GB2088862A - Intermetallic Compounds and Their Production - Google Patents

Abstract

An intermetallic compound is prepared by reacting a polymeric transition metal oxide alkoxide with a reducing metal of higher oxidation potential than the transition metal. The transition metal is suitably titanium or zirconium and the reducing metal magnesium, calcium, zinc or aluminum. The product compound can be activated with halide activator for use as a component of an olefin polymerization catalyst.

Description

1 GB 2 088 862 A 1

SPECIFICATION Intermetallic Compounds and Their Production

This invention relates to intermetallic compounds containing transition metals, and processes for their production. The intermetallic compounds can constitute catalyst precursors for interreaction with 5 halide activators to provide catalyst components for the polymerization of alpha olefins.

Polyethylene, produced by solution or slurry processes at lower pressures or in autoclave or tubular reactors at higher pressures, has been an object of commercial production for many years.

Recent interest has centered on linear low density polyethylene resins characterized by linearity and short chain branching afforded by alkene comonomers, and offering narrow molecular weight distribution, improved strength properties, higher melt viscosity, higher softening point, improved ESCR 10 (Environmental Stress Crack Resistance) and improved low temperature brittleness. These and related properties provide advantages to the user in such applications as blown film, wire and cable coating, cast film, coextrusion, and injection and rotational molding.

The linear olefin polymers have typically been produced using catalysts of the general type disclosed by Ziegler, thus comprising a transition metal compound, usually a titanium halide admixed with an organometallic compound such as alkyl aluminum. The transition metal component may be activated by reaction with a halide promoter such as an alkyl aluminum halide. Among the improved catalysts of this type are those incorporating a magnesium component, usually be interaction of magnesium or compound thereof with the transition metal component or the organometallic component, as by milling or chemical reaction or association.

There is also interest in producing intermediate to high density resins of modified characteristics employing coordination catalysts of this type. In particular, resins of broader molecular weight distribution and higher melt index are sought.

According to the present invention, transition m eta [-containing intermetallic compounds are prepared by the reaction of polymeric transition metal oxide alkoxide with at least one reducing metal, 25 i.e., metal having higher oxidation potential than the transition metal. Thus, a polymeric titanium alkoxide, or oxoalkoxide, is reacted with magnesium metal to provide a reaction product which may be activated to form an olefin polymerization catalyst element.

The polymeric transition metal oxide alkoxide may be separately prepared by the controlled hydrolysis of the alkoxide; or the polymeric oxoalkoxide may be provided by an in situ reaction, e.g., 30 hydrolysis in a reaction medium including the reducing metal. For example, titanium or zirconium tetrabutoxide may be reacted with magnesium metal in a hydrocarbon solvent, and in the presence of a controlled source of water, preferably a hydrated metal salt such as magneisum halide hexahydrate.

Transition metal alkoxides, particularly titanium alkoxides, are known for their colligative properties in organic solvents, and their sensitivity to hydrolysis. It is reported that the hydrolysis reaction proceeding from the oligomeric, usually trimeric titanium alkoxides results in polymeric titanium oxide alkoxides, generally expressed as Ti(OF)4+nH20--a-TiOn(OR)4-2n+2n ROH Condensation reactions may also occur especially at elevated temperatures to structures involving primary metal-oxygen-metal bridges such as:

OR OR 1 1 0 R-Ti -0- 11-0 h 1 1 UM OR which may in turn participate in or constitute precursors for hydrolysis reaction.

These polymeric titanium alkoxides or oxoalkoxides (sometimes also referred to as u oxoalkoxides) may be represented by the series [T'3(X+1)0,x(OR)40(+;3)l where X=0,1,2,3..., the structure reflecting the tendency of the metal to expand its coordination beyond its primary valency 45 coupled with the ability of the alkoxide to bridge two or more metal atoms.

Regardless of the particular form which the alkoxide is visualized to adopt, in practice it is sufficient to recognize that the alkoxide oligomers form upon controlled hydrolysis a series of polymeric oxide alkoxides ranging from the dimer through cyclic forms to linear chain polymer of up to infinite chain length. More complete hydrolysis, on the other hand, leads to precipitation of insoluble products 50 eventuating, with complete hydrolysis, in orthotitanicacid.

For ease of description herein, these materials will be referred to as polymeric oxide alkoxides of the respective transition metals, representing the partial hydrolysis products. The hydrolysis reaction can be carried out separately, and the products isolated and stored for further use, but this is inconvenient especially in view of the prospect of further hydrolysis, hence the preferred practice is to 55 generate these materials in the reaction medium. Evidence indicates that the same hydrolysis reaction occurs in situ.

2 GB 2 088 862 A The hydrolysis reaction itself may be controlled directly by the quantity of water which is supplied to the transition metal alkoxide and the rate of addition. Water must be supplied incrementally or in a staged or sequenced manner: bulk addition does not lead to the desired reaction, effecting excessive hydrolysis, with precipitation of insolubles. Dropwise addition is suitable as is the use of water of reaction, but it is found more convenient to provide the water as water of crystallization, sometimes referred to as cation, anion, lattice or zerolitic water. Thus, common hydrated metal salts are usually employed, where the presence of the salts themselves are not deleterious to the system. It appears that the bonding provided by the coordinated sphere of water in a hydrated salt is adapted to control release and/or availability of water, or water related species to the system as required to effect, engage in or control the reaction.

The overall amount of water employed, as aforesaid, has a direct bearing on the form of polymeric oxide alkoxide which is produced, and thus is selected relative to catalytic performance. (It is believed without limitation that the stereoconfigu ration of the partially hydrolyzed transition metal alkoxide determines, or contributes in part to the nature, or result of the catalytic action of the activated catalyst component).

In general, it has been found sufficient to provide as little as 0.5 moles of water per mole of transition metal. Amounts of up to 1.5 moles are suitable with higher amounts up to 2.0 moles being operable whenever precipitation of hydrolysis products from the hydrocarbon solvent medium may be avoided. This may be achieved in principle by reducing the rate of addition and ceasing addition upon first evidence of precipitation. While it is believed that the reaction is essentially equimolar, a certain excess of water is appropriately employed in some cases, as is customary.

It will be understood that the steroisomeric form, chain length, etc. of the hydrolysis product may be somewhat altered with the elevated temperature required by the ensuing reaction with the reducing metal, and in situ processes likewise will affect equilibria through the mass action effect. Likewise, the cogeneration of alkanol may affect equilibria, reaction rates, etc.

The hydrolysis reaction proceeds under ambient conditions of pressure and temperature, and equires no special conditions. A hydrocarbon solvent may be used, but is not required. Mere contact of the materials for a period of time, usually 10-30 minutes to 2 hours is sufficient. The resultant material is stable under normal storage conditions, and can be made up to a suitable concentration level as desired, simply by dilution with hydrocarbon solvent.

The polymeric transition metal oxide alkoxides are reacted with a reducing metal having an oxidation potential higher than the transition metal. Preferably a polymeric titanium oxide alkoxide is used. The reducing metal preferably comprises at least one of magnesium, calcium, potassium, aluminum and zinc. Combinations of transition metal alkoxide, reducing metal and hydrated metal salt are usefully selected with reference to electropotentials to minimize side reactions, as known in the art; 35 and in general to assure preferred levels of activity for olefin polymerization, magnesium values are supplied to the system by appropriate selection of reducing metal/hydrated metal salt.

In the preferred embodiment (to which illustrative reference is made in the following text, as a matter of convenience), titanium tetra-nbutoxide (TBT) is reacted with magnesium turnings and hydrated metal salt, most preferably magnesium chloride hexahydrate, at a temperature of 501501C., in a reaction vessel under autogenous pressure. TBT may constitute the reaction medium, or a hydrocarbon solvent may be used. Ti/Mg molar ratios may vary from 1:0.1 to 1:1 although for the most homogeneous reaction system a stoichiometric relationship of Tilv to MgO of 1:1 is preferred, with an amount of hydrated metal salt to supply during the reaction about 1 mole of water per mole of Mg1.

The hydrocarbon soluble catalyst precursor comprises predominently Ti values in association with Mg values, in one or more stereoconfigu ration complexes believed to constitute principally oxygenated species. Some evidence of mixed oxidation states of the titanium values suggests an interrelated system of integral species of TV, Till', and Till value s perhaps in a quasi-equilibrium relation at least under dynamic reaction conditions. The preferred precursor is believed without limitation to incorporate (Ti-O-Mg) bridging structures.

The intermetallic compounds have special interest as catalyst precursors, in support or unsupported systems, for isomerization, dimerization, oligornerization or polymerization of alkenes, alkynes or substituted alkenes in the presence or absence of reducing agents or activators, e.g., organometallic compounds of Group [A, IIA, IIIA, or 1113 metals.

j 1 1 41 In the preferred utilization of such precursors, they are reacted with a halide activator such as an 55 alkyl aluminum halide and combined with an organometallic compound to form a catalyst system adapted particularly to the polymerization of ethylene and comonomers to polyethylene resins.

The transition metal component is an alkoxide, normally a titanium or zirconium alkoxide comprising essentially -OR substituents where R may comprise up to 10 carbon atoms, preferably 2 to 5 carbon atoms, and most preferably n-alkyl such as n-butyl. The selected component is normally 60 liquid under ambient conditions and the reaction temperatures for ease of handling, and to facilitate use is also hydrocarbon soluble.

It is generally preferred for facility in conducting the related hydrolysis reaction to employ transition metal compounds which comprise only alkoxide substituents, although other substituents 4 3 GB 2 088 862 A 3 may be contemplated where they do not interfere with the reaction in the sense of significantly modifying performance in use. In general, the halide-free n-alkoxides are employed.

