 1:1 to 200:1;
Al:Ti is 0.1:1 to 1000:1;
excess X:Al is 0.0005:1 to about 5:1;
wherein excess X is the amount of excess halide above that theoretically required to convert the magnesium component into a dihalide.

2. The catalytic reaction product of Claim 1 wherein the tetrahydrocarbyloxytitanium compound has the formula Ti(OR)4 wherein each R is independently an alkyl group or an aryl group having from 1 to 12 carbon atoms; the dihydrocarbyloxytitanium oxide has the formula (RO)2TiO wherein each R is as defined above;
the molar ratio of (A-1):(A-2) is 0.2 1 to 5:1; the halide source contains aluminum and the catalytic reaction product has the following atomic ratios Mg:Ti is 2:1 to 100:1;
Al:Ti is 0.5:1 to 200:1;
excess X:Al is 0.001:1 to 2:1.

3. The catalytic reaction product of Claim 2 wherein the molar ratio of (A-1):(A-2) is 0.33:1 to 3:1; the halide source is an alkylaluminum halide; and the catalytic reaction product has the following atomic ratios Mg:Ti is 5:1 to 75:1;
Al:Ti is 1:1 to 75:1;
excess X:Al is 0.01:1 to 1.4:1.

4. The catalytic reaction product of Claim 3 wherein the organomagnesium component is a dihydrocarbyl magnesium.

5. The catalytic reaction product of Claim 4 wherein the dihydrocarbyl magnesium is n-butyl-sec-butyl magnesium, di-n-hexyl magnesium, ethyl-n-butyl magnesium, diisopropyl magnesium or ethyl-n-hexyl magnesium.

6. The catalytic reaction product of Claim 3 wherein the organomagnesium component is a complex of a dialkyl magnesium and a trialkyl aluminum wherein the atomic ratio of Mg:Al in said complex is 0.3:1 to 1000:1.

7. The process for the polymerization of an .alpha.-olefin under the conditions characteristic of Ziegler polymerization wherein the catalytic reaction product of Claim 1 is employed as a polymerization catalyst.

8. The process of Claim 7 wherein the .alpha.-olefin is ethylene or a mixture of ethylene and a higher .alpha.-olefin or .alpha.-olefins.

9. In a process for polymerizing one or more .alpha.-olefins under conditions characteristic of Ziegler polymerization using as catalyst a catalytic reaction product of (A) a tetravalent titanium compound, (B) an organomagnesium component, (C) a halide source, and if necessary (D) an organoaluminum compound, is also present, said catalytic reaction product having atomic ratios of the improvement which comprises employing as the tetravalent titanium compound, a mixture of (A-1) a tetrahydrocarbyloxytitanium compound and (A-2) a dihydro-carbyloxytitanium oxide in a molar ratio of (A-1):(A-2) of 0.1:1 to 10:1 and having atomic ratios of:
Mg:Ti is 1:1 to 200:1;
Al:Ti is 0.1:1 to 1000:1;
excess X:Al is 0.0005:1 to 5:1;
wherein excess X is the amount of excess halide above that theoretically required to convert the magnesium component into a dihalide.

10. The process of Claim 9 wherein ethylene and at least one polymerizable .alpha.-olefin having 3 to 10 carbon atoms are copolymerized under solution conditions.