CA1206353A - Intermetallic compounds of polymeric transition metal oxide alkoxides - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

Process for the preparation of intermetallic compounds useful as catalyst precursors for interreaction with halide acti-vators to provide a catalyst component for the polymerization of alpha olefins. The process comprises reacting a polymeric trans-ition metal oxide alkoxide with the transition metal being titanium or zirconium and a reducing metal of higher oxidation potential than the transition metal and wherein the molar ratio of transi-tion metal to reducing metal is from about 0.5:1 to about 3:1.

Description

~ ~ ~ ~ 3310/3415 b-j I

1 INT~IET~r.I,~ C()MPOTJ~InS ~F P~I,Y~RI~
TRANSITI~M METAT. ~XIDE AI,K~XIDES

This invention relates to intermetallic compounds of transit:ion metal a].koxides, and processes for their pro-duction. More particularly, the inventlon affords catalyst precursors for lnterreactlon wi.th halide activators to pro-vide a catalyst component adapted for the polymerlzation of alpha olefins.
Polvet.hylene, produced bv solution or slurry processes at lower pressures or in autoclave or tubular reactors at hi~her pressures, has heen an object of commer-cial Production for many years.
Recent interest has centered on linear low densitv polyethylene resins characterized by linearity and short chai.n branching afforded by alkene comonomers, and offerinq narrow molecular weight distrihution, improvecl strenqth properties, higher melt viscosity, hiqher softening point, improved ESCR (Environmental Stress Crack Resistance) and improved low temperature brittleness. These and related properties provide advantaqes to the user in such applica-tions as hlown film, wire and cable coating, cast film, coextrusion, and injection and rotational moldinq.
The linear olefin polymers have typically heen ~roduced using catalysts of the qeneral type disclosed by Zieqler, thus compri.sing a transition metal compound, usually a titanium halide admixed ~ith an organometallic compound such as alkyl aluminum. The transition metal component may be activated by reaction with a halide pro~
moter such as an alkyl aluminum halide. A~ong the improved catalysts of this tvpe are those incorporatinq a maqnesium component, usually by interaction of magnesium or a compound .. ~ .. . . .

2 ~Læ~3~i3 1 thereo~ with the transition metal component or t~e or~ano-metallic component, as by milling or chemical reaction or association.
There is also interesk in producinq intermediate to high density resins of modi~ied characteristics emploving coordination catalysts of this type. In particular, resins of broader molecular weight distribution and higher melt index are sought.
According to the presel~t ln~7entionv transition metal-containing intermetallic compounds are prepared by the reaction of a polvmeric transition metal oxide a]koxide with at least one reducing metal, i.e,l a metal having a 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 hydrolvsis of the alkoxide; or the polymeric oxoalkoxide mav be provided by an in situ reaction, e.g~, hvdrolysis 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 ma~nesium halide hexahydrateO
Transition metal alkoxides, particularly titanium alk~xides, are known for their colligative properties in organic solvents, and their sensitivity to hydrolysis. It is reported that the hydrolysis reaction proc~eding from the 3o oligo~eric, usuallv trimeric titanium alkoxides results in polymeric titanium oxide alkoxides, qenerallY expressed as t

3 ~2~

1 Ti(OR)4 + n~2~ -~Tion(oR)~ ~n + ~n R~
Condensat.ion reactions mav also occur especially at elevated temperatures to structures involvinq primary metal-oxygen-metal bridges such as:
~R OR
OR - Ti ~ O - ~i - nR
~R ~R
which may in turn partici.pate in or constitute precursors for hydrolysis reaction.
These polymeric titanium alko~i.des or oxoalkoxides (sometimes also re~erred to as u-oxoalkoxides! may be repre-sented bv the series ~Ti3(x+l)o4x( )4(x+3) 1,2,3,..., the structure reflecting the tendencv of the metal to expand its coordination beyond its primarv valency coupled with the ahilitv of the alk~xide to bridqe two or more metal atoms.
Regardless of the particular form which the alkoxi.de is visualized to adopt, in prastice it is sufficient to recoqnize that the al.koxide oliqomers form upon controlled hvdrolysis a series of polymeric oxide a].koxides ranging from the dimer through cyclic forms to linear chain polymer of up to infinite chain length. More complete hydroly.si~, on the other hand, leads to precipita-tion of insoluble products eventuating, with complete 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 hvdrolysis products. The hydrolysis reaction can be carried out separately, and the products iso].ated and stored for further use, but this is inconvenient especially in ~iew of the prospect of further hydrolysis t hence the preferred

4 ~ 3S~

1 practice is to generate these materials in the reaction medium. Evidence indicates that the same hydrolysis reaction occurs in situ.
The hvdrolysis reaction itself may be controlled directl~ bv the quantity of water whi.ch is suPplied to the transition me-tal alkoxide and the rate of addi-tion. ~ater must be supplied incrementallv or in a staged or sequenced manner: bulk addition does not lead to the desired reaction, effecting excessive hydrolYsis, with precipitation of insolubles. ~ropwise addition is suitable as is the u.se of water of reaction, but i.t i.s found more convenient ~o Pro~ide the water as water of crystallization, sometimes referred to as cation, anion, latti.ce or zeolitic water.
Thus, common hydrated metal salts are usually emploved, where the presence of the salts themselves are not deleterious to the system. It appears that the bonding provided bv the coordinated sphere of water in a hydrated salt is adapted to control release and/or avai.lability of water, or water related speci.es -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 se].ected relative to catalyti.c performance. /It is helieved without limitation that the stereoconfiquration of the paxtially hvdrolvzed transition metal alkoxide determines, or contri-butes in part to the nature, or result of the catalvtic action of the activated catalyst component.~
In general, it has been found sufficient to 30 pro~Ti.de as little as 0.5 moles of water per mole of transition metal. Amounts of uP to 1.5 molec are suitable with higher amounts up to ~0O moles being operable whenever ~L~r~9~-J~

1 precipitation of hydro]vsis products from the hydrocarbon solvent medium mav be avoided. This may be achie-ved in principle by reducing the rate of addition and ceasin~
addition upon first evidence of precipitation. ~hile it is believed that the reaction is essen~iallY equimolar, a certain excess of water is appropriatelv employed in some cases, as is customarv.
It will be understood that the stereoisomeric form, chain len~th, etc. of the h~drolvsis product mav be some~hat altered with the elevated temperature required bv the ensuing reaction with the reducing metal, and in situ processes likewise will affect equilihria through the mass action effect. Likewise, the cogeneration of alkanol may affect equllibria, reaction rates, etc.
The hydrolysis reaction proceeds under ambient conditions of pressure and temperature, and requires no special conditions. A h~drocarbon solvent mav 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 materia] is stable under normal storage condi-tions, and can be made up to a suitahle concentration level as ~esired, simplv by dilution with hydrocarhon solvent.
The polymeric transition metal oxide alkoxides are reacted with a reducing metal havinq an oxidation potential higher than the transition metal. Preferably a polymeric titanium oxide alkoxide ls 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-ence to electropotentials to minimize side reactions, asknown in the art; and in general to assure preferred levels of activity for olefin polymeriæation, magnesium values are 6 31.2~1~3~3 l supplied to the system by appropriate ~election of reducinq meta]/hydrated metal salt.
In the preferred embodiment (to which i]lustrative reference is made in the following text, as a matter of con-venience), titanium tetra n-butoxide (TBT) is reacted with magnesium turnings and hydrated metal salt, most preferably magnesium chloride hexahydrate, at a temperature of 50-150C., in a reaction vessel under autogenous pressure.
TBT may constitute the reaction medium, or a hydrocar~on solvent may be used. Ti/Mq molar ratios mav varv from ,:0.1 to l:l although for the most homogeneous reaction system a stoichiometric relationship of Ti-V to Mq of l:l i5 pre-ferred, with an amount of hydrated metal salt to sup~ly during the reaction about 1 mole of water per mole of Mg.
The hydrocarbon soluble catalvst precursor com-prises predominently Ti values in association with Mg values, in one or more stereoconflguratlon comPlexes believed to constitute prlncipally oxygenated species. Some evidence of mixed oxidation states of the ti-tanlum values suggests an interrelated system of integral species of Ti TiIII, and Ti I values perhaps in a quasi-equilihrium relation at least under dynamlc reaction conditions. The preferred precursor is believed without limitation to incor-porate (Tl-O-Mg) bridging structures.
The intermetallic compounds have speclal interest as catalyst precursors, in support or unsupported systems, for isomerization, dimerizatlon, oligomerization or poly-merization of alkenes, alk~nes or substituted alkenes in the presence or absence of reducing agents or acti~7ators, e.g., organometallic comPounds of Group IA, ITA, IIIA, or IIB
metals.