The transition metal component is best used in the highest oxidation state for the transition metal, to provide the desired stereoconfigurational structure among. other considerations. Most suitably as aforesaid, the alkoxide is a titanium or zirconium alkoxide. Suitable titanium compounds include titanium tetraethoxicle, as well as the related compounds incorporating one or more alkoxy radicals including n-propoxy, iso-propoxy, n-butoxy, isobutoxy, secbutoxy, tertbutoxy, n- pentoxy, tertpentoxy, tert-amyloxy, n-hexyloxy, n-heptyloxy,,nonyloxy and so forth.

Some evidence suggests that the rate of hydrolysis of the normal derivatives decreases with increasing chain length, and the rate decreases with molecular complexity viz. tertiary, secondary, normal, hence these considerations may be taken into account in selecting a preferred derivative. In general, titanium tetrabutoxicle has been found eminently suitable for the practice of the present invention, and related tetraalkoxides are likewise preferred. It will be understood that mixed alkoxides are perfectly suitable, and may be employed where conveniently available. Complex titanium alkoxides sometimes inclusive of other metallic components may also be employed.

The reducing metal is supplied at least in part in the zero oxidation state as a necessary element of the reaction system. A conveneient source is the familiar turnings, or ribbon or powder. As supplied commercially, these materials may be in a passivated surface oxidized condition and milling or grinding to provide at least some fresh surface may be desirable, at least to control reaction rate. The reducing metal may be supplied as convenient, in the form of a slurry in the transition metal component and/or 20 hydrocarbon diluent, or may be added directly to the reactor.

Whether in the case of the in situ preparation (or for independent preparation of the polymeric transition metal alkoxide), the source of water, or water related species is provided, whereby quantities of water are released or diffused or become accessible, as the case may be, in a delayed rate controlled manner during the reaction. As aforesaid, the coordination sphere afforded by a hydrated metal salt has 25 been found suitable for the purpose; but other sources of water in the same proportions are also useable. Thus, calcined silica gel free of other active constituents but containing controlled amounts of bound water may be employed. In general, the preferred source of water is an aquo complex where water is coordinated with the base material in known manner.

Suitable materials include the hydrated metal salts especially the inorganic salts such as the 30 halides, nitrates, sulphates, carbonates and carboxylates of sodium, potassium, calcium, aluminum, nickel, cobalt, chromium, iron, magnesium, and the like.

The interaction of these components is conveniently carried out in an enclosed reactor, preferably coupled with reflux capacity for volatile components at the elevated temperatures produced in the reaction vessel. Autogenous pressure is employed, as the reaction proceeds smoothly under ambient 35 conditions, with heating to initiate and maintain the reaction. As in any such reaction stirring is preferred simply to avoid caking or coating of vessel surfaces, to provide intimate admixture of components, and to ensure a homogeneous reaction system.

Usually a hydrocarbon solvent such as hexane, heptane, octane, clecalin, mineral spirits and the like is also used to facilitate intermixture of components, heat transfer and maintenance of a homogeneous reaction system.

Saturated hydrocarbons are preferred, having a boiling point in the range of 60 to 1 901C. The liquid transition metal component also may serve at least in part as the reaction medium, especially where no added solvent is employed. The reaction involves a stage where additional volatile components form azeotropes with the solvent, or if the components are employed neat, constitute the 45 source of reflux, but in either case it is preferred, at least to effectuate the reaction through intermediate stages with appropriate reaction times, to return volatiles to the reaction zone. Thus, butanol is generated when the titanium component is titanium tetra n- butoxide forming an azeotrope with the hydrocarbon solvent. Selection of solvent and/or alkoxide relative to possible suppression of reaction temperature is accordingly a consideration, as is known to one skilled in the art. 50 Reaction temperature will to some extent be a matter of choice within a broad range, depending upon the speed of reaction conveniently to be conducted. It has been found that the reaction system (constituted by the liquid transition metal component, dissolved hydrated metal salt, reducing metal particles and solvent, where desired) evidences visible gas generation at about 600-700C. suggesting an initiation temperature or activation energy level at about 500 C. which therefore constitutes the 55 minimum necessary temperature for reaction of the polymeric oxide alkoxide with the reducing metal.

The reaction is somewhat exothermic during consumption of the reducing metal hence may be readily driven to the ensuing stage, being the reflux temperature. As the alkanol generated is largely consumed in the course of the continuing reaction (as an independent species), the actual system temperature will change, and completion of the reaction is evidenced by consumption of visible metal and/or 60 attainment of the reflux temperature for the pure solvent within a period of as little as 30 minutes to 4 hours or more. Such temperature may reach 1401'-1 900C. and of course higher temperatures might be imposed but without apparent benefit. It is most convenient to operate within the range of 50 1 501C., preferably 70-1401C. In the absence of solvent, the upper limit will simply be established by the reflux temperature for the alkanol generated in the course of the reaction. 65 4 GB 2 088 862 A 4 Reaction of the components is most clearly apparent from the marked color change, with exotherm, that accompanies commencement of gas evolution. Where lack of opacity or turbidity of the solution admits observation, evolution of gas ranging from bubbling to vigorous effervescence is most evident at the surface of the metal, and the generally light colored solutions immediately turn greyish, 5 then rapidly darker to blue, sometimes violet, usually blue black, sometimes with a greenish tint. Analysis of the gas evidences no HCI; and is essentially H2. Following the rapid color change some deepening of color occurs during a gradual increase of temperature, with continuing gas evolution. In this stage, the alkanol corresponding to the alkoxide species is generated in amount sufficient to suppress the boiling point of the solvent, and appears to be gradually consumed in a rate related 10 manner along with the remaining reducing metal.

The reaction product is hydocarbon soluble at least in part, and is maintained in slurry form for convenience in further use. The viscous to semi-solid product when isolated evidences on X-ray diffraction analysis an essentially amorphous character.

Molar ratios of the components may vary within certain ranges without significantly affecting the performance of the catalyst precursor in ultimate use. Thus, to avoid competing reactions rendering the 15 reaction product inconveniently gelatinous or intractable, the transition metal component is ordinarily supplied in at least molar proportion relative to reducing metal, but the transition metal/reducing metal ratio may range from about 0.5:1 to about 3:1 or more, preferably 1:1 to 10:1. An insufficient level of reducing metal will result in suppression of the reaction temperature such that the reflux temperature of the pure solvent remains unattained; whereas an excess of reducing metal will be immediately apparent from the unconsurned portion thereof, hence the desired amount of this component is readily ascertained by one skilled in the art.

Within these ranges, a varying proportion of the reaction product may constitute a hydrocarbon insoluble component which however may and commonly is slurried with the soluble component for use, e.g., further reaction with a halide activator to form an olefin polymerization catalyst. The amount of such insoluble component may be controlled in part by the use of a solvent with an appropriate partition coefficient but where use of a common hydrocarbon solvent such as octane is preferred for practical reasons, equimolar ratios of, e.g., Ti/Mg/H20 components have been found most adapted to the formation of a homogeneous reaction product.

The water, or water-related species is also preferbaly supplied in molar ratio to the transition 30 metal component, for similar reasons of homogeneity and ease of reaction. Thus, in the case of MgCl2' 61-120, an amount of 0. 17 moles supplies during the reaction about 1 mole of water and this proportion up to about 2 moles of water, provides the most facile reactions, with one or more moles of transition metal component. More generally, the H20 may range from about 0.66 to 3 moles per mole of transition metal. The amount of water present at any given stage of the reaction, of course, is likely to 35 be considerably less, ranging to catalytic proportions relative to the remaining components, depending upon the manner and rate at which it participates in the reaction sequence, presently unknown. It is nevertheless specifically contemplated without limitation, as an operative hypothesis that the water, or the rate of reaction controlling water-related species is activated, released, made accessible to or diffuses in a manner providing such species in a regular, sequenced, constant or variable rate-related 40 manner. The same molar proportion of free water supplied at the commencement of the reaction is however wholly ineffective in initiating reaction at this or higher temperature, and results in undesirable complete hydolysis reactions.

The measured amount of water is essentially in molar balance or molar excess relative to the reducing metal component and appears to be related to its consumption in the reaction, as a molar 45 insufficiency of water will invariably result in excess reducing metal remaining. In general, a modest excess of water of 10-40% is suitable to ensure complete reaction. Higher proportions are suitable without limitation but should be kept in relative stoichiometric balance to the transition metal component.

The selection of aquo complexes or hydrated metal salts where employed is essentially a matter 50 of the controlled availability of water it affords to the system. Thus, sodium acetate trihydrate is suitable, as is magnesium acetate tetrahydrate, magnesium sulphate heptahydrate and magnesium silicon fluoride hexahydrate. A salt of maximum degree of hydration consistently with the controlled release afforded by the coordinate bonding relationship is preferred. Most conveniently, a hydrated magnesium halide such as magnesium chloride hexahydrate or magnesium bromide hexahydrate is employed. These salts, like other hygroscopic materials, even when supplied in commercial anhydrous form contain some sorbed water, e.g., 17 mg/kg (see UK Patent 1,401,708) although well below the molar quantities contemplated in accordance with this invention. Hence, anhydrous grade salts unless specially modified for the purpose are not suitable herein.

The reaction system, as defined in the above description does not require, although it will tolerate 60 an electron donor or Lewis base, or a solvent performing in part those functions. As shown in the Examples, the reaction is implemented in the preferred embodiment with water of crystallization, and an alcohol component in the system. It is not known with certainty, therefore, whether proton transfer or electron donor mechanisms participiate or compete in the reaction system.

No separations are necessary as at least a portion of the reaction product is soluble in the 65 1 1 1 1 1 GB 2 088 862 A 5_ saturated hydrocarbon where employed as a solvent or provides a solvation medium such that even where a precipitate also occurs and even after storage, a workable reactive slurry may be readily formed.

