NZ199048A - Intermetallic compounds of polymeric transition metal oxide alkoxides - Google Patents

Abstract

A 1-olefin is polymerised or copolymerised using a catalyst system comprising a mixture of cocatalysts, one of which is a halide activated intermetallic compd. comprising the reaction product of a polymeric transition metal oxide alkoxide a reducing metal of higher oxidation potential than the transition metal. Low density polyethylene for blown or cast film, wire and cable coating, coextrusion and injection or rotational moulding is produced having a broader molecular wt. distribution and higher melt index.

Description

New Zealand Paient Spedficaiion for Paient Number 1 99048 199043 Pri^cTcT:--^;: <& 'Jl'MfiW: I; ?J> Constats Cv-s-X'sstfcn Class WtteAM; ?///*... Pubises Bii* SU"!)®6 f*.0. Journal Wo: fm ppp^fllflS m b a a si iifs mi y$j[ y gfj tyj 9 Patents Form No. 5 NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION "INTERMETALLIC COMPOUNDS OF POLYMERIC TRANSITION METAL OXIDE ALKOXIDES11 We, NATIONAL DISTILLERS AND CHEMICAL CORPORATION, a corp-ation of the State of Virginia, U.S.A., of 99 Park Avenue, New York, New York, U.S.A., hereby declare the inventi-: for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particular described in and by the following statement 1 (followed by page 1A) p 1 g 3310/3415 b-j I 199048 1 INTERMETALLIC COMPOUNDS OF POLYMERIC TRANSITION METAL OXIDE ALKOXIDES This invention relates to intermetallic compounds 5 of transition metal alkoxides, and processes for their production. More particularly, the invention affords catalyst precursors for interreaction with halide activators to provide a catalyst component adapted for the polymerization of alpha olefins.

Polvethylene, 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 15 polyethylene resins characterized by linearity and short chain branching afforded by alkene comonomers, and offering narrow molecular weight distribution, improved strength properties, higher raelt viscosity, higher softening point, improved ESCR (Environmental Stress Crack Resistance) and 20 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 25 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 pro-30 moter such as an alkyl aluminum halide. Among the improved catalysts of this tvpe are those incorporating a magnesium component, usually by interaction of magnesium or a compound 199048 1 thereof with the transition metal component or the organo-metallic component, as by milling or chemical reaction or association. 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. metal-containing intermetallic compounds are prepared by the reaction of a polymeric transition metal oxide alkoxide with at least one reducing metal, i.e., a metal having a higher oxidation potential than the transition metal. Thus, a polymeric titanium alkoxide, or oxoalkoxide, is reacted with 15 magnesium metal to provide a reaction product which may be activated to form an olefin polymerization catalyst element. be separately prepared by the controlled hydrolysis of the alkoxide; or the polymeric oxoalkoxide mav be provided bv an 20 in situ reaction, e.g., 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 25 such as magnesium halide hexahydrate. 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 jo oligomeric, usually trimeric titanium alkoxides results in polymeric titanium oxide alkoxides, generally expressed as There is also interest in producing intermediate According to the present invention, transition The polymeric transition metal oxide alkoxide may Transition metal alkoxides, particularly titanium 199048 1 Ti(OR), + nH-0 =»TiO (OR), _ + 2n ROH -1- 4 2 n 4-2n Condensation reactions may also occur especially at elevated temperatures to structures involving primary metal-oxygen-metal bridges such as: (j)R OR OR - Ti - O - 'ti - OR Ar AR 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 fTi3)°4x4(x+3)^ where x~0' 1,2,3,..., the structure reflecting the tendency of the metal to expand its coordination beyond its primary valency 15 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 20 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 eventuating, with complete 25 hydrolysis, in orthotitanic acid.

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 20 °ut 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 23;.;;-^ 19904 1 practice is to generate these materials in the reaction medium. Evidence indicates that the same hydrolysis reaction occurs in situ.

The hydrolysis reaction itself may be controlled 5 directly bv 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 10 °f 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 zeolitic water. Thus, common hydrated metal salts are usually employed, 15 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 20 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 25 limitation that the stereoconfigurat.ion of the partially hydrolvzed 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 20 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 199048 1 precipitation of hydrolysis products from the hydrocarbon solvent medium mav 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 5 believed that the reaction is essentially equimolar, a certain excess of water is appropriately employed in some cases, as is customary. form, chain length, etc. of the hydrolysis product may be 10 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. conditions of pressure and temperature, and requires 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. reacted with a reducing metal having an oxidation potential 25 higher than the transition metal. Preferably a polymeric titanium oxide alkoxide is employed together with magnesium, calcium, potassium, aluminum or zinc, as the reducing metal. Combinations of transition metal alkoxide, reducing metal and hydrated metal salt are usefully selected with refer-2o ence to electropotentials to minimize side reactions, as known in the art; and in general to assure preferred levels of activity for olefin polymerization, magnesium values are It will be understood that the stereoisomeric The hydrolysis reaction proceeds under ambient The polymeric transition metal oxide alkoxides are 199048 1 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 con-5 venience), titanium tetra-n-butoxide (TBT) is reacted with magnesium turnings and hydrated metal salt, most preferably magnesium chloride hexahydrate, at a temperature of 50-150°C. , in a reaction vessel under autogenous pressure. TBT may constitute the reaction medium, or a hydrocarbon 10 solvent may be used. Ti/Mg molar ratios may varv from 1:0.1 to 1:1 although for the most homogeneous reaction system a stoichiometric relationship of Ti" to Mg° of 1:1 is preferred, with an amount of hydrated metal salt to supnly during the reaction about 1 mole of water per mole of Mg°. 15 The hydrocarbon soluble catalyst precursor com prises predominently Ti values in association with Mg values, in one or more stereoconfiguration complexes believed to constitute principally oxygenated species. Some evidence of mixed oxidation states of the titanium values 20 suggests an interrelated system of integral species of Ti" , Ti^and Ti"1""'" values 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. 25 The intermetallic compounds have special interest as catalyst precursors, in support or unsupported systems, for isomerization, dimerization, oligomerization or polymerization of alkenes, alkynes or substituted alkenes in the presence or absence of reducing agents or activators, e.g., go organometallic compounds of Group IA, IIA, IIIA, or ITB metals. 199048 1 In the preferred utilization of such precursors, they are reacted with a halide activator such as an alkvl aluminum halide and combined with an organometallic compound to form a catalyst svstem adapted particularly to the poly-5 mer.ization of ethvlene and comononers 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 10 carbon atoms, preferably 2 to 5 carbon atoms, and most preferably n-alkyl such as n-butyl. The selected component is normally 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 may be contemplated where they do not interfere with the reaction in the sense 20 of significantly modifying performance in use. In general, the halide-free n-alkoxides are employed.

The transition metal component is provided in the highest oxidation state for the transition metal, to provide the desired stereoconfigurational structure, among other 25 considerations. Most suitably, as aforesaid, the alkoxide is a titanium or zirconium alkoxide. Suitable titanium compounds include titanium tetraethoxide, as well as the related compounds incorporating one or more alkoxv radicals including n-propoxy, iso-propoxv, n-butoxv, isobutoxy, go secbutoxv, tertbutoxy, n-pentoxy, tertpentoxy, tert-amyloxy, n-hexyloxy, n-heptyloxy, nonvloxy and so forth. 199048 1 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 5 may be taken into account in selecting a preferred derivative. In general, titanium tetrabutoxide 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 suit-10 able, 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 Dart in the zero oxidation state as a necessary element of the 15 reaction system. A convenient 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 20 rate. The reducing metal may be supplied as convenient, in the form of a slurry in the transition metal component and/or hydrocarbon diluent, or may be added directly to the reactor.