3~

7 ~ ~ r3t''~1 1 In the preferred utiliæation of such precursors, they are reacted with a halide actil7ator such as an alkvl aluminum halide and combined with an orqanometallic compound to form a catalvst svstem ada~ted ~articularly to the pol~-merization of ethvlene and comonomers -to polvethylene resins.
The transition metal ~omponent is an alkoxide, normally a titanium or æirconium 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 liquid under amhient conditions and the reaction temperatures for ease of handling, and to facilitate use is also hvdrocarbon solub]e.
It is generallv ~referred for facility in conducting the related hydrolvsis reaction to employ transi-tion metal compounds which comprise only alkoxide substi-tuents, although other substituents may be contemplated where they do not interfere with the reaction in the sense f significantly modifyinq performance in use. In ~eneral, the halide-free n-alkoxides are employed.
The transition metal component is provided in the highest oxidation state for the transitlon 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 tetraethoxide~ as ~lell as the related compounds incorporating one or more alkoxv radicals including n-propoxy, iso-propoxv, n-butoxy, isobutoxy, secbutoxv, tertbutoxy, n~pentoxy, tertpentoxy, tert-amyloxy, n-hexvloxv, n-heptyloxy, nonvloxy and so forthe -~L2~1~4~

1 ~ome evidence suggests that the rate of hydrolysis of the normal derivatives decreases wlth increasing chain len~th, and the rate decreases with molecular complexitv viz. tertiarY, secondarv, normal, hence these considerations ma~ be taken into account in selecting a preferred deriva~
tive. In ~eneral, titanium tetrabutoxide has been found eminently sultahle for the practi.ce of the present inven-tion, and related tetraalkoxides are ].ikewise preferred. It wlll be understood that ~ixed alkoxides are per-fectlv suit-able, and may be employed where convenientlv available.Complex titanium alkoxides someti.mes inclusive of other metallic components may also be employed.
The reducing metal is supplied at least in part in the ~ero oxidation state as a necessarv element of the reaction svstem. A convenient source is the familiar turnings, or ribbon o.r powder. As supplied commercially, these materials may be in a passivated surface oxid.ized 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 hydrocarbon diluent, or mav be added directlv to the reactor.
Whether in the case of the in sitll preparati.on tor for independent preparation of the polymeric transitlon metal alkoxide), the source of water, or water related species is provided, whereby quantities o:f water are released or diffused or become accessible, as the case mav be, in a delayed rate controlled manner during the reaction.
3o As aforesaid, the coordination sphere afforded by a hvdra-ted metal salt has been found suitable :For the purpose; but other sources of water in the same proportions are also ii3~

1 useable. Thus, calcined silica gel free of other active cons-tituent~ but containing contro]led amounts of bound water may be employed. Tn 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 halides, nitrates, sulphates, carbonates and carboxylates of sodium, potassium, calcium, aluminum, nickel, cobal-t, chromium, lron, ma~ne~ium, and the like.
The interaction of these components is conven-iently carried out in an enclosed reactor, preferablv coupled with reflux capacitv for volatile components at the elevated temperatures produced in the reaction vessel.
Autogenous pressure is employed, as the reaction proceeds smoothlv under ambient conditions" with heating ~o 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 homoqeneous reaction system.
Usually a hvdrocarbon solvent such as hexane, heptane~ octane, dec~lin, mineral spirits and the like is also used to facilitate intermixture of components, heat transfer and maintenance of a homogeneous reaction svstem.
Saturated hydrocarbons are preferred, having a boiling point in the range of 60 to 1~0C. 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 3o volatile components form a~eotropes with the so]vent, or if the components are employed neat, constitute the source of re~lux, but in either case it is preferred, at least to -;3r ~

l effectuate the reaction through intermediate stage.s with appropriate reaction times, to return volatiles to the reactlon zone. Thus, butanol is generated when the titanium component is titanium tetra n-butoxide forming an azeotrope with the h~rdrocarbon 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 e~tent be a matter of choice within a broad range, depending upon the speed of reaction convenientl~7 to be conducted. It has been found that the reaction system (constituted bv the liquid transitlon metal component, dissolved hydrated metal sa]t, reducing metal particles and sol~rent, where desired) evidences visihle gas generation at about 60-70C.
suqqesting an initiation temperature or acti.vaticn energy level at about 50C~ which therefore constitutes the minimum necessary temperature for reaction of the po1.~rmeric oxide alkoxide with the reduclng metal. The reaction is somewhat 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 completion of the reaction is evidenced by consumption of visible metal and/or attainment of the reflux temperature for the pure solvent wi.thin a period of as li.ttle as 30 minutes to 4 hours or more. Such temperatures ma~r reach 140-190C. and of course higher temperatures miqht be 3o imposed but without apparent benefit. It ic most convenient to operate within the range of 50-150C., preferably 70-140C. ~n the absence of sol~.rent, the upper limit will ~%~ ;i3 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, wi~h exotherm, that accompanies commencement of gas e~Jolution. 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 liqht colored solutions immediately turn greyish, then rapidly darker to blue, sometimes violet, usually blue black, sometimes with a green:ish tint.
Anal~sis of the gas evidences no HCl; and is essentially H2.
Following the rapid color change some deepening of color occurs during a gradual increase of -tempera-ture, with con-tinuinq gas evolution. In this stage, the alkanol corres-ponding to the alkoxide species is qenerated in amount sufficient to suppress the hoiling point of the solvent~ and appears to be gradually consumed in a rate related manner `along with the remaining reducing metal.
The reaction product is hydrocarbon soluhle at least in part, and is maintained in slurry form for conven-ience in further use. The viscous to semi-solid product when isolated evidences on X-ra~ diffraction analYsls an essentially amorphous character.
Molar ratios of the components may varv within certain ranges without significantly affecting the perform-ance o the catal~st precursor in ultimate use. Thus, to avoid competing reactions rendering the reaction product inconveniently qelatinous or intractable, the transition 3o 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 l to 300:1.0 or more, preferably 1/0.1-l/1. An insufficient level of reducing meta] will result in supPression of the reaction temperature such that the reflux temperature of the pure solvent remains unattained; whereas an excess of

- 5 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 commonlv is slurried with the soluble component for use, e.g., further reaction with a halide activator to form an olefin polymeri7.ation catalvst.
The amount of such insoluble ~omponent may he controlled in part hy 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/~g/~20 components have been found most adapted to the formation of a homoqeneous 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 MgCl2 6M20, an amount o 0.17 moles supplies during the reaction about 1 mole of water and this proportion up to ahout 2 moles of water, 25 provides the most facile reactions, with one or more moles of transition metal component. More generallv, the ~0 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, 3o 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.

l3 ~ ;3~3 l It is nevertheless s~ecifically contemplated without limita-tion, 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-viding such species in a regular, sec~uenced, constant orvariable rate-related manner. The same molar proportion of free water supplied at the commencement of the reaction is however whollv ineffective in initiatinq reaction at this or hiqher temperature, and results in undesirable complete hvdrolysis 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 insufficiency of water will invar-iably result in e~ces~ reducing metal remaining. Ingeneral, a modest excess of water of 10-40% is suitable to ensure complete reaction. Hiqher proportions are suitable without limitation but should be kept in relative stoichio-metric balance to the transition metal component.
The selection of aquo complexes or hvdrated metal salts where employed is essentially a matter oE the control-led availability of water it affords to the svstem. Thus, sodium acetate trihydrate is suitable, as is magnesium acetate tetrahydrate, magnesium sulphate heptahycdrate and maqnesium silicon fluoride hexahydrate. A salt of maximum degree of hvc1ration consistentlv with the controlled release afforded bv the coorclina-te bonding relationshiP is prefer-red. Most convenientlv, a hydrated maqnesium halide such as magnesium chloride hexahyclrate or magnesium bromide hexa-3o hyclrate is employed. These salts, like other hyqroscopicmaterials, even when supPlied in commercial anhydrous form contain some sorbed water, e.g., 17 mg/kg tsee U.K. Patent 1,401,708) although well below the molar quantities contem-plated in accordance with this invention. Hence anhydrous grade salts unless specifically modified for the purpose are not suitable herein.
The reaction system, as defined in the above description does not require 7 although it will tolerate 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 participate or compete in the reaction system.
No separations are necessary as at least a portion of the reaction product is soluble in the saturated hydro-carbon where employed as a solvent or provides a solvation medium such that even where a precipitate also occurs, and even after storage9 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 9 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 p~oduct, or slurry may then be used immediately, or stored for future use. Usually, for best control over molecular 1 weight characteristics, and particularly for production of low den~ity resin, onlv the hydrocarbon washed sol.id reaction product is employed as the catalyst, The halide acti.va-tor is commonly supplied for interreaction at a molar ratio of 3-1 to 6:l (aluminum, silicon or boron, relative to the transition metal.) a]though rati.os of ~:1 or more have been used successfully.
The resultant catalvst product may ~)e used directly in the polymeri7.ation reaction although it is typically diluted, extended or reduced as required to provide in a convenient feed an amount of catalyst equivalent to ~0-100 mg/transition metal, hased upon a nominal productivity of qreater than ~00,000 grn polymer/~m transition metal in continuous polvmeri~ations whic.h the present catalyst or~inarilv exceeds. Adjustments are made by the art.isan to reflect reactivity and efficiencY, ordin-ari]y by mere di]ution, and control of feed rates.
The transiti.on metal containinq-catalyst is com-bined for use in polymerization with an o:rganornetallic co-catalyst such as triethvl aluminum or triisobutt~l aluminum or a non-metallic compound such as triethylborane.
~ typical polymerizer feed thus comprises 42 parts of iso-butane solvent, ~5 pts. of ethylene, 0.0002 pts. catalyst (calculated as Ti), and 0.009 pts. co-catalyst tTEA, calcul-ated as Al.), to a reactor maintained at 650 psiq. and 160E.In general, the amount of co-catalvst, where emploved, is calculated to ranqe from between about 30 to 50 ppm ca].cul-ated as Al or B, based upon isohutane.
Examples of metallic cocatalysts include trialky]
3o aluminums, such as triethyl aluminum, triisobutyl aluminum, trinoctyl aluminum, alkvl aluminum halides, alkyl aluminum alkoxides; dialkyl zinc, dialkyl magnesium, and metal boro-~ ~D