In a preferred aspect of the invention the reaction product (catalyst precursor) is further interreacted with a halide activator, such as an a(kyl aluminum halide, a silicon halide, an alkyl silicon halide, a titanium halide, or an alkyl boron halide. It has been found that the catalyst precursor may be activated readily, by merely combining the product with the halide activator. The reaction is vigorously exothermic, hence the halide activator is typically added gradually to the reaction system. Normally, upon completion of addition, the reaction is also complete and may be terminated. The solid reaction product, or slurry may then be used immediately, or stored for future use. Usually, for best control over 10 molecular weight characteristics, and particularly for production of low density resin, only the hydrocarbon washed solid reaction product is employed as the catalyst.

The halide activator is commonly supplied for interreaction at a molar ratio of 3:1 to 6:1 (aluminum, silicon or boron, relative to the transition metal) although ratios of 2:1 or more have been used successfully.

The resultant catalyst product may be used directly in the polymerization reaction although it is typically diluted, extended or reduced as required to provide in a convenient feed an amount of catalyst equivalent to 80-100 mg/transition metal, based upon a nominal productivity of greater than 200,000 gm polymer/grn transition metal in continuous polymerizations which the present catalyst ordinarily exceeds. Adjustments are made by the artisan to reflect reactivity and efficiency, ordinarily by 20 mere dilution, and control of feed rates.

The transition metal containing-catalyst is combinable for use in polymerization with an organometallic co-catalyst such as triethyl aluminum or triisobutyl aluminum or a non-metallic compound such as triethylborane. A typical polymerizer feed thus comprises 42 parts of isobutane solvent, 25 pts. of ethylene, 0.0002 pts. catalyst (calculated as TO, and 0.009 pts. co-catalyst (TEA, 25 calculated as Al), to a reactor maintained at 650 psig. and 1 600F. In general, the amount of co catalyst, where employed, is calculated to range from between about 30 to 50 ppm calculated as Al or B, based upon isobutane.

Examples of metallic cocatalysts include trialkyl aluminums, such as triethyl aluminum, triisobutyl aluminum, trinoctyl aiuminum, alkyl aluminum halides, alkyl aluminum alkoxides, dialkyl zinc, dialkyl 30 magnesium, and metal borohydrides; including those of the alkali metals, especially sodium, lithium and potassium, and of magnesium, beryllium and aluminum. The non-metal cocatalysts include boron alkyls such as triethyl borane, triisobutyl borane and trimethyl borane and hydrides or boron such as diborane, pentaborane, hexaborane and clecaborane.

The polymerization reactor is preferably a loop reactor adapted for slurry operation, thus employing a solvent such as isobutane from which the polymer separates as a granular solid. The polymerization reaction is conducted at low pressure, e.g., 200 to 1,000 psi and a temperature in the range of 100 to 2000F. with applied hydrogen as desired to control molecular weight distribution.

Other n-alkenes may be fed to the reactor in minor proportion to ethylene, for copolymerization therewith. Typically, butene-1 or a mixture thereof with hexene-1 is employed, in an amount of 3 to 10 40 mol %, although other alpha olefin comonomers/proportions may be readily used. In utilizing such n alkene comonomers, one may secure resin densities over the range from.91 to.96.

Still other alpha olefin comonomers, such as 4-methyl-pentene-1, 3-methylbutene-1, isobutylene, 1 -heptene, 1 -decene, or 1 -dodecene may be used, from as little as 0.2% by weight, especially where monomer admixtures are employed.

The polymerization may nevertheless be conducted at higher pressures, e.g. , 20,000 to 40,000 psi, in autoclave or tubular reactors where desired.

In referring herein to an intermetallic "compound" or "complex" it is intended to denote any product of reaction, whether by coordination or association, or in the form of one or more inclusion or occlusion compounds, clusters, or other interengagement under the applicable conditions, the integrated reaction in general being evidenced by color change and gas evolution, probably reflective of reduction- oxidation, rearrangement and association among the unconsurned elements of the reaction system.

The following Examples taken in conjunction with the foregoing description serve to further illustrate the invention, and of the manner and making and using same. All parts are by weight except as otherwise noted. Melt indices are measured under conditions E & F, respectively, of ASTM D-1 23857T, for MI and HLMI values, on powder or resin samples as specified.HLMI/Ml or MIR is melt index ratio, a measure of shear sensitivity reflecting molecular weight distribution. Other tests are as indicated, or as conventionally conducted in the related arts.

Example 1

A. 6.0 pts. of Ti(O13u)4 [T13T1 and 4.2 pts. of CrC1,61-1,0 were combined in a reaction vessel. The chromium salt was partially dissolved, and some heat was evolved upon stirring. Complete dissolution was accomplished with mild heating to 60-701 C. An additonal 3.3 pts. of chromium salt was dissolved with stirring over a period of 20 minutes. To the green solution there was added in portions a 6 GB 2 088 862 A 6 total of 0.3 pts. of magnesium shavings, which caused vigorous gas evolution. The cooled reaction product free of excess magnesium (which had completely disappeared), was a viscous green liquid, soluble in hexane.

B. In a similar run anhydrous chromium chloride was employed with the titanium alkoxide, but no reaction occurred, with heating at greater than 1 OOOC. for a half hour. Addition of zinc dust and further heating at greater than 1 501C. still evidenced no reaction. Substitution of magnesium shavings also resulted in no reaction. It was concluded that the hydrated salt was a necessary component of the reaction system.

Example 11

A. TBT (0.121 m), CrCl, - 6H,O (0.015 m) and MgO (0.0075 m) were combined in a stirred 10 reaction vessel equipped with an electric heating mantle. The chromium salt was wholly dissolved at about 601C., and reaction with the magnesium shavings was apparent from gas evolution at 850C., which was vigorous at 1 001C., subsiding at 11 61C. with some Mg remaining. After dissolution of the remaining Mg, heating was continued, to a total reaction time of 1 hour and 45 minutes. The reaction product at room temperature was a dark green liquid which dissolved readily in hexane.

B. In the same manner, a reaction product was prepared in the proportions 0. 116 m TBT, 0.029 m CrCl, - 6H,O and 0.029 m Mg. A muddy green reaction product at 1 180C. took on a definite bluish color at 120C. with continued gas evolution. The reaction was terminated upon the disappearance of magnesium in one hour and fifteen minutes. The reaction product was soluble in hexane.

C. The aforedescribed runs were again replicated in the reactant amounts 0.116 m TBT, 0.058 m 20 CrCl, - 6H201 0.0145 m Mg. The reaction was completed in 115 minutes, and a hexane soluble product resulted.

D. The ratio of the reactants was again modified in a further run, to 0. 115 m TBT, 0.0287 m CrCl, - 6H,O, and 0.0114 m Mg. A muddy green material evident at 1 141C. became blue at the Mg surface. The recovered reaction product was hexane soluble.

E. In a similar run, 0.176 m TBT, 0.30 m CrCl, - 61-120 and 0.176 m MGO were reacted in octane. The clear green color of the reaction at 700C. turned muddy with increasing gas evolution and darkened to almost black at 900C. The color returned to green at 11 90C. and the reaction was terminated at 121 1C. with complete disappearance of the magnesium. The reaction product (6.9 wgt.

%, Ti, 3.5 wgt % Mg, 1.3 wgt. % Cr) was a dark olive green liquid and a solid of darker color (about 30 50:50/volume) which settled out.

F. In yet another run in octane, the reactants were provided in the proportions 0.150 m TBT, 0.051 m CrCl,-6H20 and 0.150 m Mg. Again, the muddy green color changed to almost black with vigorous effervescence, forming at 1090 a dark blue black reaction product. (5.7 wgt. % Ti; 2.9% Mg, 2.1 wgt. % CO.

Example III

A. The reaction product HE was combined in a reaction vessel with isobutylaluminum chloride added dropwise in proportions to provide a 3:1 Al/Ti molar ratio. The green colored mixture changed initially to brown violet at 381C., which upon completion of reactant addition at 391C. had changed to red brown in appearance. After 30 minutes additional stirring, the reaction was terminated, the product 40 being a dark red brown liquid and a dark brown precipitate.

B. Reaction product IIF was similarly reacted with isobutyl aluminum chloride (3.1 AIM molar ratio). The peak temperature with complete addition was 481C., but no brown color change was evident. The reaction product was a clear liquid and a dark grey precipitate.

Example IV 45

The catalyst components prepared in Example III above were employed in the polymerization of ethylene (1 901F., 10 mol % ethylene, 0.0002 pts. catalyst calculated as Ti, triethyl aluminum about 45 ppm, calculated as Al, H2 as indicated) with results set forth in Table 1, as follows:

Table 1

H, Prod. Resin Properties 50 Catalyst psig g Pelg Ti hr m/ HLMI HL/1411M1 IIIA 60 35160 10.1 265 26.3 29220 18.9 618 32.6 IIIB 60 30380 9.6 264 27 120 26880 32.8 855 26.1 55 In the following Example, the catalyst component of the invention was prepared from the reactant admixture in the absence of added solvent.

G 1 7 GB 2 088 862 A 7 Example V

A. 0. 1212 m Ti(OBU)4 [TBT1, 0. 121 m magnesium turnings and 0.0012 M MgC12- 6H20 (TBT/Mg/MgC12. 61-1201:1:0.01 molar) were combined in a stirred reaction vessel equipped with an electric heating mantle. The magnesium salt dissolved entirely at room temperature, forming a homogeneous reaction mixture. The mixture was heated gradually and at 950C. gas evolution 5 commenced on the surface of the magnesium turnings. At 1400C. with reflux the bubbling had become vigorous. The solution darkened in color and the bubbling ceased at 1 7011C., whereupon the reaction was terminated. The reaction product contained excess magnesiumonly about 8.5 percent charged had reacted-and was soluble in hexane.

B. In another run, the molar ratio of MgCl, - 6H20 was increased (TBT/MglMgC'2. 6H20=1:1:0" 10 molar). The gold yellow liquid became greyish with gas evolution at 1040C. , and darkened with further heating to 1 680C. After 125 minutes of reaction time, the reaction product contained some excess magnesium-about 63 percent had reacted.