Whether in the case of the in situ preparation (or 25 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 mav be, in a delayed rate controlled manner during the reaction. 30 As aforesaid, the coordination sphere afforded by a hydrated metal salt has been found suitable for the purpose; but other sources of water in the same proportions are also 23D^CS98l' ■J , 1 199048 1 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 5 base material in known manner.

Suitable materials include the hydrated metal salts especially the inorganic salts such as the halides, nitrates, sulphates, carbonates and carboxylates of sodium, potassium, calcium, aluminum, nickel, cobalt, chromium, 10 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. 15 Autogenous pressure is employed, as the reaction proceeds smoothly under ambient 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 20 to ensure a homogeneous reaction system.

Usually a hvdrocarbon solvent such as hexane, heptane, octane, decalin, mineral spirits and the like is also used to facilitate intermixture of components, heat transfer and maintenance of a homogeneous reaction svstem. 25 Saturated hydrocarbons are preferred, having a boiling point in the range of 60 to 190°C. The liquid transition metal component also mav serve at least in part as the reaction medium, especially where no added solvent is employed. The reaction involves a stage where additional go volatile components form azeotropes with the solvent, or if the components are employed neat, constitute the source of reflux, but in either case it is preferred, at least to 19904$ 1 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 5 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.

Reaction temperature will to some extent be a 10 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) 15 evidences visible gas generation at about 60°-70°C. suqqesting an initiation temperature or activation energv level at about 50°C. which therefore constitutes the minimum necessary temperature for reaction of the polymeric oxide alkoxide with the reducing metal. The reaction is somewhat 20 exothermic during consumption of the reducinq 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 25 completion of the reaction is evidenced by consumption of visible metal and/or attainment of the reflux temperature for the pure solvent within a period of as little as 30 minutes to 4 hours or more. Such temperatures may reach 140°-190°C. and of course higher temperatures might be 30 imposed but without apparent benefit. It is most convenient to operate within the range of 50-150°C., preferably 70-140°C. In the absence of solvent, the upper limit will 199048 1 simply be established by the reflux temperature for the alkanol generated in the course of the reaction.

Reaction of the components is most clearly apparent from the marked color change, with exotherm, that 5 accompanies commencement of gas evolution, where lack of opacity or turbiditv 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 10 greyish, then rapidly darker to blue, sometimes violet, usually blue black, sometimes with a greenish tint.

Analysis of the gas evidences no HC1; and is essentially Following the rapid color change some deepening of color occurs during a gradual increase of temperature, with con-15 tinuing 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 manner along with the remaining reducing metal. 20 The reaction product is hydrocarbon 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 reaction product inconveniently gelatinous or intractable, the transition 30 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 to 1.0 19904 to 3.0:1.0 or more, preferably 1/0.1-1/1. 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 uncon-sumed 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/I^O components have been found most adapted to the formation of a homogeneous reaction product.

The water, or water-related species is also preferably supplied in molar ratio to the transition metal component, for similar reasons of homogeneity and ease of reaction. Thus, in the case of MgClj^H^O, 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 H^O 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 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. 13 199048 1 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 pro-5 viding such species in a regular, sequenced, constant or variable rate-related manner. The same molar proportion of free water supplied at the commencement of the reaction is however whollv ineffective in initiating reaction at this or higher temperature, and results in undesirable complete 10 hydrolysis reactions. 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 insufficiency of water will invar-15 iably 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. 20 The selection of aquo complexes or hydrated. metal salts where employed is essentially a matter of the controlled availability of water it affords to the svstem. Thus, sodium acetate trihydrate is suitable, as is magnesium acetate tetrahvdrate, magnesium sulphate heptahydrate and 25 magnesium silicon fluoride hexahydrate. A salt of maximum degree of hydration consistently with the controlled release afforded bv the coordinate bonding relationship is preferred. Most conveniently, a hydrated magnesium halide such as magnesium chloride hexahydrate or magnesium bromide hexa-30 hydrate 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 U.K. Patent The measured amount of water is essentially in 199048 1 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 an electron donor or Lewis base, or a solvent performing irt part those functions. As shown in the Examples, the reaction is implemented in the preferred embodiment with 10 water of crystallization, and an alcohol component in the system. Tt. is not known with certainty, therefore, whether proton transfer or electron donor mechanisms participate or compete in the reaction system.

No separations are necessary as at least a portion 15 of the reaction product is soluble in the saturated hydrocarbon where employed as a solvent or provides a solvation medium such that even where a precipitate also occurs, and even after storaqe, 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 alkyl aluminum halide, a silicon halide, an alkyl silicon halide, a titanium halide, or an alkyl boron halide. It has been 25 found that the catalyst precursor may be activated readilv, 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 30 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 molecular 23£}?-, >>81 199048 1 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 5 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 cata.lvst product may be used directly in the polymerization reaction although it is ]_0 typically diluted, extended or reduced as required to provide in a convenient feed an amount of catalyst equivalent to B0-100 mg/transition metal, based upon a nominal productivity of greater than 200,000 gm polymer/gm transition metal in continuous polymerizations which the present catalyst ordinarily exceeds. Adjustments are made by the artisan to reflect reactivity and efficiency, ordinarily by mere dilution, and control of feed rates.

The transition metal containing-catalyst is combined for use in polymerization with an organometallic 20 co-catalvst such as triethvl aluminum or triisobutvl aluminum or a non-metallic compound such as triethylborane. A typical polymerizer feed thus comprises 42 parts of iso-butane solvent, 25 pts. of ethylene, 0.0002 pts. catalyst (calculated as Ti), and 0.009 pts. co-catalyst (TEA, calcul-25 ated as Al), to a reactor maintained at 650 psig. and 160°F. In general, the amount of co-catalvst, 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 30 aluminums, such as triethyl aluminum, triisobutyl aluminum, trinoctyl aluminum, alkvl aluminum halides, alkyl aluminum alkoxides, dialkyl zinc, dialkyl magnesium, and metal boro- 23 1981 16 199048 1 hydrides 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 t'riethyl borane, triisobutyl borane and 5 trimethyl borane and hydrides or boron such as diborane, pentaborane, hexaborane and decaborane.

The polymerization reactor is preferably a loop reactor adapted for slurry operation, thus employing a solvent such as isobutane from which the polymer separates ]_0 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 200"F. with applied hydrogen as desired to control molecular weight distribution. Other n-alkenes may be fed to the reactor in minor 15 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 mol%, although other alpha olefin comonomers/proportions may be readilv used. Tn utilizing such n-alkene comonomers, one may secure resin 20 densities over the range from .9] to .96.