, ~, hydrides including those of the alkali metals, especiallysodium, 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 decarborane.
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 inthe range of 100 to 200F. with applied hydrogen as desired to control molecular weight distribu-tion. Other n-alkenes may be fed to the reactor in minor proportion to ethylene, for copolymerization therewith.
Typically, butene-l- or a mixture thereof with hexene-l is employed, in an amount of 3 to 10 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-methyl-butene-1, isobutylene l-heptene, l-decene, or l-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 auto-clave 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 coordina~ion or association, or in the form of one or more inclusion or occlusion compounds, .,~

1 7~ S3 l clusters, or other interengagement under the aPplicahle conditions, the inte~rated reaction in general beinq evidenced by color change and gas evolution, probably reflective of reduction-oxidation, rearrangement ~nd association among the unconsumed elements of the reaction system .
The followinq ~xamp]es taken in conjunction with the foregoing description serve to further i].lustrate the invention, and of the manner and making and using same. All parts are by wei~ht e~cept as otherwise noted. Melt indices are measured under conditions E & F, respectively, of ASTM
D-1238-57T, for MI and HI,MI values, on powder or resin samples as .specified. HL~I/MI or MIR is melt index ratio, a measure of shear sensitivity ref].extin~ m~lecular weiqht di.stribution. Other -tests are as indicated, or as convention~1.ly conducted i.n the related arts.

3o :~LZ~ 3 A. 6.0 pts. of Ti(OBu)4 [TBT] and 4.2 ~ts. of CrC1~6H2O 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 60-70C. 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 0.3 pts. of magnesium shavings, which caused vigorous gas evolution. The cooled react,ion 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 heatinq at greater than 100C. for a half hour. Addition of ~inc dust and further heatlng at qreater than 150C. still evidenced no reaction. Substitution of maqnesium shavings also resulted in no reaction. It was concluded that the hydrated salt was a necessary component of the reaction system.

3o 1~ ~ r .ILZ~bi3 A- TBT 10~121m), CrCl3 6H2O (0.015mj and ~lg (0.0075m) were combined in a stirred reaction vessel equipped with an electric heating mantle. The chromium salt was whollv dissolved at about 60C., and reaction with the magnesium shavings was ap~arent from gas evolutlon at 85C., which was vigorous at 100C., subsiding at 116C. with some Mg remaining. After dissolution of the remaining Mq, heating was continued, to a total reaction time of 1 hour and 45 minutes. The reaction proAuct at room temperature was a dark qreen li~uid which dissolved readlly in hexane.
B. In the same manner, a reaction product was prepared in the proportions 0.116m TBT, 0.029m CrCl3 6H~O
and 0.029m Mg. A muddy green reaction product at 118C.
took on a definite bluish color at 120C. with continued gas evolution. The reaction was terminated upon the disappear-ance 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 CrC13 hH2O, 0.0145m ~g. 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 TRT, 0.0?87m CrC13 ~H2O, and 0.0144m Mg. A muddy green material evident at 114C. became blue at the Mg surface. The recovered reaction product was hexane soluble.
E. In a similar run, 0.176m TBT, 0.30m CrCl3 6H2O
3o and 0.176m Mg were reacted in oc-tane. The clear green color of the reaction at 70C. turned muddy with increasing gas evolution and darkened to almost black at 90C. The l color returned to qreen at 119C. and the reaction was terminated at 121C. with complete disappearance of the magnesium. The reaction product (6,9 wgt,%, Ti, 3.5 wgt.%
Mg, 1.3 wqt.~ Cr) was a dark o]ive green liquid and a solid of darker color (about 50:50/volume) which settled out.
~ . In vet another run in octane, the reactants were provided in the proportions 0.150m T~T, O. 051m CrC13-~H2O and 0.150m Mg. Again, -the muddv green color changed to almost black with vigorous effervescence, forming at 109 a dark blue black reaction product. (5.7 wgt.% Ti;
2.9% r~g, 2.1 wgt% Cr).

-2 1 ~J~3~i3 1 EXAMPL~ III

A. The reaction product IIE was combined in a reaction vessel with isobutvl~luminum chloride added drop-wise in proportions to provide a 3:1 Al/Ti molar ratio. Thegreen colored mi~ture changed initia],lv -to brown violet at 38C., which upon completion of reactar-t addition at 39C.
had chanqed to red brown in appearance. ~fter 30 minutes additional stirring, the reaction was terminated, the pro-duct bei,ng a dark red brown liquid and a dark brown precipi-tate.
B. Reaction product IIF was simi]arly reacted with isobutyl aluminum chloride (3.1 Al/Ti molar ratio).
The peak temperature with complete addition was 48C., but no hrown color change was evident. The reaction product was a clear li~uid and a dark grey precipitate.

~5 3o 22 ~L~n~r~

l EXAMPLF, IV

The catalyst components prepared .in Example Il~
above were employed in the pol~merization of ethylene (190F., 10 mol% ethYlene, 0.0002 pts. catalyst calculated as Ti, triethyl aluminum about 45 ppm, calculated as Al, H2 as indicated) with results se-t forth in Table I, as follows:

-3o ~ q e-TABLE I

H Prod . Re s in Prope rt ie s Catalyst~ g Pe/g Ti hr _ HLMI HLMI/MI

IIIA 60 35160 10.1 265 26.3 1~0 ~9220 18.9 618 32.

10 IIIB 60 30380 9.6 264 27 1~0 26880 3~.8 855 26.1 3o 2~l In the following Example, the catalyst component of the invention was prepared from the reactant admixture in the absence of added solvent.

EXAMP~E V

A. 0.1212m Ti (OBu)4 ~TBT~, 0.121m magnesium turnings and 0.0012m MgC12 6H20 (TBT/Mg/MgC12 6H20 =
1:1:0.01 molar) were combined in a stirred reaction vessel equipped with an electric heating man~le. The magnesium salt dissolved entirely at room temperature, forming a homo-geneous reaction mixture. The mixture was heated gradually and at 95C. gas evolution commenced on the surface of the magnesium turnings. At 140C. with reflux the bubbling had become vigorous. The solution darkened in color and the bubbling ceased at 170C., whereupon the reaction was terminated. The reaction product contained excess mag-nesium -- only about 8.5 percent charged had reacted -- and was soluble in hexane.
B. In another run, the molar ratio of MgC12 6H2O
was increased (TBT/Mg/MgC12 6H2O = 1:1:0.1 molar). The gold yellow liquid became greyish with gas evolution at 10~C., and darkened with further heating to 168C. 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.

~ ~; r 25 ~ 63~3 l The following Example shows the preparation carried out in a hydrocarbon solvent.