C. In a further run, the molar ratio employed was 1:1:0.17. The dark blue reaction product was very viscous and could not be readily diluted with hexane. All of the magnesium was consumed. 15 The following Example shows the preparation carried out in a hydrocarbon solvent.

Example VI

A. 50.2 pts. (0.148 m) of TBT was added to a stirred reaction vessel equipped with an electric heating mantle, and 58.6 pts. octane. The magnesium turnings (0.074 m) were added, stirring commenced and then 0.0125 m M9C12. 6H20 added with heating over one minute. At 751C. (20 20 minutes) the magnesium salt had entirely dissolved, and at 95'C. (25 minutes) gas evolution at the surface of the magnesium turnings commenced, the evolution increasing as the solution turned greyish and then deep blue, with refluxing at 11 71C. (35 minutes). The magnesium metal had entirely reacted within 1 hour (1 28-1129'C.) and the reaction was terminated. The dark blue reaction product, solubilized in octane (a small amount of a greenish precipitate remained), was calculated to contain 6.8 25 wgt % Ti and 2.0 wgt % Mg values (Ti/Mg 3.4 to 1 by weight, 1.7 to 1 molar).

B. The foregoing run was essentially repeated except that molar ratios of the reactants were modified with results as follows:

TW91M9C12.6H,0 n1M9 MoIRatio (Molar) Notes 30 1.0/0.65/0.11 1.32 Dark blue black liquid and green precipitate. 6.6 wgt % Ti, 2.6 wgt % Mg values (calc) 1.0/0.75/0.128 1.14 Blue solution with greenish tint. 6.5 wgt % TI, 2.8 wgt % 35 Mg values (calc) 1.0/1.0/0.085 0.92 Blue black liquid with light green precipitate (insoluble in acetone, alkane and methylene chloride) Some 40 unreacted Mg' 1/1/0.17 0.85 Dark blue black liquid, 6.6 wgt % Ti, 3.9 wgt % Mg values (calc) 1/11/0.34 0.75 Dark blue black liquid, 6.7 45 wgt % Ti, 4.6 wgt % Mg values (ca1c) 1/1/0.51 0.66 Milky blue liquid, 3.7 wgt % Ti, 2.9 wgt % Mg values (calc) 1/2/0.17 0.46 Dark blue black liquid and 50 viscous green gel. Some unreacted Mg' 1/2/0.34 0.43 Dark blue black liquid and viscous gel. Some unreacted Mg.

8 GB 2 088 862 A 8 T11M91M9C12 6H20 n1M9 Mol Ratio (Molar) Notes 2/1/0.17 1.70 Example IIA 2/1/0.34 1.50 Blue black solution. 7.1 wgt % Ti, 2.3 wgt % Mg values (calc) 5 3/1/.51 1.99 Blue black liquid with slight green tint. 6.1 wgt % Ti, 1.6 wgt % Mg values (calc) C. The preparation 1/1 /0.34 obtained above was repeated except that 63.7 pts. TBT was employed with 67.5 hexane as the solvent reaction medium. A dark blue black liquid resulted, containing by calcination 8.2 wgt % Ti and 1.6 wgt % Mg values.

The following Example shows the stepwise preparation of the catalyst component.

Example VIII

2.61 PtS' MgCl2 ' 6H,O and 34.2 pts. TBT were combined with stirring. Within 30 minutes, the yellow liquid-crystalline salt mixture was replaced with a milky yellow, opaque, viscous liquid.

Prolonged stirring resulted in a fading of the cloudiness to yield within 2 hours a clear yellow liquid (In a second run conducted in octane within 30 minutes the salt had totally dissolved to yield a yellow liquid with no intervening precipitate or opaqueness.) ATM Mg reaction product was prepared in the manner of foregoing Examples, utilizing the clear yellow liquid prepared above, and 1.83 pts. of Mg', for a 1/0.75/0.128 molar ratio of components in 20 octane. The reaction proceeded smoothly to a dark blue black liquid and green precipitate in the same manner as other reported reactions.

The reaction product was activated with ethyl aluminum dichloride at a 3/1 AI/6ri ratio to form a catalyst component for olefin polymerization.

The following Example evidences the significance of level of bound water.

2 Example V1111

A series of identical runs were performed at the molar. ratio 1/0.75/0. 128 (T13TIMg/M9C12. 6H20) except that the degree of hydration of the magnesium salt was modified.

When M9C12. 41-1,0 was employed (H20/Mg=.68/1 as compared to 1:1 for M9C12. 6H20), only 89.1 % of the magnesium metal reacted. Use Of M9C'2. 2H20 at the same overall molar ratio (H20/Mg 30 0.34/1) resulted in only 62.1 % reaction of Mgl.

In repeat runs, the amount of hydrated salt supplied was increased to provide a 1/1 H20/M9 ratio.

All of the magnesium metal reacted. It was also observed that the amount of insoluble reaction product increased with increasing salt levels.

The following Example illustrates the use of other titanium compounds.

Example IX

A. 45.35 pts. (0.1595 m) Ti(OPr')4,0.1595 m Mg' and 50.85 pts. octane added to a stirred reaction flask fitted with an electric heating mantle, and 0.027 m of MgC12. 6H20 were added. The milky yellow mixture became grey with reflux, at about 881C., and turned blue at 901C. with gas effervescence. Based upon magnesium remaining, it was concluded that the reaction was partially suppressed by the octane/lisopropanol azeotrope present.

B. The reaction described in A was repeatedi at a reactant mol ratio of 1/0.75/0.128 using decalin (b.p. 185-1 891C) as the diluent. After six hours, the reflux temperature had attained 1400, and the reaction was terminated. A dark blue black liquid was obtained with a small amount of dark precipitate. Only 8.8% of the magnesium had reacted.

C. In a similar manner, reaction with tetra isobuty[tita nate was carrried out, at a mole ratio of 1/0.75/0.128, providing a blue black liquid and dark precipitate. About 50% of the magnesium reacted.

D. Titanium tetranonylate was similarly employed, with magnesium and M9C12. 6H20, at a mole ratio of 1/0.75/ 0.128. A blue liquid was formed, 45% of the magnesium having been consumed.

E. The reaction product of titanium tetrachloride and butanol, (believed to be dibutoxy titanium 50 dichloride) was reacted with magnesium and magnesium chloride hexahydrate at a molar ratio of 1/0.75/0.128 under conditions similar to the above examples. About half the magnesium was consumed in about 3 hours, whereupon a dark blue black liquid and an olive green precipitate (50/50 v/v) was recovered.

The following Example employs a zirconium metal alkoxide.

Example X

A. 12.83 parts of Zr(O13U4. BuOH (0.028 m); 0.34 pts. Mg' (0.14 m) in the form of i 4 j 9 GB 2 088 862 A 9 commercially available turnings, and 8.8 pts. octane were placed in a reaction vessel and heated to reflux at 1250C. with stirring for 15 minutes, without evidence of any reaction. 0.97 pts. of MgC12- 6H20 (0- 005 m) was added whereupon vigorous effervescence was noted, and the reaction mixture became milky in appearance.

B. In a second run 31.7 pts. of the zirconium compound (0.069 m) was combined with the magnesium metal turnings (0.069 m) and 57.6 pts. mineral spirits (bp 170-1 950C.) and 4.79 pts. MgC12 6H20 (0.0235 m) was added with stirring. Heat was applied to the reaction vessel via an electric mantle. Within 5 minutes, the reaction mixture had become opaque in appearance, and gas evolution from the surface of the magnesium metal was evident when the temperature had attained 850C., at 8 minutes reaction time. Gas evolution continued with vigorous effervescence, the temperature rising to 10 118011C. when a whitish solid appeared. With continued heating to 1330C. (1 hour reaction time) all of the magnesium metal had disappeared, the reactor containing a milky white liquid and a white solid. The reaction mixture was cooled and 92 pts. of a mixture collected, containing 6.8 wgt % Zr and 2.4% Mg (2.8:1 Zr/Mg by weight; 0.75 Zr/Mg molar ratio) which was soluble in hydrocarbons.

The reaction product may be activated in known manner with, e.g., an alkyl aluminum halide by 15 reaction therewith conveniently at a molar ratio of about 3/1 to 6/1 AI/Zr to provide, in combination with an organic or organometallic reducing agent, an olefin polymerization catalyst system adapted to the formation of polyethylene resin.

The following Example shows the substitution of calcium for magnesium as the reducing metal.

Example XI

A. 0.074 m Ti(OBu),; 0.074 m Cal (thick turnings supplied commercially, mechanically cut into smaller pieces) and 0.0 126 m MgCl,. 6H,O were combined in octane in a stirred reaction vessel equipped with an electric heating mantle. Upon attaining 1051C., the solution darkened in color, and at 11081C., with gas evolution, the solution took on a dark grey appearance. At 1 10.50C. rapid gas evolution was evidenced, followed by formation of a dark blue liquid. At 90 minutes, the reaction was terminated and a reaction product comprising a dark blue black liquid with a greenish tint isolated.

The run was repeated at the same molar ratio. 50% of the calcium reacted to provide a dark blue liquid and grey solid containing 6.2 wgt % Ti, 2.6 wgt % Ca, and 1.1 wgt % Mg (molar ratio 1/0.5/0.34) (XI Al).

In another run the same reactants were combined in the molar ratio 0.75/0. 128. 63% of the 30 calcium reacted, to provide a blue black liquid and a green solid. The reaction product (molar ratio 1/0.47/0.128) contained 6.6 wgt % Ti, 2.6 wgt % Ca and 0.4 wgt % Mg (XI A2).

B. The reaction product XI Al were further reacted with ethyl aluminum chloride at a 3/1 and 6/1 Altri molar ratio. The reaction products were diluted with hexane and the halide activator added slowly to control the highly exothermic reaction. In the 3/1 run the off white slurry initially formed resolved 35 upon completion of the reaction to a pink liquid and a -white precipitate. At 6/1 AIJ'Ti ratio, the slurry changed in color to grey, and then lime green.