Still other alpha olefin comonomers, such as 4-methvl-pentene-1, 3-methyl-butene-l, isobutvlene, 1-heptene, 1-decene, or 1-dodecene may be used, from as little as 0.2% by weight, especiallv where monomer 25 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, 2 3 r. 8! 199048 1 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 5 association among the unconsumed 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 10 parts are by weight except as otherwise noted. Melt indices are measured under conditions E & F, respectively, of ASTM D-1238-57T, for MI and HLMI values, on powder or resin samples as specified. HLMI/MI or MIR is melt index ratio, a measure of shear sensitivity reflexting molecular weight 15 distribution. Other tests are as indicated, or as conventionally conducted in the related arts. 199048 1 EXAMPLE I A. 6.0 pts. of Ti(OBu)^ [TBT] and 4.2 pts. of CrCl^SH^O 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 60-70°C. An additional 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 total of 10 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 15 was employed with the titanium alkoxide, but no reaction occurred, with heating at greater than 100°C. for a half hour. Addition of zinc dust and further heating at greater than 150°C. still evidenced no reaction. Substitution of magnesium shavings also resulted in no reaction. It was 20 concluded that the hydrated salt was a necessary component of the reaction system. 199048 EXAMPLE II A. TBT (0.121m), CrCl3*6H20 (0.015m) and Mg° (0.0075m) were combined in a stirred reaction vessel equipped with an electric heating mantle. The chromium salt was wholly dissolved at about 60°C., and reaction with the magnesium shavings was apparent from gas evolution at 85°C., which was vigorous at 100°C., subsiding at 116°C. with some Mg remaining. After dissolution of the remaining Mg, heating was continued, to a total reaction time of 1 hour and 4 5 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 0.116m TBT, 0.029m CrCl^^I^O and 0.0 2 9m Mg. A muddy green reaction product at 118°C. took on a definite bluish color at 120°C. 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 0.116m TBT, 0.058m CrCl^'GI^O, 0.0145m 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 0.115m TBT, 0.0287m CrCl^'fif^O, and 0.0144m Mg. A muddy green material evident at 114°C. became blue at the Mg surface. The recovered reaction product was hexane soluble.

E. In a similar run, 0.176m TBT, 0.30m CrCl^^^O and 0.176m Mg° were reacted in octane. The clear green color of the reaction at 70°C. turned muddy with increasing gas evolution and darkened to almost black at 90°C. The 199048 1 color returned to green at 119°C. and the reaction was terminated at 121°C. 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 5 of darker color (about 50:50/volume) which settled out.

F. In vet another run in octane, the reactants were provided in the proportions 0.150m TBT, 0.051m CrCl3~6H20 and 0.150m Mg. Again, the muddy green color changed to almost black with vigorous effervescence, forming 10 at 109° a dark blue black reaction product. (5.7 wgt.% Ti; 2.9% Mg, 2.1 wgt% Cr). 21 EXAMPLE III 199048 A. The reaction product HE was combined in a reaction vessel with isobutvlaluminum chloride added drop- wise in proportions to provide a 3:1 Al/Ti molar ratio. The green colored mixture changed initially to brown violet at 38°C., which upon completion of reactant addition at 39°C. had changed to red brown in appearance. After 30 minutes additional stirring, the reaction was terminated, the pro-10 duct being a dark red brown liquid and a dark brown precipitate .

B. Reaction product IIF was similarly reacted with isobutyl aluminum chloride (3.1 Al/Ti molar ratio). The peak temperature with complete addition was 48°C. , but no brown color change was evident. The reaction product was a clear liquid and a dark grey precipitate. 22 EXAMPLE IV 199048 The catalyst components prepared in Example III above were employed in the polymerization of ethylene 5 (190°F., 10 mol% ethylene, 0.0002 pts. catalyst calculated as Ti, triethyl aluminum about 45 ppm, calculated as Al, as indicated) with results set forth in Table I, as follows: 23 199048 TABLE I H Prod.

Catalyst pgig g Pe/g Ti hr Resin properties MI HLMI HLMI/MI IIIA 60 120 35160 29220 .1 18.9 265 618 26.3 32.6 tub 60 120 30380 26880 9.6 32.8 264 855 27 26.1 \ J ' V. 199048 In the following Example, the catalyst component of the invention was prepared from the reactant admixture in the absence of added solvent.

EXAMPLE V A. 0.1212m Ti(ORu)^ [TBT], 0.121m magnesium turnings and 0.0012m MqCl2'6H20 (TRT/Mg/MgCI'bH?0 = 1:1:0.01 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 95°C. gas evolution commenced on the surface of the magnesium turnings. At 140°C. with reflux the bubbling had become vigorous. The solution darkened in color and the bubbling ceased at 170°C., whereupon the reaction was terminated. The reaction product contained excess magnesium -- only about 8.5 percent charged had reacted -- and was soluble in hexane.

B. Tn another run, the molar ratio of MgCl^'611^0 was increased (TBT/Mg/MgCl^'6H^n = 1:1:0.1 molar). The gold yellow liquid became greyish with gas evolution at 104°C., and darkened with further heating to 168'C. 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. 199048 1 The following Example shows the preparation carried out in a hydrocarbon solvent.

EXAMPLE VI A. 50.2 pts. (0.148m) of TBT was added to a stirred reaction vessel equipped with an electric heating mantle, and 58.6 pts. octane. The magnesium turnings (0.074m) were added, stirring commenced and then 0.0125m MgC^^HjO added with heating over one minute. At 75°C. (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 15 refluxing at 117°C. (35 minutes). The magnesium metal had entirely reacted within 1 hour (128-129°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 wgt% Ti and 2.0 20 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: 26 199048 1 Ti/Mg/MgCl '6H-0 Ti/Mg Mol Ratio (Molar) 1.0/0.65/0.11 1.0/0.75/0.128 1.0/1.0/0.085 1/1/0.17 1/1/0.34 1/1/0.51 1/2/0.17 1/2/0.34 2/1/0.17 2/1/0.34 3/1/.51 1. 32 1.14 0. 92 0.85 0.75 0. 66 0.46 0.43 1.70 1.50 1.99 Notes Dark blue black liquid and green precipitate. 6.6 wgt% Ti, 2.6 wgt% Mg values (calc) Blue solution with greenish tint. 6.5 wgt% Ti, 2.8 wgt% Mg values (calc) Blue black liquid with light green precipitate (insoluble in acetone, alkane and methylene chloride) Some unreacted Mg° Dark blue black liquid, 6.6 wgt% Ti, 3.9 wgt% Mg values (calc) Dark blue black liquid, 6.7 wgt% Ti, 4.6 wgt% Mg values (calc) Milky blue liquid. 3.7 wgt% Ti, 2.9 wgt% Mg values (calc) Dark blue black liquid and viscous green gel. Some unreacted Mg° Dark blue black liguid and viscous gel. Some unreacted Mg.

Example IIA Blue black solution. 7.1 wgt% Ti, 2.3 wgt% Mg values (calc) Blue black liquid with slight green tint. 6.1 wgt% Ti, 1.6 wgt% Mg values (calc) 199048 C. The preparation 1/1/0.34 obtained above was repeated except that 63.7 pts. TRT was employed with 67.5 hexane as the solvent reaction medium. A dark blue black liquid resulted, containing bv calcination 8.2 wgt% Ti and 1.6 wgt% Mg values. 199048 1 The following Example shows the stepwise prepara tion of the catalyst component.

EXAMPLE VII 2.61 pts. MgC^^I^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. Prolonqed stirring resulted in a 2_0 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.) A TM Mg reaction product was prepared in the 15 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 octane. The reaction proceeded smoothly to a dark blue black liquid and qreen precipitate in the same manner as other reported reactions. 2o The reaction product was activated with ethyl aluminum dichloride at a 3/1 Al/Ti ratio to form a catalyst component for olefin polymerization. 199046 2 The following Example evidences the significance of level of bound water.

EXAMPLE VIII A series of identical runs were performed at the molar ratio 1/0.75/0. 128 (TBT/Mg/MgCl.," 61^0) except that the degree of hydration of the magnesium salt was modified.