F.XAMPLR VI

A. 50 . 2 pts. tO. 148m) of TBT was added to a stirred re~ction vessel equipped with an electric heatin~
mantle, and 58.6 pts. octane. The magnesium turninqs tO.074m) were added, stirring commenced and then 0.0125m ~IgC12 6~20 added with heating over one minute. At 75C. (20 minutes) the magnesium salt had entirely dissolved, and at 95C. (~5 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 117~C. t35 minutes). The magnesium metal had entirely reacted within 1 hour (128-129C.) and the reaction was terminated. The dark blue reaction product, solubiliæed in octane ta small amount of a greenish precipitate remained), was calculated to contain 6.8 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 essentlally repeated except that molar ratlos of the reactants were modified with results as follows:

3o Ti/Mg/MgC12 6H20 Ti/Mg . (Molar ) Notes Mol Ratlo _ _ 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%
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 unreacted Mg 1/1/0.17 0.85 Dark hlue black liquid, 6.6 wgt% Ti, 3.9 wgt% Mg values (calc) 1/1/0.34 0-75 Dark blue black liquid, 6.7 wgt% Ti, 4.6 wgt% Mg values (calc) 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 viscous green gel. Some unreacted Mgo 1/2/0.34 0.43 Dark blue black liquid and viscous gel. Some unreacted Mg.
2fl/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) 3/1/.51 1.99 Blue black liquid with slight green tint. 6.1 wgt% Ti, 1.6 wgt% Mg values (calc) ~ ....
.-- . .

27 ~.~V~3~3 1 C. The preparation 1/1/0.34 obtained ahove was repeated except that 63.7 pts. T~T was employed with 67.5 hexane as the solvent reaction medium. A dark blue black liquid resulted, containing ~v calcination 8.2 wgt~ Ti and 1.6 wgt~ Mg ~7alues.

3o 35;~

The following Example shows the stepwise prepara-~ion of the catalyst component.

EXAMPLE VII

2.61 pts. MgC12 6H20 and 34.2 pts. TBT were com bined 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 octaine 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 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 green precipitate in the same manner as other reported reactions.
~he reaction product was activated with ethyl aluminum dichloride at a 3/1 Al/Ti ratio to form a catalyst component for olefin polymerization.

, 29 ~ 3~i3 1 The following Example evidences the significance of level of bound water.

~XAMPLE VIII
A series of identical runs were performed at the molar ratio 1/0.75/0.128 (TBT/Mg/MgC12 6H20) except that the degree of hydratlon of -the magnesium salt was modified.
~ hen MgC12 4H20 was employed (H~0/Mg = .68/1 as compared to 1:1 for MqC12 6H20), only 89.1% of the magnesium metal reacted. IJse of MgC12 2H20 at the same overall molar ratio (H20/Mg 0.34/1) resulted in only 62.1% reaction of Mg.
In repeat runs, the amount of hydrated salt supplied was increased to provide a 1/1 H20/Mg ratio. All of the magnesium metal reacted. It was also observed that the amount of i~soluble reaction product increased with increasing salt levels.

3o 3 o ~LZ~G3~i3 l The following Example illus-trates -the use of other titanium compounds.

EXAMPLE IX

A. 45.35 pts. ~0.1595m) Ti(OPr )4, 0.1595m Mg and 50.85 pts. octane added to a stirred reaction flask fitted with an electric heating mantle, and 0.027m of MgCl2 6H~O were added. The milky yellow mixture became grev with reflux, at about 88C., and turned blue at 90C. with gas effervescence. Based upon magnesium remaining, it was concluded that the reaction was partially suppressed by the octane/isopropanol azeotrope presen-t.
B. The reaction described in ~ was repeated~ at a reactant m~l ratio of 1/0.75/0.128 using decalin (b.p 185-189C) as the diluent. After slx hours, the reflux temperature had attained 140, and the reaction was terminated. A dark blue black liquid was obtained with a small amount o~ dark precipitate. Only 8.8~ of the mag-nesium had reacted.
C. In a simi]ar 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 preci-pitate. About 50% of the magnesium reacted.
D. Titanium tetranonylate was similarly employed, with magnesium and MgCl2 6H2O, 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 dibutoxv titanium dichloride) was reacted with magnesium and maqnesium chloride hexa-hydrate at a molar ratio of l/Q.75/0.128 under conditions 31 :a21~i3~3 l similar to the above examples. Ahout 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 recov-ered.

3o 32 ~ ~635~

l The following Example emplo~s a zirconium metal alkoxide.

EXAMPLE X

A. 12.83 parts of Zr(O~u)~ ~uOH (0.028m); 0.34 pts. Mg(0.14m) in the form of commerciallv available turn-ings, and 8.8 pts. octane were placed in a reaction vessel and heated to reflux at 125C. with stirring for 15 minutes, without evidence of any re~ction. 0.97 pts. o~ MgCl~ ~H~o (0.005m) was added whereupon vigorous ef~ervescence w~s noted, and the reaction mix-ture bec~me milky in appearance.
~ . In a second run 31.7 pts. of the zirconium compound (0.069m) was combined with the magnesium metal turnin~s (O.Oh9m) and 57.6 pts. mineral spirits (hp 170-195C.) and 4.79 pts. MgCl2 6~20 (0.0235m) was added with stirring. Heat was applied to the reac-tion 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 et7ident when the temperature had attained 85C., at 8 minutes reaction time Gas evolution continued with vigorous effervescence, the temperature rising to 108C. when a whitish solid appeared.
With continued heating to 133C. (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, contalning 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 reaction 33 ~ 3 1 therewith conveniently at a molar ratio of about 3/1 to 6/1 Al/Zr to provide, in combination with an organic or organo metallic reducing agent, an olefin polymeri~ation catalyst system adapted to the formation of polyethylene resinO

3o r 34 ~ 3S~

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

~XA~PLE XI

A. n. 074m Ti(OBu)4; 0.074m Ca (thick turnings supplied commercially, mechanically cut into smaller pieces) and 0.0125m MgC12 6H2O were combined in octane in a stirred reaction vessel equipped with an electric heating mantle.
~pon attaining 105C., the solution dar'~ened in color, and at 108C., with gas evolution, the solution took on a dark grey appearance. At 110.5C. 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 ~lack liquid with a greenish tint isolated.
The run was repeated at the same molar ratio. 50 o~ 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) (Xl Al).
In another run the same reactants were combined in the molar ratio 0.75/0.128. 63% of the calcium reactecl, to provide a blue black liquid and a green so]id. The reaction product (molar ratio 1/0.47/0.128) contained 6.6 wqt~ Ti, 2-6 wgt% Ca and 0.4 wgt% Mg (XI A2).
B. The reaction product ~I ~1 were further reacted with ethyl aluminum chloride at a 3/1 and 6/1 Al/Ti molar ratio. The reaction products were dlluted with hexane and the halide acti~ator added slowly to control the highly 3o e~othermic reaction. In the 3/1 run the oEf white slurrv initially formed resolved upon completion of the reaction to 35 ~ ~q~ 3 S 3 1 a pink liquid and a white precipitate. At 6/1 Al/Ti ratio, the slurry changed in color to qrey, and then lime green.
Reaction product XI A2 was likewise treated with EtAlC12 at a 3/1 and 6/1 Al/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 indi-cated in the following Table.

3o 36~)63~3 ,~ ~ ~9 r~ ~ o IH ~ ~ ~` In ~ ~D
~ ~ ~ ~ ~r ~ ~

r~ r~ o r~ ~ o ~ ~D
1 ~ ~ r 5: ~ ,~ .
O
~ In In u~ ~ a~ Cr~ o ~ r~
a~ ~
~ ,~,I r~ o :~-- r~
~) h 1~ v o oo o o o ~-, J ,~ n ~~ ~D N In ~
U ~ a~ 00 ~ N ~ O
o ~ o ~ r~
N --1 N ~V7 ~:1 h ~1 O

t~' ~1 O C) O o c) o ~ `J
P~ ~ ~
-C . U~C
25.,, o o.~
r~ ~ ~ ~ ~ rl ~ ~ ~ ~ r~ rl a ~; ~~ ~ U~
o ~ s o\o a.
o ~ O r~
h ~ o ~ rl ~ C
O ~) ~ C. h 0 ~-1 O ~
3 o N 1~ O I U~ I O C
U:' o Q) U~
.,1 P~ H ~J ~) ~) 0::~ ~1 1 U~ I I
a N a) I ~ V^~
U h ~ ~ ~ ~ ~ o ai ~ ~ ~ ~ C ~
S~ ~ o o ~ h t~ ~ Cl -rl ~ O U~ ~ ~J O i~l r~
r~ ~ ~ r- ~ ~. h t) ~
U O In ~r S ~ ~ I S C
I ~ . . O rl a) ~ o -~ ~
~,_ o o ~::

37 ~363~

1 The runs evidenced a somewhat broader molecular weight distribution in the resin as compared to the use o magnesium as the reducing metal.