Reaction product XI A2 was likewise treated with EtAIC12 at a 3/1 and 6/1 All'Ti molar ratio. The reactions were smooth, producing at 3/1 a deep brown slurry, and at 6/1 a red brown liquid with a brown precipitate.

C. Reaction products prepared in part B were employed in ethylene polymerization, with results as indicated in the following Table.

Table 11

Resin Powder Properties TBT-Ca-MgCl, - 6H20 Reaction H2 Productivity 45 (molar ratio) Ratio Wig) (gPEIgTi.hr) M/ HLM1 MIR 1/0.5/0.34 3/1 60 40,950 3.84 131 34.1 11 6/1 60 43,810 1.03 47.7 46.3 1/0.47/0.128 3/1 60 20,930 1.73 73.7 42.6 120 11,260 7.0 320 45.7 50 6/1 60 27,420 0.35 21.0 60.1 33,050 1.75 116 66.0 Bench Scale Reactor Conditions Diluent-Isobutane Temperature-1 90'F. 55 Hydrogen-as indicated Co-catalyst-Triethylaluminum (TEAL) at about 45 ppm AI Ethylene-1 0 mole % Run Time-60 minutes The runs evidenced a somewhat broader molecular weight distribution in the resin as compared to 60 the use of magnesium as the reducing metal.

The substitution of zinc as the reducing metal is shown in the following Example.

GB 2 088 862 A 10 Example X11

A. 0.204m TBT, 0.153 m of Znl granules, and 0.026 M Of MgCl2- 6H,O were combined in octane in a stirred enclosed system equipped with reflux, and externally heated. Within 13 minutes (85"C.) a rapid color change to blue black occurred, with increasing gas evolution to vigorous effervescence and foaming. The reaction product, a blue black liquid (no precipitate) comprising 7.7% Ti, 0.9% Zn, and 0.5% Mg by weight, fades to yellow on exposure to air.

B. The reaction productTiZnMg (molar ratio 1/0.86/0.128) was reacted with isobutyl aluminum chloride, at a 3/1 AI/Ti molar ratio, in hexane at 10-1 3lC. (XII 131).

C. Preparation of the TiZnMg reaction product (XII A) was repeated, employing Zn dust, with similar results. A further run with mossy zinc utilized only 7% of the zinc, and evidenced formation of a 10 green layer on the zinc surface.

D. The activated reaction product XI I B 1 prepared above was washed thoroughly in hexane and employed in the preparation of low density polyethylene resin. The reactor was preloaded with sufficient butene-1 to secure target density, and the reaction conducted (with incremental addition of butene-1 along with the ethylene) at 1700F. and 35 psig H, in the presence of triethyl aluminum as co- 15 catalyst. The resin recovered had the following properties: Density.91 65, MI 1.68, HILMI 52.1 and MIR 31.

The following Example involves the use of potassium as the reducing metal.

Example X111

62.7 m mol of TBT, 47 m mol of fresh potassium metal (scraped clean of its oxide/hydroxide 20 coating under octane), and 8.0 m mol of MgCI, - 6H20 were combined in octane in an enclosed system equipped with reflux, and externally heated. Within 2 minutes at 351C. the color changed to blue black, and bubbles appeared. Vigorous gas evolution and effervescence followed. Upon disappearance of the potassium metal, the reaction was terminated (at 5 hours). A dark blue black liquid with a small amount of dark blue precipitate was recovered.

Examples XIV-XV describe the use of aluminum as the reducing metal.

Example XIV

A. 112.31 pts. of Ti(013u), (0.33 m), 8.91 pts. of All (Alfa Inorganicspherical aluminum powder, -45 mesh) and 11.4 pts. of MgCI, - 61120 (0.056 m) [molar ratio 1:1:0.171 were admixed in a reaction vessel with stirring, and heat applied, employing an electric mantle.

When 1 00C. was attained in about 10 minutes, the yellow color deepened, and at 11 80C.

vigorous effervescence commenced, with gas evolution. At 1220C. the refluxing liquid took on a grey cast, and the temperature stabilized, as the reaction mixture changed in color from a deep grey with bluish tint to dark blue then blue black at 27 minutes reaction heating time. The temperature was maintained, rising to 1450C., within 1 hour and 20 minutes, whereupon gas evolution was essentially 35 complete and the reaction was terminated.

The reaction product at room temperature was a viscous liquid, evidencing unreacted aluminum particles. The unreacted aluminum was separated, washed and weighed, indicating that 6.7 pts. All reacted. The reaction product contained 7.9 wgt % Ti, 3.4 wgt % N and 0.7 wgt % Mg (molar ratio 1:0.75:0.17).

B. 9.10 pts. of the reaction product prepared above (0.719 pts. Ti, or 0. 015 m Ti) was added in hexane (13.0 pts) to a reaction vessel in a cooling bath. 0.045 m ethyl aluminum dichloride was added gradually, the temperature being maintained at 1 5-200C. The admixture, stirred for 30 minutes provided a dark red brown slurry and an intractable solid. (131).

A second run was carried out (0.175 m Ti/0.0525 m Al) without cooling to a peak temperature of 45 381C., and a red brown slurry again formed, with an intractable solid deposit. (132).

Example XV

The reaction products of Example XIV were employed as catalysts in the polymerization of ethylene under standard conditions (1 901F., 60 psig H,) employing triethyl aluminum as a co-catalyst, with results as follows:

M/ HLMI MIR 131 0714 6.45 -46.1 B2 0.38.17.4 45.7 Example XVI

A. Ina similar mannerto the foregoing, 0.133 m TBT, 0.100 m All, and 0. 017 m AIC'.- 61-120 55 were combined in octane and reacted over 7 hours and 15 minutes to provide a dark blue black liquid and a small amount of a grey solid. About 40 per cent of the aluminum reacted to provide a reaction product comprised of 6.6 wgt % Ti and 1.6% a[. (XV1 Al).

In the same manner, the same reactants were combined in a 1/1 /0. 17 m ratio. About 58% of the Al reacted to provide a reaction productcontaining 6.5 wgt % Ti and 2.7 wgt % Al. (XV1 A2).

-j t i 11 GB 2 088 862 A 11 B. The reaction products (XVI Al) and (XVI A2) were activated with ethyl aluminum chloride at 3/1 AIM.

C. The solid portion of the activated reaction product (XVI A2) was isolated from the supernatant and employed with TEA as co-catalyst in the polymerization of ethylene, at 1 701F., 15 psig H2 to produce resin characterized by MI.02, HLMI 1.01, MIR 50.5 and in a second run MI.02, HLMI.45 and 5 MIR 22.5.

The following Examples are drawn to catalyst components prepared employing other aquo complexes.

Example XVII

A. 0.0335 mol TBT and 0.0335 mol MgO were stirred in octane in a heated reaction vessel, to 10 which.0057 mol of MgBr2 - 6H,O was added. (Reaction molar ratio 1/1 /0. 17). The salt dissolved in six minutes with heating to 650C. A grey color developed with gas effervescence, and the solution turned blue, then blue black with a greenish tint. The reaction was terminated at 1230C. (about 10% unreacted Mg) after a reaction period of 4 hours and 10 minutes. (XVII A).

In a similar manner, a reaction product was prepared at a mole ratio of (Ti/Mg/MgBr, - 6H20=1/0.65/0.1 1), which was a blue black liquid and dark green precipitate (6.5 wgt % Ti 2.5 wgt % Mg (calc)).

B. The decanted reaction product (XVII A) was combined with isobutyl aluminum dichloride at Al/Ti levels of 3/1 and 6/1 by gradually adding the alkyl aluminum halide. In the first run (3/1 AI/Ti) a peak temperature of 420C. was attained with addition at a rate of 1 drop/2-3 sec, whereupon the 20 green liquid turned brown. The reaction product was a red brown liquid and brown precipitate. (IV B-1) The 6/1 product (IV B-2) was prepared in similar manner with the same results.

In a separate run, the reaction product (XVII A) was combined with SiC14 in the same manner. The reaction product of a 30 minute reaction at a 3/1 Si/Ti ratio was a light yellow liquid and a brown precipitate. A similar run provided a 6/1 SitTi reaction product.

C. The activated reaction products XVII B-1 and XVII B-2 (1 % TI by weight) were employed in the polymerization of ethylene (10 mol % in isobutane) at 1900F., with hydrogen modifier and triethyl aluminum cocatalyst (45 ppm A[) and compared to an identical run using magnesium chloride hydrate, with results set forth in Table III as follows:

Table Ill 30

Powder Resin Properties Catalyst A l/ Ti' H2 Productivity Ti(08u),-Mg-A (molar) (psig) (g PE1g Ti-hr) m/ HLMI HL/1411M1 A=M9C12. 61-1,0 3/1 60 42,870 1.7 61 35.9 120 49,100 12.2 348 28.5 35 Mg&2. 6H20 3/1 60 105,190 24 698 29 77,390 102 - - 6/1 60 34,780 10.3 371 36 37,050 17.8 639 35.9 Example XVIII

A. 42.23 pts. ofTBT(O.124 m) were combined with 3.02 pts. Mg (0.124 m) in octane (42.8 pts.) in the presence of 5.7 pts. FeC13- 61-120 (0.02 m) (TMgFe=1/1/0.1 7 molar) in an enclosed stirred reaction vessel equipped with reflux, and an electric heating mantle. Heating commenced, and within 6 minutes, at 650C. gas evolution began. The muddy yellow color turned dark brown at 801C. (7 minutes) and gas evolution increased. In about 30 minutes gas evolution had slowed and then ceased with consumption of MgO, and the reaction was terminated. The very dark liquid evidenced no residue.

(XVI I I Al).