When MgCl2"4H20 was employed (H^O/Mg = .68/1 as 10 compared to 1:1 for MgCl2'6H20), only 89.1% of the magnesium metal reacted. Use of MgCl2*2H20 at the same overall molar ratio (U^O/Ma 0.34/1) resulted in only 62.1% reaction of Mg° .

In repeat runs, the amount of hydrated salt 15 supplied was increased to provide a 1/1 H^O/Mg ratio. All of the magnesium metal reacted. It was also observed that the amount of insoluble reaction product increased with increasing salt levels. 199048 1 The following Example illustrates the use of other titanium compounds.

EXAMPLE IX A. 45.35 pts. (0.1595m) TifOPr1)^, 0.1595m Mg° and 50.85 pts. octane added to a stirred reaction flask fitted with an electric heating mantle, and 0.027m of MgC^" 611^0 were added. The milky yellow mixture became grey ]_0 with reflux, at about 88°C. , and turned blue at 90°C. with gas effervescence. Based upon magnesium remaining, it was concluded that the reaction was partially suppressed by the octane/isopropanol azeotrope present.

B. The reaction described in A was repeated, at a 15 reactant mol ratio of 1/0.75/0.128 using decalin (b.p 185-189°C) as the diluent. After six hours, the reflux temperature had attained 140°, and the reaction was terminated. A dark blue black liquid was obtained with a small amount of dark precipitate. Only 8.8% of the mag-20 nesium had reacted.

C. In a similar manner, reaction with tetraiso-butyltitanate was carried 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 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 30 an|3 butanol, (believed to be dibutoxv titanium dichloride) was reacted with magnesium and magnesium chloride hexahydrate at a molar ratio of 1/0.75/0.128 under conditions 199048 1 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. 32 199048 1 The following Example employs a zirconium metal alkoxide.

EXAMPLE X A. 12.83 parts of Zr(OBu)^'BuOH (0.028m); 0.34 pts. Mg°(0.14m) in the form of commercially available turnings, and 8.8 pts. octane were placed in a reaction vessel and heated to reflux at 125°C. with stirring for 15 minutes, without evidence of any reaction. 0.97 pts. of MgCl^'fiH^O (0.005m) 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 (0.069m) was combined with the magnesium metal turnings (0.069m) and 57.6 pts. mineral spirits (bp 170-195°C.) and 4.79 pts. MgC^^F^O (0.0235m) 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 20 surface of the magnesium metal was evident when the temperature had attained 85°C., at 8 minutes reaction time. Gas evolution continued with vigorous effervescence, the temperature rising to 108°C. when a whitish solid appeared. With continued heating to 133°C. (1 hour reaction time) all 25 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 30 hydrocarbons.

The reaction product may be activated in known manner with, e.g., an alkyl aluminum halide by reaction ^cCj93/ 199048 therewith conveniently at a molar ratio of about 3/1 to 6/1 Al/Zr to provide, in combination with an organic or organometallic reducing agent, an olefin polymerization catalyst system adapted to the formation of polyethylene resin. 34 199048 1 The following Example shows the substitution of calcium for magnesium as the reducing metal.

EXAMPLE XI A. 0.074m Ti(OBu)^; 0.074m Ca° (thick turnings supplied commercially, mechanically cut into smaller pieces) and 0.0125m MgCl2*6H70 were combined in octane in a stirred reaction vessel equipped with an electric heating mantle.

Upon attaining 105°C., the solution darkened in color, and at 108°C., with gas evolution, the solution took on a dark grey appearance. At 110.5°C. rapid gas evolution was evidenced, followed bv formation of a dark blue liquid. At 90 minutes, the reaction was terminated and a reaction 15 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% 20 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 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, 25 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 Al/Ti 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 upon completion of the reaction to 199048 1 a pink liquid and a white precipitate. At 6/1 Al/Ti ratio, the slurry changed in color to grey, and then lime green.

Reaction product XI A2 was likewise treated with EtAlC^ at a 3/1 and 6/1 Al/Ti molar ratio. The reactions 5 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.

U) VJ1 uo o ro VJ1 TBT-Ca-MgCl "6H O (molar ratio) 1/0.5/0.34 1/0.47/0.128 Reaction Ratio 3/1 6/1 3/1 6/1 Bench Scale Reactor Conditions Diluent - Isobutane Temperature - 190°F.

Hydrogen - as indicated Co-catalyst - Triethylaluminum Ethylene - 10 mole % Run Time - 60 minutes TABLE II I "2 I (psiq) Productivity (gPE/qTi.hr) 60 40 ,950 60 43,810 60 ,930 120 11, 260 60 27,420 120 33,050 Resin Powder Properties MI HLMI " MIR 3.84 131 34.1 1.03 47.7 46.3 1.73 73.7 42.6 7.0 320 45.7 0.35 21.0 60.1 1.75 116 66.0 u> O-i (TEAL) at about 4 5 ppm Al tO QO 19904$ 1 The runs evidenced a somewhat broader molecular weight distribution in the resin as compared to the use of magnesium as the reducing metal. 199048 1 The substitution of zinc as the reducing metal is shown in the following Example.

EXAMPLE XII A. 0.204m TBT, 0.153m of Zn° granules, and 0.026m of MgC^^^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 ]_0 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 product TiZnMg (molar ratio 1/0.86/0.128) was reacted with isobutyl aluminum chloride, at a 3/1 Al/Ti molar ratio, in hexane at 10-13°C. (XII Bl).

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 green layer on the zinc surface.

D. The activated reaction product XII Bl 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 170°F. and 35 psig in the presence of triethyl aluminum as co-catalyst. The resin recovered had the following proper- gO ties: Density .9165, MI 1.68, HLMI 52.1 and MIR 31. <99048 The following Example involves the use of potassium as the reducing metal.

EXAMPLE XIII 62.7m mol of TBT, 47m mol of fresh potassium metal (scraped clean of its oxide/hydroxide coating under octane), and 8.0m mol of MgClj'Gl^O were combined in octane in an enclosed system equipped with reflux, and externally heated. Within 2 minutes at 35°C. 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. 199048 1 Examples XIV-XV describe the use of aluminum as the reducing metal.

EXAMPLE XIV A. 112.31 pts. of Ti(OBu)^ (0.33m), 8.91 pts. of Al° (Alfa Inorganicspherical aluminum powder, -45 mesh) and 11.4 pts. of MgCl2"6H20 (0.056m) [molar ratio 1:1:0.17] were admixed in a reaction vessel with stirring, and heat applied, employing an electric mantle.

When 100°C. was attained in about 10 minutes, the yellow color deepened, and at 118°C. vigorous effervescence commenced, with gas evolution. At 122°C. 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 145°C., within 1 hours and 20 minutes, whereupon gas evolution was essentially 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. Al° reacted. The reaction product contained 7.9 wgt% Ti, 3.4 wgt% Al 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 0.015m Ti) was added in hexane (13.0 pts.) to a reaction vessel in a cooling bath. 0.045m ethyl aluminum dichloride was added gradually, the temperature being maintained at 15-20°C. The admixture, 199048 stirred for 30 minutes provided a dark red brown slurry and an intractable solid. (Bl).

A second run was carried out (0.175m Ti/0.0525m Al) without cooling to a peak temperature of 38°C., and a red brown slurry again formed, with an intractable solid deposit. (B2). 199048 1 ' EXAMPLE XV The reaction products of Example XIV were employed as catalysts in the polymerization of ethylene under 5 standard conditions (190°F., 60 psig H^) employinq triethyl aluminum as a co-catalvst, with results as follows: Ml HLMI MIR Bl 0.14 6.45 46.1 B2 0.38 17.4 45.7 4 3 199048 1 EXAMPLE XVI A. In a similar manner to the foregoing, 0.133m TBT, 0.100m Al°, and 0.017m A1C13'6H.,0 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% al.