1~

3o 38 ~ 35;3 1 The substitution of zinc as the reducing me-tal is shown in the following Example.

EXAMPLE XII

A. 0.204m TBT, 0.153m of 2n granules, and 00026m of ~gC12 6H2O were combined in octane in a stirred enclo.sed system equipped with reflux, and ex~ternally heated. Within 13 minutes (85C.) a rapid color change to blue black occurred, with increasing gas evolution to vigorous effer-vescence and foaming. The reaction product, a blue black liquid (no precipitate) comprising 7.7~ ~i, n.9% Zn, and 0.5~ Mg by weight, fades to yellow on exposure to air.
B. The reaction product TiZnM~ (molar ratio 1/0.86/0.128) was reac~ed with isobutyl aluminum chloride, at a 3/1 Al/Ti molar ratio, in hexane at 10-13~. lXII Bl).
C. Preparation of the TiZn~g reac-tion product (XII Al was repeated, employing Zn dust, wi-th similar results. A further run with mossy æinc utilized only 7% o~
the æinc, and evidenced format.ion of a qreen layer on the zinc surface.
D. The activated reaction product XII Bl prepared above was washed thorouqhlY in hexane and emploYed in the preparation of low density polyethylene resin. The reactor was preloaded with sufficlent butene-l to secure target density, and the reaction conducted ~with incremental addition of butene-l along with the e-thylene) at 170F. and 35 psig H2 in the presence of triethyl aluminum as co-catalyst. The resin recovered had the following proper-ties: Density .9165, MI 1.68, HhMI 52.1 and MIR 31.

39 ~2~Ei3~;3 1 The following Rxample involves the use of potassium as the reducing me-tal.

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 MgC12 6H2O were combined in octane in an enclosed system equipped with reflux, and externally heated.
Within 2 minutes at 35C. the color changed to blue black, and bubbles appeared. Vigorous gas evolution and efferves-cence 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.

3o 40 ~ 3~3S~

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

EXAMPLE XIV

A. 112.31 pts. of Ti(OBu)4 (0.33m), 8.91 pts. of Al IAlfa Inorganicspherical aluminum powder, -45 mesh) and 11-4 pts- of MgC12 6H2O (0.056m) [molar ratio 1:1:0.17] were admixed in a reaction vessel with stirring, and heat applied, emplo~ing an electric mantle.
When 100C. was attained in about 10 minutes, the yellow color deepened~ and at 118C. vigorous effervescence cornmenced, with gas evolution. At 122C. the refluxing liquid took on a grey cast, and the temperature stabili~ed, as the reaction mi~ture changed in color from a deep grey with bluish tint to dark blue then blue black at 27 minutes reaction heatinq time. The temperature was maintained, rising to 145C., 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 li~uid, 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 (mo]ar 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 coolinq bath. 0.045m 30 ethyl aluminum dichloride was added gradually, the temperature being maintained at 15-20C. The admixture, 4 ~ 3S3 , l stirred for 30 minutes provided a dark red brown slurry and an lntractable solid. (Bl).
A second run was carried out (0.175m Ti/0.0525m Al) without cooling to a peak temperature of 38C., and a red brown slurry again formed, with an intractable solid deposit. (B2~.

3o 42 ~ 53 l EXAMPLE XV

The reaction products of Example XIV were employed as catalysts in the polvmerization of ethylene under standard conditions ~190F., 60 psig ~2) employinq triethyl aluminum as a co-catalvst, with resu]ts as follows:

MI HLMI MIR
-~1 0.14 6.45 46.1 ~. 0.38 17.4 45.7 3o ~3 3 Z~63S3 1 ~XAMPLE XVI

A. In a similar manner to the foregGin~, 0.133m TBT, O.lOOm Al, and 0.017m AlC13 6H~ 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.~ wgt% Ti and 1.6~ al.
~XVI Al).
In the same manner, the same reactants were combined in a 1/1/0.17m ratio. About 58% of the Al reacted, t~ provide a reaction product containinq 6.5 wgt% Ti and 2.7 wgt% Al. (XVI A2).
B. The reaction products (XVI Al) and (XVI A2) were activated with ~thyl aluminum chloride at 3/1 Al/Ti.
C. The solid portion of the activated reaction product (XVI A21 was isolated from the supernatant and employed with TEA as co-catalyst in the polvmerization of ethylene, at 170F., 15 psig H2 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.

3o 44 ~ 63~;j3 1 The following Examples are drawn to catalyst com-ponents prepared emPloying other aquo complexes.

EX~MPLE X~II

A. 0.~335 mol T~T and 0.0335 mol Mg were stirred in octane in a heated reaction vessel, to which .0057 mol of ~gBr2 6H2O was added. (Reaction molar ratio 1/1/0.17). The salt dissolved in six minutes with heating -to 65C. A grey color developed with gas effervescence, and -the solution turned blue, then blue black with a greenish -tint. The reaction was terminated at 123C. (about 10% unreacted Mg) after a reaction period of 4 hours and 10 minutes. (XVII A).
In a similar manner, a reac-tion product was pre-pared at a mole ratio of (Ti/Mg/MqBr2 6H2O = 1/0.65!0.11),which was a hlue black liquid and dar]c green precipitate (6.5 w~t~ Ti 2.5 wgt% Mg(cr~lc)).
B. The decanted reaction product (XVII A) was combined with isobutyl aluminum dichloride a-t Al/Ti levels of 3/1 and 6/1 b~ ~radually addinq the alkyl aluminum halide. In the first run (3/1 Al/ri~ a peak temperature of 42C. 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 precipita-te. (IV
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 SiC14 in the same manner. The reaction product of a 30 minute reaction at a 3/l Si/rri ratio was a 3o liqht yellow liquid and a hrown precipitate. A similar run provided a 6/1 Si/Ti reactlon product~

~ 53 l C. The activated reaction products XVII B-1 and XVII B-2 (1% Ti bv welght) w~re employed in the polymeriæation of ethylene (10 mol % in isobutane) at 190F., with hydrogen modifier and triethyl aluminum cocatalyst (45 ppm Al) and compared to an ldentical run using magnesium chloricle hydrate, wi-th results set forth in Table III as follows:

3o 46 12~36~3 U~
~ ~ C5 .,, ~
.,., ~ Lr CO C~ I ~ Ln ~1 ~ 1~) N
~:,L ~:
P. . .

IHr-lCO ~ I r-l r ~
~D I ~ ~D

H . , ~) CC
3 ~ r ~ o 1--10 n. ~It~l O H
. .

~`
.,1 1 rl E-' I` o ~ a~ co Lt~
CO~1~It~ ~-- O
~ ~ ~ O~ ~ r~
H ~1 ~r ~r o r~
~ P~ t~
~1 I_ 20 ,~

.,1 o o C o o o X
Q

+
., E~ ~ ~
~o ,¢--3o ~: o o l ~
~ ~ ~9 u, I
r ~_ o m r~
~m o E~

47 lZ~1~353 l .XAMPLE XVI T I

A. 42. 23 pts. of TBT (0.1?4m) were comblned with 3. 02 pts. lMg (0 .124m) in octane (42.8 pts.) in the presence of 5.7 pts. FeCl3 6H~O (().02m) (TMqFe = l/1/n.]7 molar~ in an enclosed stirred reactlon vessel equipped with reflux, and an electric heating mantle. I~eating commenced, and within 6 minutes, at 65C. gas evolutiorl began. The muddy yellow color turned dark brown at 80C. (7 minutes3 and gas evolution increased. In about 30 minutes gas evolution had slowed and then ceased with consump-tion of Mg, and the reaction was terminated. The very dark liquid evidenced no residue. (XVIII A1).
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 precipita-te or deposition of residue. lXVIII A2).
B. Reaction product XVIII A1 was activated by reaction with a 50 wgt% solution of ethyl aluminum chloride in hexane at a 3/1 A1/Ti ratio. A brown liquid and solid was recovered, containing 16.5 Mg Ti/g. (XVIII B1).
In a similar manner, reaction product lXVIII A2) was activated. The dark brown liquid chanqed 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 B1 was employed in the polymerization of ethylene at 190F., 60 psi H2. 114,320 g PE/g Ti/hr were recovered, e~hibi-ting the following properties: MI 5.1, HLMI 155.3, MIR 30.3.
3o ~8 ~ 635;~3 l EXA~IPLE XIX