In a second run, the same reactants were combined in the molar ratio TMgFe=1/1/0.34 with similar results. Dilution with hexane caused no precipitate or deposition of residue. (XVIII A2).

B. Reaction product XVIII Al was activated by reaction with a 50 wgt % so4ution of ethyl aluminum chloride in hexane at a 3/1 Al/Ti ratio. A brown liquid and solid was recovered, containing 16.5 MgTi/g. (XVIII 131).

In a similar manner, reaction product (XVIII A2) was activated. The dark brown liquid changed to a violet slurry and then to a dark grey slurry. The resulting clear liquid and grey precipitate contained 16 Mg Ti/g.

C. Activated reaction product XVIII 131 was employed in the polymerization of ethylene at 1 900F., psi H2. 114,320 g PE/g TI/hr were recovered, exhibiting the following properties: MI 5.1 HLMI 155.3, MIR 30.3 Example XIX

A. 1. 0.160 m Ti (OBU)41 0.160 m magnesium turnings and 0.027 m COC12. 6H20 were 60 combined in a stirred reaction vessel with 61.2 pts. of octane. The violet cobalt salt crystals provide 12 GB 2 088 862 A 12 upon dissolution a dark blue solution. The admixture is heated, employing an electric mantle, and gas evolution on the magnesium surfaces appears at 580C., increasing to vigorous effervescence of 1070C. within 12 minutes. The clear blue color becomes greyish on further heating and becomes almost black at 123-1250C. when all the magnesium has disappeared and the reaction is terminated, at 90 minutes. The milky blue reaction product was hydrocarbon soluble, and resolved into a dark blue 5 liquid and a dark precipitate upon standing.

The run was repeated, with essentially identical results.

B. The reaction product of the foregoing preparation was shaken, and 0. 0111 rn (Ti) was combined with isobutyl aluminum chloride (0.0333 rn Al) supplied dropwise to a reaction vessel. The temperature peaked at 400C., with formation of a greyish precipitate, which upon further addition of 10 BuAIC12 turned brown. After stirring for an additional 30 mir)utes the reaction was terminated, providing a dark red brown liquid and a brown precipitate.

C. The catalyst component prepared in Example XIX above was employed in the polymerization of ethylene 0 900F., 10 mol % ethylene, 0.0002 pts. catalyst calculated as TI, triethyl aluminum about 45 ppm calc as Al, H, as indicated) with the results set forth in Table IV, as follows:

Table IV

Resin Properties H2 Prod Catalyst psig g PE1g Tilhr m/ HLMI HL/1411M1 XIX B 60 105,180 6.2 206 33.6 20 75,290 33.9 950 28.1 Example XX

A. 0.169 mTi(OBu), [T13TI, 0.169 m magnesium turnings, and 0.029 m AIC13. 61-1,0 in octane as a diluent were combined in a stirred reaction vessel equipped with an electric heating mantle. The hydrated aluminum salt partly dissolved and at 111 'C. the solution rapidly darkened to a black liquid 25 with vigorous effervescence originating with gas evolution at the surface of the magnesium. The - solution took on a blue coloration and, with smooth refluxing to 1221C. formed a dark blue-black liquid with some remaining magnesium. At 1251C., all the magnesium metal disappeared, the solution exhibiting a slight green tint. The reaction was terminated, and dark blue black liquid and green precipitate recovered, in a volume ratio of about 95/5. - B. The reaction product described above was combined with isobutyl aluminum chloride in a molar ratio of 3:1 and 6:1 AI/Ti by dropwise addition of the chloride to a reaction vessel containing the titanium material. In the first reaction (3:1), the alkyl chloride was added at a rate of 1 drop/2-3 seconds until a peak temperature of 420C. was attained, with a color change from blue-green to brown. After stirring for an additional 30 minutes, the reaction product, a red-brown liquid anda brown 35 precipitate, was isolated. (XX B).

C. In a similar manner, a 6:1 AI/11 product was secured, with the same results. (XX C).

D. Reaction products XX B and XX C were employed with triethylaluminum cocatalyst (45 ppm A0 in the polymerization of ethylene (10 mol %) with isobutane diluent at 19011F. and hydrogen as indicated. The runs were terminated after 60 minutes, with results indicated in Table V, as follows: 40 Table V

Resin Properties H, PE Prod Catalyst psig mole g PE1g Tilhr m/ HLMI HL/1411M1 XX B 60 406 84,580 17.2 517 30.1 45 542 75,280 54.9 1413 25.7 XX C 60 245 54,440 4.11 129 31.4 183 34,860 26.2 801 30.5 Example XXI

A. 0.153 rn Ti(OBu), [TBT], 0.153 rn Mg" turnings and 0.026 m MC12-61-120 were combined 50 with 61.75 pts. of octane in a stirred reaction vessel equipped with an electric heating mantle. With heating to 44cC. the yellow solution deepened in color, and gas evolution on the magnesium metal surface became observable at about 57"C. With continued heating, the gas evolution increased until at 1020C. (15 minutes reaction) the reaction system turned a light muddy brown color.Vigorous effervescence continued with darkening of the brown color until at 1261C. (75 minutes) all the 55 magnesium had disappeared, and the reaction was terminated. The reaction product (XXIA-1) was a hydrocarbon soluble dark brown liquid and a small amount of a fine precipitate.

In a second run 0. 149 m TBT, 0. 149 m Mg, and 0.051 m NiCI2--6H20 were combined in octane in the same manner. Mg metal disappeared at 11 5C., 120 minutes, and the reaction resulted in a dark t i 13 GB 2 088 862 A 13 brown black hydrocarbon soluble liquid, which resolved on standing to a very fine dark precipitate and a yellow liquid, about 50/50 by volume (XXIA-2).

B. Reaction product IA-1 was shaken, and a portion (0.0137 rn Ti) was placed in a reaction vessel with hexane diluent, to which iBuAIC12 (0.0411 m AO was added dropwise, at a rate of 1 drop/2-3 sec. to 280C., and 1 drop/sec. to a peak temperature of 390C. After completion of addition the vessel 5 contents were stirred for 30 minutes, and the reaction product, a dark red brown liquid and a dark grey precipiate, isolated. (XXIB-1).

The same reaction product (XXIA-1) was combined with ethyl aluminum chloride in the same manner, at a 3/1 AIM molar ratio. The reaction product was a dark red brown liquid and a dark grey solid (XXIB-2).

In an essentially identical manner, reaction product XXIA-2 (Ti/Mg/Ni molar ratio 1/11/0.34) was combined with iBuAIC12 at a 3:1 AI/Ti ratio, with the same results, except that the supernatant liquid was a pale red brown color. (XXIB-3).

In a further run, reaction product XXIA-2 was reacted in the same manner with iBuAICI2 at a 6:1 AIM molar ratio, to for, similarly, a dark liquid and dark precipitate. (XXIB-4).

The same reaction product XXIA-2 was combined with ethyl aluminum chloride in the same manner, producing a dark red brown liquid and a dark grey solid. (XXIB-5).

Example XXII

A. Example XXIA was repeated, with the reactants supplied in the molar ratio Ti:mg:Ni of 1:0.65:0.11. The color change was from deep brown yellow to dark brown with gas evolution, and 20 thence through a grey brown to dark blue black upon consumption of magnesium, in a reaction occurring over a period of 6 hours. (XXIIA).

B. Reaction product XXIIA was combined with ethyl aluminum chloride in the manner of Example XXIB at a 3:1 All'11i molar ratio. A red brown liquid and red brown precipitate was recovered.

(XXIIB).

Exarnple XXIII Example XMA was repeated, with the reactants supplied in the molar ratio 1/0.75/0.128. The dark brown reaction product contained 5.9% Ti, 2.2% Mg and 0.97% Ni.

3/11.

The reaction product was then treated with isobutyl aluminum chloride at an A[/Ti molar ratio of 30 Example XXIV

A series of TMgNi catalysts, prepared as set forth in Examples XXIB and XXIIB, were employed as catalyst components in the polymerization of ethylene (11 900F., 10 mol % ethylene, triethyl aluminum about 45 pprn calc as Al, H2 as indicated) with the results set forth in Table VI, as follows:

Table VI 35

Resin Properties H2 Productivity Catalyst psig g PE1g T1 Hr m/ HL/141 HLMIIML XXIB-3 60 90,750 9.55 270 28 120 104,980 24.6 683 27.8 40 111,940 0.29 10.7 36.8 112,260 3.1 119 38.9 M13-4 60 59,790 0.25 10.9 43.6 62,720 1.0 43.6 43.6 XXH13 60 57,890 1.66 54.9 33.1 45 64,740 6.13 183 29.8 XXIB-2 60 238,670 0.65 19.5 30.2 271,560 6.7 188 28.1 M13-5 30' 175,000 Low - - 'Runs at higher levels of hydrogen were extremely rapid, resulting in polymer buildup requiring 50 termination of runs.

Example XXV

A. TBT, Mgo and MgSW,. 6H20 were combined in octane in a heated reaction vessel equipped 14 GB 2 088 862 A 14 with reflux in the manner of the foregoing Examples, to provide reaction products at molar ratios of 1/1/0.34 and 1/0.75/0.128, respectively.

B. The latter reaction product was activated by reaction with ethyl aluminum chloride at a ratio of 3/1 Al/Ti.

C. The resulting brown precipitate was separated from the supernatant red brown liquid, and 5 employed with TEA to provide about 45 ppm N under standard conditions for polyethylene polymerization (1 901F, 60 psig H2) producing resin at 107,500 g PE/gTi/hr characterized by MI 2.85, HLMI 84.5 and MIR 29.6.

D. The 1/1/0.34 reaction product prepared above was likewise activated with isobutyl aluminum chloride at 3/1 Al/Ti. The solid reaction product was washed several times with hexane and employed with TEA in a polyethylene polymerization reactor preloaded with butene-1 to provide resin of targeted density at 1700F., 30 psi H, from the ethylene/butene-1 feed. The resulting resin had a density of.9193, MI 1.9 1, HLMI 60.8 and MIR 31.8.