(XVI Al). ]_0 In the same manner, the same reactants were combined in a 1/1/0.17m ratio. About 58% of the Al reacted, to provide a reaction product containing 6.5 wgt% Ti and 2.7 wgt% Al. (XVI A2).

B. The reaction products (XVI Al) and (XVI A2) were activated with ethyl aluminum chloride at 3/1 Al/Ti.

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 170°F., 15 psig to produce resin character- ized by MI .02, HLMI 1.01, MIR 50.5 and in a second run MI .02, HLMI .45 and MIR 22.5. < 7 -X -W ■■ ^'4?/ " 44 199048 1 The following Examples are drawn to catalyst com ponents prepared employing other aquo complexes, EXAMPLE XVII A. 0.0335 mol TBT and 0.0335 mol Mg° were stirred in octane in a heated reaction vessel, to which .0057 mol of MgBr2'6H20 was added. (Reaction molar ratio 1/1/0.17). The salt dissolved in six minutes with heating to 65°C. A grey color developed with gas effervescence, and the solution turned blue, then blue black with a greenish tint. The reaction was terminated at 123°C. (about 10% unreacted Mg) after a reaction period of 4 hours and 10 minutes. (XVII A).

In a similar manner, a reaction product was pre-15 pared at a mole ratio of (Ti/Mg/MgBr?'6H20 = 1/0.65/0.11), 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 Al/Ti) a peak temperature of 42°C. was attained with addition at a rate of 1 drop/2-3 sec, whereupon the green liquid turned brown. The reaction product was a red brown liquid and brown precipitate. (IV 25 B-l) 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 SiCl. in the same manner. The reaction 4 product of a 30 minute reaction at a 3/1 Si/Ti ratio was a go light yellow liquid and a brown precipitate. A similar run provided a 6/1 Si/Ti reaction product. 199048 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 190°F., with hydrogen modifier and triethyl aluminum cocatalyst (45 ppm Al) and compared to an identical run using magnesium chloride hydrate, with results set forth in Table III as follows: '"Si uo ui U) o Catalvst Al/Ti+ Ti(OBu).-Mg-A (molar) A = MgCl2"6H20 3/1 ro H H o ui o ui i TABLE III H2 Productivity Powder Resin Properties (psig) (g PE/g Ti-hr) MI HLMI HLMI/MI 60 42,870 1.7 61 35.9 120 49,100 12.2 348 28.5 60 105,190 24 698 29 120 77,390 102 60 34,780 10.3 371 36 120 37,050 17.8 639 35.9 CP <x> o QO 199048 1 EXAMPLE XVIII A. 42.23 pts. of TBT (0.124m) were combined with 3.02 pts. Mg (0.124m) in octane (42.8 pts.) in the presence of 5.7 pts. FeCl3*6H20 (0.02m) (TMgFe = 1/1/0.17 molar) in an enclosed stirred reaction vessel equipped with reflux, and an electric heating mantle. Heating commenced, and within 6 minutes, at 65°C. gas evolution began. The muddy yellow color turned dark brown at 80°C. (7 minutes) and gas 20 evolution increased. In about 30 minutes gas evolution had slowed and then ceased with consumption of Mg° , and the reaction was terminated. The very dark liquid evidenced no residue. (XVIII Al).

In a second run, the same reactants were combined 15 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% solution of ethyl aluminum chloride in hexane at a 3/1 Al/Ti ratio. A brown liquid and solid was recovered, containing 16.5 Mg Ti/g. (XVIII Bl).

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 25 liquid and grey precipitate contained 16 Mg Ti/g.

C. Activated reaction product XVIII Bl was employed in the polymerization of ethylene at 190°F., 60 psi . 114,320 g PE/g Ti/hr were recovered, exhibiting the following properties: MI 5.1, HLMI 155.3, MIR 30.3. 48 EXAMPLE XIX 199048 A. 1. 0.160m Ti (OBu)^, 0.160m magnesium turnings and 0.027m CoClj'SHjO were combined in a stirred reaction vessel with 61.2 pts. of octane. The violet cobalt salt crystals provide upon dissolution a dark blue solution. The admixture is heated, employing an electric mantle, and gas evolution on the magnesium surfaces appears at 58°C., increasing to vigorous effervescence at 107°C. within 12 ]_0 minutes. The clear blue color becomes greyish on further heating and becomes almost black at 123-125°C. 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 liquid and a dark 15 precipitate upon standing.

The run was repeated, with essentially identical results.

B. The reaction product of the foregoing preparation was shaken, and 0.0111m (Ti) was combined with isobutyl aluminum chloride (0.0333m Al) supplied dropwise to a reaction vessel. The temperature peaked at 40°C. , with formation of a greyish precipitate, which upon further addition of BuAlC^ turned brown. After stirring for an additional 30 minutes the reaction was terminated, pro-25 viding 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 (190°F., 10 mol % ethylene, 0.0002 pts. catalyst calculated as Ti, triethyl aluminum about 45 ppm calc as Al, H0 as indicated) with the results set forth in Table IV, as follows: 49 199048 1 TABLE IV H Prod Resin Properties Catalyst psiq g PE/g Ti/hr MI HLMI HLMI/MI XIX B 60 105,180 6.2 206 33.6 120 75,290 33.9 950 28.1 50 199048 1 EXAMPLE XX A. 0.169m Ti(OBu)4 [TBT], 0.169m magnesium turnings, and 0.029m A1C13"6H?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 with vigorous effervescence originating with gas evolution at the surface of the magnesium. The solution 10 took on a blue coloration and, with smooth refluxing to 122°C. formed a dark blue-black liquid with some remaining magnesium. At 125°C., all the magnesium metal disappeared, the solution exhibiting a slight green tint. The reaction was terminated, and a dark blue black liquid and green pre-]_5 cipitate 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 Al/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 42°C. 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 and a brown precipitate, was 25 isolated. (XX B).

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

D. Reaction products XX B AND XX C were employed with triethylaluminum co-catalyst (45 ppm Al) in the poly- merization of ethylene (10 mol %) with isobutane diluent at 190°F. and hydrogen as indicated. The runs were terminated 51 199048 1 after 60 minutes, with results indicated in Table V, as follows: 52 199048 l H2 ^ Catalyst psiq XX B 6 0 120 XX C 60 120 TABLE V PE Prod mole g PE/q Ti/hr 406 84,580 542 75,280 245 54,440 183 34,860 Resin Properties MI HLMI HLMI/MI 17.2 517 30.1 54.9 1413 25.7 4.11 129 31.4 26.2 801 30.5 199048 1 EXAMPLE XXI A. 0.153m Ti(OBu)4 [TBT], 0.153m Mg° turnings and 0.026m NiCl2"6H20 were combined with 61.75 pts. of octane in a stirred reaction vessel equipped with an electric heating ■ mantle. With heating to 44°C. 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 102°C. (15 minutes 10 reaction) the reaction system turned a light muddy brown color. Vigorous effervescence continued with darkening of the brown color until at 126°C. (75 minutes) all the magnesium had disappeared, and the reaction was terminated. The reaction product (XXIA-1) was a hydrocarbon soluble dark 15 brown liquid and a small amount of a fine precipitate.