A. l. 0.l6nm Ti (OBu)4, 0.160m maqneslum turnings and 0.0~7m CoCl2 6H2O were combined in a s-tirred reaction vessel with 61.2 pts. of octane. The violet cobalt salt crystals provide upon dissolution a dark hlue solution. ~he admixture is heated, employinq an electric mantle, and gas evolution on -the magnesium surfaces appears at 58C., increasing to vigorous effervescence at 107C. within l~
minutes. The clear blue color becomes greyish on fur-ther heating and becomes almost black at 123-125C. when all the magnesium has disappeared and the reaction is -terminated, at 90 minutes. The milky blue reaction product was hydrocarhon soluble, and resolved into a dark blue liquid and a dark precipitate upon standing.
The run was repeated, with essentially identical result.s .
~ . The reaction product of the foregoing prepara-tion was shaken, and 0.0lllm (Ti) was combined with isobutyl aluminum chloride (n.0333m Al) supplied dropwise to a reactlon vessel. The temperature peaked at 40C., with formation of a greyish precipitate, which upon further addition of BuAlCl2 turned brown. AEter stirring Eor an additional 30 minutes the reaction was terminated, pro-viding a dark red hrown liquid and a brown precipitate.
C. The catalyst component prepared in Example XIXabove was employed in the polymeri~ation of ethvlene (190F., ln mol % ethylene, n.ooo2 pts. catalyst calculated a5 Ti, triethy] aluminum about 45 ppm calc as Al, ~ as indicated) with the results set for-th in Tab:Le IV, as ~ollows:

~ g ~ 3.5~
,.~ ~

l TABLE IV

H Prod Resin Properties Catalyst psigg PE/g Tl/hr MI HLMI HLMI/MI
XIX B 60105,180 6.2 206 33.6 12075,290 33.9 950 28.1 3o 50 ~ 63S3 A. 0.169m Ti(oBu34 ~TBTl, O.l~9m magnesium turnings, and 0.029m AIC13-6H20 in octane as a diluent were combined in a stirred reaction ves~sel equipped with an elec-tric heating rnantle. The hydrated a]alminum salt partlv dis-solved and at 111Co the solution rapidlv darkened to a black liquid with vigorous effer~rescerlce originating with gas evolution at the surface of the magnesium. The solution took on a blue coloration and, with srnooth refluxing to 1~2C. formed a dark blue black liquid with some remaining ma~nesillm. At 125C., all the magnesium metal disappeared, the solution exhibiting a slight green tint. The reaction was terminated~ and a dark blue black liqui~1 and green pre-cipitate recovered, in a volume ratio of about 95/5.
B. The reaction prodl1ct described abcve was com-bined with isobutvl aluminum chloride in a molar ratio of 3:1 and 6:1 Al/Ti by dropwise addition of the chloride to a reaction vessel containin~ the titanium materia3. In the first reaction (3:1), the a]kvl chloride was added at a rate of 1 drop/2-3 seconds until a peak temperature of 42C. was attained, with a color chan~e from hlue-~reen to brown.
~fter stirring for an additional 30 minutes, the reaction product, a red-brown liquid and a brown precipitate, was isolated. (XX B).
CO In a similar manner, a 6:1 Al/Ti product was secured, with the same results. (XX C).
D. Reaction products XX B ~ND XX C were emploYed with triethylaluminum co-catalyst (45 ppm A]) in the poly-3o merization of ethylene (10 mol %) wlth isohutane diluent at190F. and hydro~en as indicated~ The runs were terminated 5 1 ~Z~353 1 after 60 minutes i h ~ollows: ~, w t results indicated i.n Tahle V, as 3o 5 2 ~2~53 _A~3LE V

H2 P~: Prod Resin Properties Catalystpslg mole g P~/q Ti/hr ~II HT~1I HLMJ./MI

XX B 6n 406 84 ,580 17. 2517 30. 1 12û 542 75,280 54.9l413 ?5.7 10 XX c 60 ?45 54,440 4.11129 31.'1 120 183 34, 860 26 . 2 ~301 30 . 5 3o 53 ~20~3~ii3 EXAMPLE XXT

A. 0.153m Ti(OBu)4 [TBT], 0.153m Mq turnings and 0.026m NiCl2 6H20 were combined with hl.75 pts. of octane in a stirred reaction vessel equipped with an electric heating mantle. I~Jith heating to 44C. the yellow solution deepened in color, and gas evolution on the magnesium metal surface became observable at about 57~. With contin~ed heatinq, the ~as evolution increased until at 102C. (15 minutes reaction) the reaction system turned a light muddy brown color. Vi~orous effervescence continued with darkening of the brown color until at 126C. (75 minutes) all the magnes-ium had disappeared, an~ the reaction was terminated. The reaction product (XXIA-1) was a hydrocarbon soluble dark brown liquid and a s~all am~unt of a fine precipitate.
In a secon~ run 0.149m T~T, 0.149m Mg, and O.OSlm NiCl?-6H~O were combined in octane in the same manner. Mg metal disappeared at 115C., 120 minutes, and the reaction resulted in a dark brown black hydrocarbon soluhle liquid, which resolved on standing to a very fine dark precipitate and a yelJow liquid, about 50/50 by volume IXXIA-2).
B. Reaction product IA-1 was shaken, and a por-tion (0.0137m Ti) was placed in a reaction vessel with hexane diluent, to which iBuAlCl2 [0.0411m A1) was added dropwise, at a rate of l drop/2-3 sec. to 28C., and 1 drop/sec. to a peak temperature of 39C. After completion of addition the vessel contents were stirred for 30 minutes, and the reaction product t a dark red brown liquid and a dark gre~ precipitate, isolated. (XXIB-I).
3o The same reaction product (XXIA-1) was combined with ethyl aluminum chloride in the same manner, at a 3/1 54 ~ 3~

1 Al /Ti molar ratio. The reaction product was a ~ark re~
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/C.34) was combined with iBUAlCl2 at a 3:1 A1/Ti ratio, with the same results, except that the supernatant liquid was a pale red brown co]or. (XXIB-33.
In a further run~ reaction product XXIA-2 was reacted in the same manner with iBuAlC12 at a 6:1 A].-Ti molar ratio, to for, similarl~, a dark liquid and dark precipitate. (XXIB-43.
The same reaction product XXIA~2 was combined with ethyl aluminum chloride in the same manner, produclng a dark red brown liquid and a dark grey solid. (XXJB-5).

3o ~2~ S~
5~
EXAMPLE XXI I

A. Example XXIA was repeated, with the reactants supplied in the molar ratio Ti:Mg:Ni of 1:0. 65 O r 11~ The color change was from deep brown yellow to dark brown with gas evolution, and thence through a grev br~wn to dark blue black upon consumption of magnesium, in a reaction occurring over a ~eriod o 6 hours. (XXIIA)~
B, Reaction product XXIIA was combined with ethyl aluminum chloride in the manner of Example XXIB at a 3-1 Al/Ti molar ratio. A red brown liquid and red brown preci-p.itate was recovered~ (XXIIB).

.

3o 56 ~ 5~

EXAMPLE XX I I I

Example XXII~ 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.~ Mq and 0~97% Ni.
The reaction product was then treated with isobutyl aluminum chloride at an Al/Ti molar ratio of 3/' 3o 57 ~.2~353 A series of TMgNi catalysts, prepared as set forth in Examples XXIB and XXIIB, were employed as catalyst com-ponents in the polymerization of ethylene (190F.~ 10 mol %ethylene, triethyl aluminum about 45 ppm calc as Al, H2 as indicated) with the resul~s set forth in Table VI, as follows:

3o 58 ~ 5~3 l TABLE VI
.
H2Productivity Resin Properties Catalyst psigg PE/g Ti Hr MI HI.MI HLMI/MI
XXIB-3 6090,750 9.55 270 28 1~0104,980 24.6 683 27.8 60111,940 0.29 10.7 36.8 120112,260 3.1 119 38.9 XXIB 4 6059,790 0.25 10.9 43.6 l~Q62,7~0 1.0 43.6 43.6 XXIIB 6057,890 1.66 54.9 33.1 12~64,740 6.13 183 ~9.8 XXIB-2 60238,670 0.65 19.5 30.2 120271,560 6.7 188 28.1 XXIB-5 30175,000 Low lRuns at higher levels of hydrogen were extremely rapid, resulting in polymer buildup requiring termination of runs.

3o 59 ~ 6353 l EXAMPLE XXV

A. TBT, Mg and MgSiF6-6H2O 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/O.75/OA128 respectively.
B. The latter reaction product was activated bv 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 polyeth,vlene polymerization (190F, 60 psig H2) producing resin at 107,500g PE/gTi/hr characterized by Ml 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 170F., 30 psi H2 from the ethylene/~ut~ne-l feed. The resulting resin had a density of .9193, MI l.91, HLMI 60.8 and MIR 31.8.