In the following Example, catalyst components were activated by reaction with a halide component.

Example XXVI

A. In the following runs, TMMg reaction products were reacted with the halide component added gradually thereto, usually dropwise to control the exothermic reaction. The reaction was conducted under ambient conditions for a period of time sufficient to comolete addition with stirring of reactant, for 10 to 30 minutes after occurence of peak temperature (where applicable, TMMg solid and 20 liquid components were intermixed into a slurry and employed in that form). Reactants and reactant proportions are set forth as follows:

Catalyst Component, mol ratio T11M91M9C12.6H20 (HO) HalideActivator Mol Ratio 1/0.65/0.11(0.66) BulAIC12 2/1 AI/Ti 25 1/0.65/0.11(0.66) B&AIC12 3/1 110.65/0.11(0.66) B&AIC12 4/1 1/0.65/0.11(0.66) WAIC12 6/1 1/0.65/0.11(0.66) EtAIC1' 3/1 1/0.65/0.11(0.66) EtBC12 1.25/1 (B/Ti) 30 1/0.65/0.11(0.66) EtBCI, 3/1 (Biri) 110.6510.11(0.66) S'C14 3/1 (Sini) 1/0.65/0.11(0.66) Sicl, 6/1 (Si/Ti) 1/0.75/0.128(.768) EtAICI, 3/1 1/0.75/0.128(.768) Et,Al,Cl, 3/1 35 110.75/0.128(.768) Bu'AICI, 3/1 1/0.75/0.128(.768) BulAIC12 6/1 1/0.75/0.128(.768) Et13C12 3/1 Wri) 1/0.75/0.128(.768) (CHIS'C12 6/1 (S M 1/0.75/0.128(.768) (ChIS'Cl 6/1 (SiTi) 40 1/0.75/0.128(368) (Ch3),SiHCI 6/1 (Si/M 1/0.75/0.128(.768) sic], 3/1 (Si/ri) 1/0.75/0.128(.768) SiC14 6/1 (Si/TO 1/0.75/0.128(.768) T04 1.5/1 (Ti/Ti) 1/0.75/0.128(.768) MC14 3/1 (Ti/Ti) 45 1/11.17(1.02) B&AIC12 3/1 1/1/.17(1.02) EtAIC12 3/1 1/1/34(2.04) BulAICI, 3/1 1/1/.34(2.04) BulA1C12 6/1 1/1/0.51(3.06) BulAIC12 3/1 50 1/110.51(3.06) BulAICI, 6/1 2/1/0.17(1.02) WAIC12 3/1 2/1/0.17(1.02) B&AIC12 6/1 2/1/0.34(2.04) B&AICI, 3/1 2/1/0.34(2.04) B&A02 6/1 55 3/1/0.51(3.06) B&AIC12 3/1 3/1/0.51(3.06) BulAICI, 6/1 Example XXVIII A. Catalyst samples activated with WAIC12 (21:1 AI/Ti) were employed in a series of polymerization runs, with results set forth in Table V11 as follows:

i GB 2 088 862 A 15 Table VII

Resin Powder Properties TilMgC12. 6H,0 H, Productivity (molar ratio) (molar ratio) (psig) (g PE1g T1-hr.) m/ KM1 HL/A1/M1 1/1/0.17 5.9 60 42,870 1.7 61 35.9 5 49,102 12.2 348 28.5 1/1/0.34 2.9 60 63,385 3.8 135 35.5 43,655 15.7 519 33.0 2/1/0.34 5.9 60 57,510 2.5 81 32.3 120 54,200 12.5 452 36.2 10 3/1/0.51 5,9 60 53,975 2.4 89 37.1 56,560 13,2 430 32.6 1/0.75/0.128 7.8 60 124,930 5.3 179 33.8 116,990 22.8 630 27.6 1/0.65/0.11 9.1 60 76,785 8.1 245 30.2 15 61,550 44.5 1300 - 2/1/0.17 11.8 60 138,820 2.25 67.3 29.9 89,900 17.4 491 28.2 Reactor Conditions 20 Diluent-Isobutane Temperature-1 901F. Hydrogen-as indicated Co-catalyst-triethylaluminum (45 ppm AI) Catalyst-Ti(OBU)4-Mg-M9C12. 6H20 reaction product activated with Bu'AICI 2(31 A11/TO Ethylene-1 0 mol % Run Time-60 minutes As may be seen from a comparison of Ti/M9C12. 6H20 molar ratio, peak melt index is observed at a 9:1 ratio (1.5A T1/H2o) B. In the following additional runs the effect of AI/'Ti ratio in the activated TMMg (molar ratio of 1/0.65/0.11) catalysts was explored in the polymerization of ethylene. Results ie set forth in Table 30 Vill as follows:

Table Vill

Activating Resin Powder Properties Activating CompoundITi H, Productivity Compound (molar) (psig) (g PE1g T1-hr) m/ HLMI KM11M1 35 BulAIC12 2/1 60 '54,285 16.8 489 29.1 45,670 51 1436 28.2 BulAICI, 3/1 60 76,785 8.1 245 30.2 61,550 44.5 - - B&AIC12 4.5/1 60 66,410 7.7 257 33.4 40 67.255 35.5 1119 31.5 BulAIC12 6/1 60 43,830 2.7 105 39 44,370 15.0 495 33 EtAIC12 3/1 60 60,790 7.0 214 30.6 120 97,310 39 - - 45 EtB12 3/1 60 94,755 3.7 128 34.6 56,290 21.5 616 28.6 EtBC12 1.25/1 60 34,300 3.5 105 30 27,290 18 560 31 16 GB 2 088 862 A 16 Reactor Conditions Diluent-Isobutane Temperature-1 901 F. Hydrogen-as indicated Co-catalyst- triethylaluminum (45 ppm AI) Catalyst-Ti(OBu)2-Mg-M9C12. 6H20 reaction product, activated as above. Ethylene-1 0 mole % Run Time-60 minutes. C. In a further series of experiments, employing a TMMg catalyst at 1/0.75/0. 128 molar ratio, 10 the effect of activating agent was analyzed, with results set forth in Table VIX as follows:

Table VIX

Resin Powder Properties Activation Mole Ratio H2 Productivity Agent CIM (psig) (g PE1g Ti-hr) m/ HLM1 HLM11M1 BulAICI, 6 60 124,930 5.3 179 33.8 15 116,990 22.8 630 27.6 Et13C12 6 60 94,850 3.2 103 32.2 80,060 29.0 - Me2S'C12 12 60 24,860 2.44 58.5 24.0 120 21,120 10.4 259 24.9 20 Me3S'Cl 4 60 32,225 7.25 214 29.5 28,770 16.3 460 28.2 Me2SWU 6 60 33,010 1.94 51.7 26.6 18,140 7.29 198 27.2 S'C14 12 60 61,210 8.86 210 23.7.25 5.5,435 25.2 611 24.2 S'C14 24 60 145,830 0.99 29.0 29.3 71,670 7.96 229 28.7 T04 6 60 31,950 1.8 61.7 34.2 120 24,555 8.8 297 33.7 30 Reactor Conditions S 1p 1 Diluent-Isobutane Temperature-1 90OF Hydrogen-as indicated Co-catalysttriethylaluminum, (45 pprn Al) Ethylene-1 0 mole % Run Time-60 minutes D. Larger scale polymerization runs were conducted at 1601F. with the TMMg 1/0.75/0.128 catalyst (slurry, separated from supernatant liquid, and washed with hexane) and TEA co-catalyst - employing ethylene and butene- 1 as a comonomer, utilizing varying butene-1 feed, activators and activator ratios. Results are set forth in Table X as follows:

i Table X

Ethylene Feed Butene-1 Feed (Wgt. % monomer (Wgt. % Total HlEthylene Pellet Density Run No. in reactor) monomer) (mol ratio) M/ HLM11M1 Annealed Activator A 4.41 7.55.12 12.7 1300 0.948 6/1 AVri iBuAIC), B 2.39 7.14.06 1.9 40 0.939 6/1 AIM iBuAICI, c 3.02 11.56.05 1.0 41.2 0.934 6/1 AI/Ti iBuAICI, D 2.43 11.59.07 3.2 28.5 0.939 3/1 AIM EADC E - 3.9 28.6 0.934 3/1 AIM EADC F - - 0.6 33.4 0.931 3/1 AIM EADC G 2.32 14.66.03 0.7 30:2 0.929 3/1 Wri EADC H 2.34 15.77.03 0.6 31.3 0.928 3/1 AVr) EADC 1 - - 5.8 29.7 0.935 3/1 AIM EADC j 1.75 17.82.06 1.1 43.9 0.924 6/1 AIM EADC 0 CO CO CO CD -4 18 GB 2 088 862 A 18 The resin batches collected as noted above were stabilized with 100 ppm calcium stearate and 1000 pprn Irganox 1076; characterized by conventional tests; and converted into blown film in a 1 1/2" Hartig extruder (60 rpm screw; 3' die at 0.082" die gap; cooling air 37-400F.) and further tested, all as set forth below in Tables Xl and XII:

9 ip Table Xl

Linear Low Density Resins Resin Properties A c D E F G H Eta 1 OOOX 10-3 1.56 3.67 4.36MF 3.56 3.35 3.95MF 4.00MIF' 3.90MF' 2.89 4. 15 Die Swell @ Eta 1000 146 164 - 152 150 - - - 146 165 Tensile Strength, psi @ 2011/min 3960 1790 1850 1810 1700 2250 3420 3310 1660 1910 Yield Strength, psi @ 2011/min - 3210 2770 3220 2830 2670 2480 2400 2910 2050 Elongation, % @ 2011/min 100 130 680 160 290 740 750 740 100 810 Tensile Modulus, psi X 103 66.3 52.0 42.2 49.1 39.0 39.5 33.8 34.8 44.3 27.7 Tensile Impact, ft-ibPin 2 47.7 94.6 130 88.3 79.2 213.7 267.4 299.0 96.6 181.9 Vicat, OC. 115 115 114 115 114 112 112 110 109 100 LTB, 'C. -76 -76 -76 -76 -76 -76 -76 -76 -76 -76 Shore Hardness, -D- 61 58 57 59 58 57 57 56 58 52 extrusion.