In a second run 0.149m TBT, 0.149m Mg, and 0.051m NiCl?-6H,,0 were combined in octane in the same manner. Mg metal disappeared at 115°C., 120 minutes, and the reaction resulted in a dark brown black hydrocarbon soluble liquid, 20 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 (0.0137m Ti) was placed in a reaction vessel with hexane diluent, to which iBuAlC^ (0.0411m Al) was added dropwise, at a rate of 1 drop/2-3 sec. to 28°C., and 1 drop/sec. to a peak temperature of 39°C. After completion of addition the vessel contents were stirred for 30 minutes, and the reaction product, a dark red brown liquid and a dark grey precipitate, isolated. (XXIB-I).

The same reaction product (XXIA-1) was combined with ethyl aluminum chloride in the same manner, at a 3/1 199048 1 Al/Ti 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 1/1/0.34) was combined 5 with iBuAlClj, at a 3:1 Al/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 iBuAlC^ at a 6:1 Al:Ti 10 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). 199048" i 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 5 color change was from deep brown yellow to dark brown with gas evolution, and thence through a grey brown to dark blue black upon consumption of magnesium, in a reaction occurring over a period of 6 hours. (XXIIA). aluminum chloride in the manner of Example XXIB at a 3:1 Al/Ti molar ratio. A red brown liquid and red brown precipitate was recovered. (XXIIB).

B. Reaction product XXIIA was combined with ethyl \ •~s 199048 1 EXAMPLE XXIII Example XXIIA was repeated, with the reactants supplied in the molar ratio 1/0.75/0.128. The dark brown 5 reaction product contained 5.9% Ti, 2.2% Mg and 0.97% Ni.

The reaction product was then treated with isobutyl aluminum chloride at an Al/Ti molar ratio of 3/1. 57 199048 1 EXAMPLE XXIV A series of TMgNi catalysts, prepared as set forth in Examples XXIB and XXIIB, were employed as catalyst com-5 ponents in the polymerization of ethylene (190°F., 10 mol % ethylene, triethyl aluminum about 45 ppm calc as Al, as indicated) with the results set forth in Table VI, as follows: 1 TABLE VI H„ Productivity Catalyst psig g PE/g Ti Hr Resin Properties MI HLMI HLMI/flli XXIB-3 60 120 90,750 104 ,980 9. 55 24.6 270 683 28 27.8 60 120 111,940 112,260 0.29 3.1 .7 119 36. 8 38.9 XXIB-4 60 120 59,790 62 ,720 0.25 1.0 . 9 43.6 43.6 43.6 XXIIB 60 120 57,890 64,740 66 13 54.9 183 33. 1 29.8 XXIB-2 60 120 238,670 271,560 0.65 6.7 19.5 188 . 2 28.1 XXIB-5 175,000 Low Runs at higher levels of hydrogen were extremely rapid, resulting in polymer buildup requiring termination of runs. 19904 1 EXAMPLE XXV A. TBT, Mg° and MgSiFg'6H20 were combined in octane in a heated reaction vessel equipped 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 employed with TEA to provide about 45 ppm Al under standard conditions for polyethylene polymerization (190°F, 60 psig H2) producing resin at 107,500g 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 170°F., 30 psi H2 from the ethylene/butene-1 feed. The resulting resin had a density of .9193, MI 1.91, HLMI 60.8 and MIR 31.8. 60 199048 l 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 10 conditions for a period of time sufficient to complete addition with stirring of reactant, for 10 to 30 minutes after occurence of peak temperature (where applicable, TMMg solid and liquid components were intermixed into a slurry and employed in that form). Reactants and reactant propor-15 tions are set forth as follows: 199048 Catalyst Component, mol ratio Ti/Mg/MgCl2'6H20 (H20) 1/0.65/0.11 (0. 66) 1/0.65/0.11 (0. 66) 1/0.65/0. 11 (0.66) 1/0.65/0.11 (0.66) 1/0.65/0.11(0.66) 1/0.65/0.11(0.66) 1/0.65/0.11(0.66) 1/0.65/0.11(0.66) 1/0. 65/0. 11 (0. 66) 1/0. 75/0. 128 (.768) 1/0.75/0.128(.768) 1/0. 75/0. 128 (. 768) 1/0 . 75/0 . 128 (. 768) 1/0. 75/0. 128 (.768) 1/0. 75/0. 128 (.768) 1/0.75/0.128 (.768) 1/0.75/0.128(.768) 1/0.75/0.128(.768) 1/0.75/0. 128 (.768) 1/0. 75/0. 128 (.768) 1/0. 75/0. 128 (.768) 1/1/.17(1.02) 1/1/.17 (1.02) 1/1/. 34 (2.04) 1/1/.34 (2.04) 1/1/0.51 (3.06) 1/1/0.51 (3.06) 2/1/0.17 (1.02) 2/1/0,17 (1.02) 2/1/0.34(2.04) 2/1/0.34(2.04) 3/1/0.51 (3.06) 3/1/0.51(3.06) Halide Activator Mol Ratio Bu AlCl, 1 i Bu AlCl, Bu1AlCl, 1 i Bu AlCl EtAlCl„ 2 EtBCl EtBCl SiCl, 4 SiCl .

EtAlCl, Et A12C13 BU A1C12 Bu1A1C12 EtBCl (CH3)2SiCl2 (Ch3)3SiCl (Ch3)2SiHCl SiCl, 4 SiCl, 4 TiCl, 4 TiCl, 1 ^ Bu A1C12 EtAlCl„ Bu AlCl, 1 * Bu AlCl, 1 " Bu AlCl, 1 ' Bu AlCl, 1 * Bu AlCl, 1 i Bu AlCl, 1 Bu AlCl, 1 Bu AlCl, 1 A Bu AlCl, 1 ^ Bu AlCl, 2/1 Al/Ti 3/1 4/1 6/1 3/1 1.25/1(B/Ti) 3/1 (B/Ti) 3/1 (Si/Ti) 6/1 (Si/Ti) 3/1 3/1 3/1 6/1 3/1 (B/Ti) 6/1 (Si/Ti) 6/1 (Si/Ti) 6/1 (Si/Ti) 3/1 (Si/Ti) 6/1 (Si/Ti) 1.5/1 (Ti/Ti) 3/1 (Ti/Ti) 3/1 3/1 3/1 6/1 3/1 6/1 3/1 6/1 3/1 6/1 3/1 6/1 199048 1 EXAMPLE XXVII A. Catalyst samples activated with Bu^AlC^ (3:1 Al/Ti) were employed in a series of polymerization runs, 5 with results set forth in Table VII as follows: • • • • - 35 ro VJl ro o VJl TABLE VII H O ui • H Ti/MgCl* 6H„0 (molar ratio) (ps£g) Productivity Resin Powder Properties (molar ratio) (g PE/g Ti-hr.) MI HLMI HLMI/MI 1/1/0.17 .9 60 42,870 1.7 61 . 9 120 49,102 12.2 348 28.5 1/1/0.34 2.9 60 63,385 3.8 135 .5 120 43,655 .7 519 33.0 2/1/0.34 .9 60 57,510 2.5 81 32.3 120 54,200 12.5 452 36.2 3/1/0.51 .9 60 53,975 2.4 89 37.1 120 56,560 13.2 430 32.6 1/0.75/0.128 7.8 60 124,930 .3 179 33. 8 120 116,990 22. 8 630 2 7.6 CT, UI 1/0.65/0.11 9.1 60 76,785 8.1 245 . 2 120 61,550 44.5 1300 - 2/1/0.17 11.8 60 138,820 2. 25 67.3 29. 9 120 89,900 17.4 491 28. 2 Reactor Conditions Diluent - Isobutane Temperature - 190°F.