3o ^:~

1 ~0 6 3 ~ 3 1 In the following ~xample~ catalyst components were activated by reaction with a halide component.

EXAMPLE XXVI
-A. In the following runs, T~g reacti~n products were reacted with the halide component added gradually there~o, usually dropwise to control the exothermic reaction. The reaction was conducted under ambient 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-tions are set forth as follows:

3o 3~3 Catalyst Component, mol ratio Ti!Mg/MgCl 6H O (H~O) Halide Activator Mol Ratio 1/0.65/0.11(0.66) Bu AlCl2 2/1 Al/Ti 1/0.65/0.11(0.66) Bu AlCl~ 3tl 1/0.65/0.11(0.66) Bu AlCl2 4/1 1/0.65/0.11(0.66) Bu ~lCl~ 6/1 1/0.65/0.11(0.66) EtAlC12 3/1 1/0.65/0.11(0.66) EtBCl2 1.25/l(B/Ti) 1/0.65/0.11(0.66) EtBC12 3/1 (B/~i) lO 1/0.65/0.11(0.66) SiCl4 3/1 (Si/Ti~
1/0.65/0.11(0.66) SiC14 6/1 (Si/Ti~
1/0.75/0.128t.768) EtAlC12 3/1 1/0.75/0.128t.768) ~t~Al2Cl3 3/1 1/0.75tO.128(.768) Bu AlC12 3/1 15 1/0.75/0.128(.768) BulAlCl2 6/1 1/0.75/0.128(.768) EtBC12 3/1 (B/Ti) 1/0.75/0.128(.768) ( 3)2 2 6/1 (Si/Ti) 1/0.75/0.128(.768) (Ch333SiCl 6/1 (Si/Ti) 1/0.75/0.128(.768) (ch3)2siHC1 6/1 (Si/Ti) 20 1/0.75/0.128(.768) SiC14 3/1 (Si/Ti) 1/0.75/0.128(.768) SiC14 6/1 (Si/Ti) 1/0.75/0~128(.7683 TiC14 1.5/1 (Ti/Ti~
1/0.75/0.128(.768) TiCl4 3/1 (Ti/Ti) 1/1/.17(1.02) Bu AlCl2 3/1 25 1/1/.17(1,02) EtAlCl2 3/1 1/l/.34(2.04) Bu AlCl2 3/1 1/1/.34l2.04) Bu AlCl2 6/1 1/1/0.51(3.06) Bu AlCl2 3/1 1/1/0.51(3.06) Bu AlCl2 6/1 30 2/1/0.17(1.02) Bu AlCl2 3/1 2/1/0,17(1.02) Bu AlC12 6/1 2/1/0.34(2.04) BulAlC12 3/1 2/1/0.34(2.04) BulAlCl2 6/1 3/1/0.51(3.06) BulAlC12 3/1 35 3/1/0.51(3.06) BulAlC12 6/1 v ~
62 ~ 3 -EXAMPLE XXVII

A. Catalyst samples activated with BuiAlC12 (3:1 Al/Ti) were employed in a series of poly~erizati.on runs, with results set forth in Table VII as follows:

63 3~
H

U~ ~ ~ Ul11~ 0 ~ N r-l ~D CO ~ N Cl~ N
W~ ~ .. .. .. . - . - . ..
.~ H ~ co u~ o I O~ co IJ ~ ') N ~ ~ ~) ~ t~ r~ 1 N N
~1 ~
~ _. 'E~
~1 H~I CO 11~ 1 N C:~ o~ O In O~) ~I r~l co Inco ~ 1--~~r o ~ ~
3 :~ ~ ~1 u7 ~r ~,~ ~D ~` r~I` ;r o U~ U~
Ht--N OD 1`In 11')d' N~ 0 ~ Ll'~ N '~
~1 ~ t~ Lflt~ N N ~L~ N CO ~r~ I` ~¢
J ~ N ~

_ ,~

o ~3 ~ .n o c~ ~n oo o In O O O r~
rl E~r~ o~o n ~ o r~ co u,~ o 1. ~ ~ ~ ~r~ Der ~D ~1 ) ~I CO ~ ~) HO ~~ ~r ~D ~rU') Ll~If) Lt~ N ~I`` ~D ~ CO (~
:~ ~ ~
_ ~C o E~ Ql _ _ ~:
~ o o o o o o o o o o o o o o ~ rl ~D ~ D N~D ~`J ~D N ~D N~D N ~D N ~) _ Q! rd QJ a~
n ~ O
~o E~ ~D
2 5 ~D ~) ~ N
N~ ~ ~ O~ ~ oo ~I CO Ei ,~ la ~1 ~ ~d I
O

a~ ~4 v ~ ~
U~ ~ o ~
0 ~ ~o ~d ~ m ~o ~
~ Q ~1 ~ O E3 E~
_ ~ O I U~ I rl O o O oc~ ~ u~ D
~ ~ H nw ~
~1 ~1 0 3-1 1 U~ I I I
~ ~ ~ C) I ~ ~
5~ r ~r ~r ~ o o r ~ ~ nw r~ n ~ ~ ~ h ~ ~
. . Inu~l O ~ 5~ ~ ~ ~ nW ~1 ~ O o r~D O ~ O ~w O 1~ ~ ~I E~
-1 ~ ~ ~ ~ ~ ~ V
~ ~ 1 0 ~
Ei ~ ~ ~ ~ ~ ~1 n~ ~ o ~ ~;

i3~ii3 l As may be seen from a comparison of Ti/MqCl2 6H2O
molar ratio, peak melt index is observed at a 9:1 ratio (1.5:1 Ti/H2o).

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 e-thylene.
Results are set forth in Table V~II as follows:

3o rl H . ., ,, , .
~ ~ ~ 00o I ~ ~C~ ~ o I ~ oo o ~
Q~¦ ~ ~~) I ~) r~) ~ ~) ~ I ~) N rf ) ~) ~1 .
~ H c~ r a~ o a) ~ ~ ~~ I In ~ o ~ ~ I ~ ~ o ~D
~1 ~ ~ ~ N ~1 ~1 ~r ol ~ ,, I

r~ CO ~ ~ r In r o o U~ H .. .. .. . ..
a) ~:~ ~ co ~r u~ r ~ ~ ~ ~ oo o Q
_~ U~
I ` .
.~, .~ In O U~ OO U~O OO O In o o o a r ~ n ~ rcr ~1 m ~ o a~ ~
` In~ ~0~ ~1- ~ r ~ ~ ~ rd ~ .~~ L~ ~ ~~ r~ ~ro r~ r ,~
1 F O P~
r~
H P~
, h ~' ~
~' o o o oo oo o o o o o o o ~ o ,, ~ ~ ~ ~ ~ ~ ~ ~
~_ ~ ~) h~ ~ N
O O N ~ 1~ 1 ~I $ ~ 0 O O ' ~ O
0 ~ o ~
~0 ~ e ~ Q
~ O 1 0 1 r~ O O
~ 0 t~ O h I u~ I I I
~: ~ ~1 ~ ~1 ~ h O ~ h t o ,, ~ ~ ~ u ~ ~ ~ a) ~ o ~,1 ~ ~ o L) ::~ ~ h O
~ ~ l 1 ~ m m ~ ~ ~
~ o ~ ~ o ~ ~ ~
~ u m m m m ~ ~ ~ K a E~

66 ~ 3~j3 l C. In a further series of experiments, employinq 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:

3o ~2~:~6353 U~
(U H
-1~00 ~D NO C~ L~ N~C~ N r-- N ~) 1--h H ~ ~ ~ - . - .. .. .. ..
0 1:1t~) ~`J ~) It'~l ~`1 t~ l N ~ `J N t~

o r~ o r H ~ O~ iCO ~ ~r Or-l 0~ 0 ~I Cl~ ~ ~1 1`
3 1~lr~ ~O I In 1~ D Ln ~ ~1~1 ~ N
5 P~ :r~ ~ ~ N~ ~ ~ N iD N
. ~r L~
a~~ O~ ~ ~ r~~ ~ t~ N t~
H . .. D
Ln t~ ~ o r~ co Ln o ~ N ~1 ~1 ~

~. h .,,~ I
oo oo oo ~ooooL~ oo oLn N 1--~ ~r ~ f~ ~ ~ Ln L ) ~)~ ~CO OCO ~1 t~0 ~~ ~r ~ ~D cr, In ~r ~~ oet~ 1 Lr~ LO ~1 ~1 ~cr ~ ~:1~ ~!~ CO ~ ~r.~ ~ ~ ~ ~ Ln ~ r~
h~ , ~~4 ~
H ~_ E~
20 ~1 o o o o o o o oo o o o o o o. o S~ UJ ~ D N~D N~D N ~ N ~D N
Q ~1 ~1 ~ ~1~ ~ ~t L