1 MIF=at least some melt fracture, indicating need for optimization of conditions for actual G) CW hi 00 0) bi cio N) 0 Table X11 Linear Low Density Resins Blown Film Properties c F G H j Film Thickness, mils 2.0 1.0 2.0 1.0 2.0 2.0 1.0 2.0 1.0 2.0 1.0 Haze, % 45.5 30.0 2&4 32.2 18.3 24.4 22.6 24.4 18.9 24.5 20.0 Gloss, 601, % 3.3 4.4 4.9 3.9 7.1 5.6 5.6 5.6 6.1 6.0 6.0 Tensile Strength, psi MD 3740 4130 5620 6060 5500 5710 6930 5710 7700 4340 6180 TD 2940 2070 3320 4410 4900 5250 5290 5250 5010 3290 3610 Yield Strength, psi MD 2610 2550 2390 2250 2180 1960 1960 1960 2010 2070 1930 TD 2840 2400 2620 2330 2410 2210 2090 2210 2020 1840 1640 Elongation, % MD 750 560 670 670 700 680 590 680 520 670 610 TD 830 320 780 880 550 850 830 850 810 830 860 Elmendorf Tear, g/mil MD 16 6 21 21 35 80 53 80 32 80 99 TD 17 346 177 492 256 277 429 277 559 366 503 Tear ASTM D 1004, Lb/mil MD 1.07 1.12 0.94 0.74 0.99 1.03 0.98 1.03 1.25 0.83 0.86 TD 0.97 0.97 0.94 0.82 0.96 0.95 1.21 0.95 1.14 0.80 0.80 Tensile Modulus, psi MD 72350 68440 60130 55250 49830 46200 46585 46200 42940 37450 35360 TD 92930 87910 74340 67800 68520 56590 54880 56590 50343 44770 48370 Dart Drop, gms (mils) 72(2.2) 10.5(1.0) 92(2.2) 45(1.3) 81(2.0) 109(2.1) 38(1.0) 109(2.1) 36(1.0) 85(2.5) 43(1.2) Dynamic Ball Burst 2,44 1.40(1.0) 3.94(2.2) 2.48(1.2) 4.26(2.0) 6.50(2.3) 3.11(1.0) 6.50(2.3) 3.14(1.0) 6.62(2.4) 3.62(1.2) cm-kg (mils) Drawdown, mils - 0.25 0.2 0.3 0.3 Melt Temp., 'F. 331 330 359 359 405 405 405 406 405 360 360 Head Pressure 3400 3400 3850 3850 4450 4500 4500 4800 4800 3900 3900 Cooling Air Temp. IF. 38 38 39 39 38 38 38 37 37 40 40 1.

G) eu 0 CO 00 CO m r-i 1 1 11 21 GB 2 088 862 A 21 E. In further larger scale polymerizations conducted in similar manner employing TMMg catalyst (slurry, separated from supernatant liquid and hexane washed) at molar ratio 1/0.75/0.128 (3/1 AIM, EADC), hexene-1 was fed to the reactor as a comonomer with ethylene, and then butene-1 was substituted providing, as followed by off-gas analysis, ethylene/butene- 1/hexene-1 copolymers 5 and terpolymers in the course of the operation. Results are set forth in Table XIII, as follows:

Table X11111

Comonomer Density m/ KM1 KM11M1 Hexene 0.9339 0,83 26.9 32 er 0.9293 0.73 23.9 33 Hexene/Butene 0.9157 0.94 31.4 33 10 Butene 0.9148 0.70 25.2 36 of 0.9148 0.70 25.2 36 el 0.9135 0.94 29.9 32 Example XXVIII TMMg catalyst prepared in accordance with the Examples and activated with isobutyl aluminum15 chloride (3/1 AIM) was also employed to produce other copolymers at varying comonomer preload, isobutane diluent, 1700F. reactor temperature, 30-40 psig H2 and TEA to provide 60 ppm Air with results as follows:

m/ MIR Ethylene/3-MethYlbutene-1 1.25 27.4 0.9488 20 1.25 28.9 0.9483 1,36 27.9 0.9507 1.55 27.7 0.9497 1.56 27.5 0.9495 1.87 29.9 0.9496 25 1.63 28.5 0.9455 2.25 28.8 0.9437 1.46 30.0 0.9428 5.01 30.3 0.9411 1.59 31.9 0.9400 30 lsobutylene 0.37 32.4 0.9518 1.35 29.6 0.9564 1.79 31.1 0.9542 1.17 31.7 0.9567 4.20 30.1 0.9582 35 3.30 32.9 0.9557 Polymerization or copolymerization of other alpha olefin monomers such as propylene, 4-methyl pentene-1, the alkyl acrylates and methacrylates and alkyl esters may be accomplished in similar manner.

The following comparative experiments were also conducted:

Comparative Examples A. In the same reaction vessel used in other preparations TBT, MgO and anhydrous M9C12 were combined in octane at a molar ratio of 2/1/0.34 and heated to ref lux for 15 minutes without evidence of reaction. The anhydrous MgC12 remained undissolved. See also Example IB above.

B. To the same system, an amount of free water equivalent to an Mgo/MgC'2, 61-120 ratio of 45 1/0.34 was added in bulk, but no change was evident.

G. TBT and Mg" were combined in a 2/1 molar ratio in octane and heated to reflux. While the yellow color became somewhat more intense, no evidence of reaction occurred.

D. To the system C above, an amount of free water equivalent to can Mg/MgC'2. 61-120 ratio of 1/0.34 was added. A small amount of light yellow precipitate was formed evidencing hydrolysis of the 50 titanium compound, but the magnesium remained unreacted.

E. TBT and MgC'2. 61-120 were combined in octane at a molar ratio of 1/0. 34 and heated to ref lux. After the salt had entirely dissolved, the solution became cloudy and somewhat viscous with continued refluxing for three hours but cleared and settled to a cloudy yellow liquid and whitish precipitate overnight. A further run at molar ratio 1/0.128 developed a clear golden yellow liquid with 55 heating to reflux over only 16 minutes. At a molar ratio of 1/1.17 foaming and formation of a thick cream colored gal terminated reaction after 45 minutes. Compare Example VII, above.

22 GB 2 088 862 A 22

Claims (26)

Claims

1. A process for the preparation of an inter-metallic compound which comprises reacting polymeric transition metal oxide alkoxide with reducing metal of higher oxidation potential than the transition metal.

2. A process according to claim 1 wherein the polymeric transition metal oxide alkoxide is 5 produced by partial hydrolysis of the transition metal alkoxide.

3. A process according to claim 2 wherein the hydrolysis is effected with an aquo complex as a water source.

4. A process according to claim 3 wherein water is provided in the form of hydrated salt.

5. A process according to claim 4 wherein water is provided in the form of hydrated salt selected 10 from hydrates of aluminum, cobalt, iron, magnesium and nickel salts.

6. A process according to claim 3 wherein water is provided in the form of hydrated oxide.

7. A process according to claim 6 wherein water is provided in the form of silica gel.

8. A process according to any of claims 3 to 7 wherein the molar ratio of transition metal to water is from about 1:0.5 to about 1:1.5.

9. A process according to any preceding claim wherein the reducing metal comprises at least one of magnesium, calcium, zinc, aluminum and potassium.

10. A process according to any preceding claim wherein the transition metal comprises titanium or zirconium.

11. A process according to any preceding claim wherein the transition metal and reducing metal are present in a molar ratio of from about 0.5:1 to about 3: 1.

12. A process according to any of claims 1 to 10 wherein the transition metal and reducing metal are in a molar ratio of from about 1:1 to about 10:1.

13. A process according to any preceding claim wherein the reaction is initiated by heating to an elevated temperature to initiate exothermic reaction.

14. A process according to claim 13 wherein heating is continued until up to the stoichiometric amount of reducing metal is consumed.

15. A process according to any preceding claim wherein the product is further reacted with a 1 halide activator.

16. An intermetallic compound comprising the reaction product of polymeric transition metal 30 oxide alkoxide and at least one reducing metal of higher oxidation potential than the transition metal.

17. An intermetallic compound according to claim 16 wherein the transition metal comprises titanium or zirconium.

18. An intermetallic compound according to claim 16 or 17 wherein the reducing metal comprises at least one of magnesium, calcium, zinc, aluminum and potassium.

19. An intermetallic compound according to any of claims 16 to 18 wherein the polymeric transition metal oxide alkoxide comprises the product of the controlled partial hydrolysis of a titanium alkoxide.

20. An intermetallic compound according to any of claims 16 to 19 wherein the transition metal and reducing metal are present in a molar ratio of at least 0.5:1.

21. An intermetallic compound according to claim 20 wherein the said ratio is from about 1:1 to about 10:1.

22. An intermetallic compound according to claim 16 and substantially as hereinbefore described in any Example.

23. The product of the reaction of a compound according to any of claims 16 to 22 with halide 45 activator.

24. A process for the preparation of an intermetallic compound, the process being substantially as hereinbefore described in any Example.

25. A process for the preparation of a halide-activated intermetallic compound, the process being substantially as hereinbefore described in any Example.

Example.

26. A halide-activated intermetallic compound substantially as hereinbefore described in any Printed for Her Majesty's Stationery Office by the Courier Press, Leamington Spa, 1982. Published by the Patent Office, 25 Southampton Buildings, London, WC2A 'I AY, from which copies maybe obtained.