Hydrogen - as indicated Co-catalyst - triethylaluminum (45 ppm Al) Catalyst - Ti(OBu).-Mg-MgCl_'6H_0 reaction product activated with Bu1AlCl? (3:1 Al/Ti) Ethylene - 10 mol I Run Time - 60 minutes <o OO 199048 As may be seen from a comparison of Ti/MqC^*6H20 molar ratio, peak melt index is observed at a 9:1 ratio (1.5:1 Ti/H20).

B. In the following additional runs the effect of Al/Ti ratio in the activated TMMg (molar ratio 1/0.65/0.11) catalysts was explored in the polymerization of ethylene. Results are set forth in Table VIII as follows: LO VJl uj ro o UI ro o TABLE H H UI O VIII ui H Activating Activating Compound/Ti H2 (psig) Productivity Resin Powder Properties Compound (molar) (g PE/g Ti-hr) MI HLMI HLMI/MI Bu1AlCl2 2/1 60 120 54 , 285 45,670 16.8 51 489 1436 29.1 28.2 BU1A1C12 3/1 60 120 76 ,785 61,550 8.1 44.5 245 .2 Bu1A1C12 4.5/1 60 120 66,410 67,255 7.7 35.5 257 1119 33.4 31.5 BU1A1C12 6/1 60 120 43,830 44,370 2.7 15.0 105 495 39 33 EtAlClp 3/1 60 120 60,790 97,310 7.0 39 214 .6 EtBl2 3/1 60 120 94,755 56,290 3.7 21.5 128 616 34.6 28.6 EtBCl 1.25/1 60 120 34,300 27,290 3.5 18 105 560 31 <n Ui Reactor Conditions Diluent - Isobutane Temperature - 190°F.

Hydrogen - as indicated Co-catalyst - triethylaluminum, (45 ppm Al) Catalyst - Ti(OBu)_-Mg-MgCl_'6H_0 reaction product, activated as above. Ethylene - 10 mole % Run Time - 60 minutes CO CO QO 199048 1 C. In a further series of experiments, employing a TMMg catalyst at 1/0.75/0.128 molar- ratio, the effect of activating agent was analyzed, with results set forth in Table VIX as follows: u> UI (jO O ro ui ro o ui H O UI Reactor Conditions TABLE VIX Activation Agent Bu1AlCl„ Mole Ratio Cl/Ti (psjg) 60 120 Productivity (g PE/g Ti-hr) 124,930 116,990 Resin Powder Properties MI HLMI HLMI/MI .3 22.8 179 630 33.8 27.6 EtBCl. 60 120 94,850 80,060 3.2 29.0 103 32. 2 Me2SiCl2 12 60 120 24,860 21,120 2.44 10.4 58.5 259 24.0 24.9 Me^SiCl 60 120 32,225 28,770 7.25 16.3 214 460 29.5 28.2 Me2SiHCl 60 120 33,010 18,140 1.94 7. 29 51.7 198 26.6 27.2 cr\ -J SiCl, SiCl, TiCl, 12 60 61,210 8. 86 210 23.7 120 55,435 . 2 611 24.2 24 60 145,830 0.99 29.0 29.3 120 71,670 7. 96 229 28.7 6 60 31,950 1.8 61.7 34.2 120 24,555 8.8 297 33.7 Diluent - Isobutane Temperature - 190°F.

Hydrogen - as indicated Co-catalyst - triethylaluminum, Ethylene - 10 mole % Run Time - 60 minutes (45 ppm Al) CO CO OO 68 199048 1 D. Larger scale polymerization runs were con ducted at 160°F. 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 5 as a comonomer, utilizing varying butene-1 feed, activators and activator ratios. Results are set forth in Table X as follows: u> VJl uo o ro UI Run No.

A B C D E F G H I J Ethylene Feed (Wgt. % monomer in reactor) 4.41 2. 39 3.02 2. 43 2.32 2.34 1.75 Butene-1 Feed (Wgt. % Total monomer) 7.55 7.14 11.56 11. 59 14. 66 . 77 17.82 TABLE X H /Ethylene (mol ratio) Pellet MI HLMI/MI Density Annealed Activator .12 12.7 1300 0. 948 6/1 Al/Ti iBuAlC^ .06 1.9 40 0.939 6/1 Al/Ti iBuAlCl2 .05 1.0 41.2 0.934 6/1 Al/Ti iBuAlCl2 .07 3.2 28.5 0.939 3/1 Al/Ti EADC — 3.9 28.6 0.934 3/1 Al/Ti EADC — 0.6 33. 4 0.931 3/1 Al/Ti EADC . 03 0.7 . 2 0. 929 3/1 Al/Ti EADC . 03 0.6 31.3 0 . 928 3/1 Al/Ti EADC — .8 29.7 0. 935 3/1 Al/Ti EADC . 06 1.1 43. 9 0.924 6/1 Al/Ti EADC CO CD O eo i * 199048 1 The resin batches collected as noted above were stabilized with 100 ppm calcium stearate and 1000 ppm Irganox 1076 ; characterized by conventional tests; and converted into blown film in a 1 1/2" Hartig extruder (60rpm 5 screw; 3" die at 0.082" die gap; cooling air 37-40°F.) and further tested, all as set forth below in Tables XI and XII: u> ui uo o ro ui ro o ui H O UI TABLE XI Linear Low Density Resins Resin Properties A B C D E F G H I J Eta 1000 x 10 3 1.56 3.67 4.36MF 3.56 3. 35 3.95MF 4.00MF1 3.90MF1 2. 89 4.15 Die Swell @ Eta 1000 146 164 — 152 150 — — — 146 165 Tensile Strength, psi @ 20"/min 3960 1790 1850 1810 1700 2250 3420 3310 1660 1910 Yield Strength, psi @ 20"/min — 3210 2770 3220 2830 2670 2480 2400 2910 2050 Elongation, % @ 20"/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 2 Tensile Impact, ft-lb/in 47.7 94.6 130 88.3 79.2 213.7 267.4 299.0 96. 6 181.9 Vicat, °C. 115 115 114 115 114 112 112 110 109 100 LTB, °C. -76 -76 -76 -76 -76 -76 -76 -76 -76 Shore Hardness, "D" 61 58 57 59 58 57 57 56 58 52 MF = at least some melt fracture, indicating need for optimization of conditions for actual extrusion.

CO CO oo ijo lo ro VJl o VJl Film Thickness, mils Haze, % Gloss, 60°, % Tensile Strength, psi MD TD Yield Strength, psi MD TD Elongation, % MD TD Elmendorf Tear, g/mil MD TD Tear ASTM D1004, lb/mil MD TD Tensile Modulus, psi MD TD ro o VJl VJl TABLE XII Linear Low Densitv Resins Blown Film Properties B 2.0 45.5 3.3 3740 2940 2610 2840 750 830 16 17 1. 07 0.97 72350 92930 1.0 30.0 4.4 4130 2070 2550 2400 560 320 6 346 1.12 0.97 68440 87910 2, 28. 4. 5620 3320 2390 2620 670 780 21 177 0.94 0.94 60130 74340 1.0 32.2 3.9 6060 4410 2250 2330 670 880 21 492 0.74 0.82 55250 67800 2.0 18.3 7.1 5500 4900 2180 2410 700 550 35 256 0.99 0.96 49830 68520 -j KJ CO to GO UJ UI uo o Dart Drop, gms (mil Dynamic Ball Burst cm-kg (mils) Draw down mils Melt Temp., °F.

Head Pressure, psig Cooling Air Temp., ro o UI H O UI TABLE XII (CONT'D) Linear Low Density Resins Blown Film Properties 72(2.2) .5 (1.0) 92 (2.2) 45 (1.3) F 81 (2.0) 2.44 1.40 (1.0) 3.94(2.2) 2.48(1.2) 4.26 (2.0) 0. 25 0.2 331 3400 330 3400 359 3850 359 3850 405 4450 -j u> 38 38 39 39 38 CO CO QO IjO UI UJ O Film Thickness, mils Haze, % Gloss, 60°, % Tensile Strength, psi Yield Strength, psi Elongation, % Elmendorf Tear, g/mil Tear ASTM D1004, lb/mil Tensile Modulus, psi w ro H H ui o ui o ui TABLE XII (CONT'D) Linear Low Density Resins Blown Film Properties G H 2.0 1.0 2.0 1.0 2.0 1.0 24.4 22.6 24.4 18.9 24.5 20.0 .6 5.6 5.6 6.1 6.0 6.0 5710 6930 5710 7700 4340 6180 5250 5290 5250 5010 3290 3610 1960 1960 1960 2010 2070 1930 2210 2090 2210 2020 1840 1640 680 590 680 520 670 610 850 830 850 810 830 860 80 53 80 32 80 99 277 429 277 559 366 503 1.03 0.98 1.03 1.25 0.83 0.86 0.95 1.21 0.95 1.14 0.80 0.80 46200 46585 46200 42940 37450 35360 56590 54880 56590 50343 44770 48370 -j to to QO U) UI (JO O ro ui Dart Drop, gms (mils) 109 (2.1) Dynamic Ball Burst cm-kg (mils) 6.50(2.3) O <&/ o / > / £*! Drawdown, mils Melt Temp., °F. Head Pressure 405 4500 Cooling Air Temp. °F. 38 ro M H o ui o ui TABLE XII (CONT'D) Linear Low Density Resins Blown Film Properties H 38 (1.0) 109 (2. 1) 36 (1.0) 85 (2.5) 43 (1.2) 3.11(1.0) 6.50(2.3) 3.14(1.0) 6.62(2.4) 3.62(1.2) 0.3 — — — 0.3 405 406 405 360 360 4500 4800 4800 3900 3900 ^ 38 37 37 40 40 CO OO 199048 1 E. In further large scale polymerizations con ducted in a similar manner employing TMMg catalyst (slurry, separated from supernatant liquid and hexane washed) at molar ratio 1/0.75/0.128 (3/1 Al/Ti, EADC), hexene-1 was fed 5 to the reactor as a comonomer with ethylene, and then butene-1 was substituted providing, as followed by off-gas analysis, ethylene/butene-l/hexene-1 copolymers and ter-polymers in the course of the operation. Results are set forth in Table XIII, as follows: • • LO UI U) o ro ui Comonomer Density Hexene 0.9339 *7 / -V/ y /-^/ N. r Sj , /W Hexene/Butene Butene 0.9293 0.9157 0.9148 0.9148 0.9135 rv> H H o ui o vn TABLE XIII MI HLMI HLMI/MI 0.83 26.9 32 0.73 23.9 33 0.94 31.4 33 0.70 25.2 36 0.70 25.2 36 0.94 29.9 32 -j -j CO CO OO 78 199048 EXAMPLE XXVIII TMMg catalyst prepared in accordance with the Examples and activated with isobutyl aluminum chloride (3/1 Al/Ti) was also employed to produce other copolymers at varying comonomer preload, isobutane diluent, 170°F. reactor temperature, 30-40 psig and TEA to provide 60 ppm Al, with results as follows: Ethvlene/3-Methylbutene-l MI MIR Density 1.25 27.4 0.9488 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 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 Isobutylene 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 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. 79 199048 1 The following comparative experiments were also conducted: COMPARATIVE EXAMPLES A. In the same reaction vessel used in other preparations TBT, Mg° and anhydrous MgCl2 were combined in octane at a molar ratio of 2/1/0.34 and heated to reflux for 15 minutes without evidence of reaction. The anhydrous MgCl2 remained undissolved. See also Example IB above.

B. To the same system, an amount of free water equivalent to an Mg°/MgCl2*6H20 ratio of 1/0.34 was added in bulk, but no change was evident.;C. TBT and Mg° were combined in a 2/1 molar ratio in octane and heated to reflux. While the yellow color;15 became somewhat more intense, no evidence of reaction occurred.;D. To the system C above, an amount of free water equivalent to an Mg/MgCl2'6H20 ratio of 1/0.34 was added. A small amount of light yellow precipitate was formed eviden-;20 cing hydrolysis of the titanium compound, but the magnesium remained unreacted.;E. TBT and MgCl2*6H20 were combined in octane at a molar ratio of 1/0.34 and heated to reflux. 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 heating to reflux over only 16 minutes. At a molar ratio of 1/1.17 go foaming and formation of a thick cream colored gel terminated reaction after 45 minutes. Compare Example VII, above. \99043

Claims (20)

WHAT WE CLAIM IS;

1. A process for the preparation of an inter-metallic compound which comprises reacting , a polymeric transition metal oxide alkoxide with a 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 produced by partial hydrolysis of the transition metal alkoxide.

3. A process according to Claim 2 wherein the hydrolysis is effected with an aguo complex as the water source.

4. A process according to Claim 3 wherein water is provided in the form of a hydrated salt such as a hydrate of a salt of aluminium, cobalt, iron, magnesium or nickel.

5. A process according to Claim 3 wherein water is provided in the form of a hydrated oxide, preferably silica gel.

6. A process according to any of Claims 3-5 wherein the molar ratio of transition metal to water is from 1:0.5 to 1:1.5.

7. A process according to any of Claims 1-6 wherein the reducing metal is magnesium, calcium, zinc, aluminium or mixtures thereof.

8. A process according to any of Claims 1-7 wherein the transition metal is titanium or zirconium.

9. A process according to Claim 8 wherein during the formation of said intermetallic compound the transition metal and the reducing metal are present in a molar ratio of from 0.5:1 to 3:1.

10. A process according to any of Claims 1-9 wherein % the reaction is initiated by beating to a temperature of more than 50°C.

11. A process according to Claim 10 wherein heating is continued until up to the stoichiometric amount of reducing metal is consumed.

12. A process according to any of Claims 1-11 wherein the product is further reacted with a halide activator.

13. An intermetallic compound comprising the reaction product of a polymeric transition metal oxide alkoxide and a reducing metal of higher oxidation potential than the transition metal.

14. The intermetallic compound of Claim 13, wherein the transition metal is titanium or zirconium.

15. The intermetallic compound of Claim 12 or 14, wherein the reducing metal is magnesium, c&lcium, zinc, aluminium or mixtures thereof.

16. The intermetallic compound as in any of Claims 13-15 wherein the polymeric transition metal oxide alkoxide is the product of the controlled partial hydrolysis of a titanium alkoxide.

17. The intermetallic compound as in any one of claims 13-16 further characterized in that during its formation "the transition metal and reducing metal are present in a molar ratio of from 0.5:1 to 3:1

18. The intermetallic compound as in any of Claims 13-17, further reacted with a halide activator.

19. A process for the preparation of an intermetallic compound substantially as specifically described herein with reference to any one of the Examples. pecifically described herein with reference to any one of

20. An intermetallic compound substantially as he Examples. nation/! :mical corporation by thei bau3kxn. son & carey