~ ~ ~ ~ ~D N ~' ~D
~ r-l ~I N
C~
~ ~ o o ~. ~ ~ ~

~D

~rl ~ ~ ~ ~ ~
C~ ~ V O ~ o r ~ a) ~ o ~ r-l ~1 ~4 r~ ~ h () :~
35~ fl~ ~ q ~ f~l ~ U ~.) V 11 O tJl :~ ~) f~ a) f~ a) rl a) ~`' O ~ :~
~ ~c m ~ a E~

68 ~ 3~3 l D. Larger scale polymerization runs were con ducted at 160F. with khe T~Mg 1/0.75/0.128 catalyst (slurry, separated from supernatant liquid, and washed with hexane) and TEA co-catalyst employing ethylene and butene-l as a comonomer, utilizing varying butene-l feed, activators and activator ratios. Results are set forth in Table X as follows:

3o 69 ~ i353 N 5~ N
U O U
~1 ~I ,_1 U ~ U
~ ~ ~ a a a m m m ~
U U U U

~1 ~ ~ r~
.~ ~ ~ ~ ~ ~ ~ r ~ ~1 w w ~D ~ ~ ~ ~ ~ ~ ~
'13 a) r~ ~ ~ ~ r~ N N (~) ~' OOOOOOOOOO

. u ) W ~r ~ ~ I~ ~
H O O ~! 00 CO ~ O r-l ~ ~1 ~ o ~r ~r ~ ~I ~ ~ ~ ~ ~
~ ,_1 ~; I` C~ O ~ ~ ~ r- ~ oo H ...
N~1~1 ~ )oo o a) ,~
~c a)--~ ~ o ~? O ,1 m ~ ~
F:t ~ r~ ~ ~ r I I ~ ~7 1 ~
E~ ~~ o o o I 1 5 0 ~ O
~ .... . ~
`~e p~--~1 o E~ a) ~1 ~In ~ ~ ~ r N
. I o~o O ~ ~ u~ In ~ r CO
C ~~ ~ O I~ r ~l ~ I I ~ U~ I r ~ t~ ~ ~ ~
m--O O h a) ~ o ~0 ~ O ~
J ~, ~r ~ o ~ I I ~ ~ I r~
~o q~ . . . . I I . . I
a) h ~ `1 ~ ~`I
S ~ rl ~ .~

zl U ~ ~ ~1 0 5i H 1':) ~1 ~i ILI

;3~CL3 l 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 screw; 3" die at 0.082" die gap; cooling air 37-4~F.) and further tested, all as set forth below in Tables XI and XII:

3o 71 ~L2~3~
In ~ O O O ~ o ~D
~) r-l ~D r~
r l ~ O CO 1~ r~l r-l I
~r -1 N N CO
r~
~ ~ O O O ~ ~ ~ ~D CO
H CO ~ ~ r-l O ~ O 1~ U~
~ r-l ~D ~ r~ ~r ~ r-l ) Ul N r~ N ~r a'~
o r-l I O O O 01~ 0 0 ~D
14 I r-l O ~r ~1 1 O ~ N t~
,~
r-l I O O O CO~ N I 1~ 0 li~ I N CO 151 ~ r~
O ~ N ~ I O

14 1 0 0 0 11~) ~ N ~D 1~ rl I Lt ) 5~ ~r r~
0 In N ~D !-- ~rf) r-l I ri 14 a~ N N ~r~
o In o o o o. o ~ D a) O
U~ ¢~ ~) Il') O ~') ~ ~1 i`` Lf) 4 ~ r~ co ~ ~ ~ ~ I
~r~~ ~I rJ ~) ~ a) 1 5 ~ ~a ~D N O O Ot~
a) 1~11~ N~D ~ r~l 1~ LO
. ~rl . r-l CO ~Z~I cnCO r-l I
HU~ W ~ ~-1 ~ eJ~ ~ . ,1 i I Q ~ I O O O N O ~r D 1~ (1 ~I) O ~; I L~ r) r-l ~ Ln ~
3 C )~9 ~ 1~U~N ~--1 r l I rl S~ ~ ~ o o o o ~ Ln ~ oo a) p:; a ~ ~ ~ Ln h r l 1~ N r 1 ~1 ~r r~
~) ~1 ~ Ll'') O
~D ~ o l o ~ ~ n ~ rl I o r-l ~~ ~D ~1 ~ rl a~ -I
r1 ~ ~ ~ r~

.,1 0 rl rl ~ U~
~i O _5 O ~ U~
~1 : 0 ~
O r-l ~ ~ X
rl X ~
Q alr-l O U~ ~rl r~l r~
o ~. rl Ou, o ~ ~ a O ~ P r~ O
r l O
X ~ ~ ~ ,0 ~ ~ ~
H U~ S-l O ;~ H C ) h ~1 O r l ~1 rl ~ 0 3 5 o 3 r-l 0 r-l r-l ~ O
r l U~ rl ~ tr~ ~rl rl ~
Ul rl S U~ M 0 ~ ~1 o ~ ~ t m o ~ rl (1~ rl ~--1 a) Il) rl E~ ~

~J~3~

o ~ ~1 ~ cr~
N 0~ 0 0 0 0 0 0 1~1 ~0 O O O
1~ -1 0 ~ co ~1 o 1~ ~) o ~) Cl~ ~ J cr r~ N CO t~l ~r co -l t`l ~
... ..
~;~OOOOOO~OOcO
, ~ ~ ~ ~ I` ~ ~ ~ In o O 'SP N ~ ~D C10 ~ N
~D ~r N N Ltl 1--1 ~r cr ... ..
I ~ roooooo .-1 r~oooo t~l ~3 N ~ N 1 ~D (~ ~1 ~D ~O r ~
U~ Il') ~ N t"l O ~r ~ ~ I`
~a O;
~ ~
H ~ C~
H rl 0 ~ 1 x ~n ~ o o ~r ~ ~ .
a) _,c~rooooo'o~D~OOO
Il ~ ~ ) O U~
m ~ ~ o ~ r a~
~ 3 .,~ ~r ~ N ~1 CO l--E'l ~ ¢l ~g oo ~ m ,~ O Ln ~ O cn ~ ... ..
~In~ooooo~s;I~ooo r~ ~ ~o co 1` o~
~) ~ ~ N
~_ ~
a a a a a ~ a a a a a a r-l r-l r~l rl r-l r--l Q~rl E~ ,4 U~
r~
E3 ` ~ tJ`

u~ ~ ~ s~ O
U~ rA ~ ~o~ 1~ 0 r--l a) Q)t) ' O r-l E~ ar~
,y o ~ ~ ~ O
t~ o ~n h o ~ ~ ~
rl ~ ~,1 hE~
.~ rAO a~U~ IJ O U~ (U
r-l ~r~
. U? r-lr~
e~ . r~
3 5 r--l N O ~(I) O e ,;s ~:
rl ~r--l O r-lr--l r--l ~; a) o 73 ~2~ 5~
o . ~
t~,.
o o~
o I

~?
, ., CO
J r~
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u~ ~ o ~ o cr~
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C~
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3~ ~i Lr~ ~
U~
rl Ul UJ
_ a~ ~1 ~ ~; ~ ,_ O
E~ ~ ~ . ,;
~i ~ ~ ,~ _ ~ rl O ~ O 11 C~ U~ ~ U~
_ ~ ~ ~ ~ ~
C~ O r~ O O 0 00 H Q ~ r1 H r l tr~
X 3 rl .') O E'l ~ ~ 3 m _ ~m . ~r ~P
~ ~`J I rt O CO
r~ ~) G ~1 -u. O
,~
rl ~ rl E~UJ U~
-- ~, u, m u.
O a) E~
r~ _ ~rl S-l 11~ r l ~ U~ rl Q m ,1 ~ o~
C) ~ o a rl rl ~ o ~ a) a) o ~ x ~

~O~i3~3 U:~ o o o o co o~
~ o ~ o o o o o o C~ ~ o o o o o ,~ o ~ ~g ~ ~ ~ ~ U~

O Irl G 1`-) 0 ~ ~r ~D o o o o o o o ~D o G O G
~ ~ o~ g m r ~ ~ o co ~9 a) ~ ~r r--o ~
r; CO ~D O O O O O O 1~ Cl~ ; G t~
.-1 o ~I r-l ~ ~ ~ ~) L ) 1-- 0 o O 11~ 00 U) I` U~
U~
~ U) U~
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_ h o d~ ~
E~ ~a~ ~ cooooooi~.;ooo ~; Z ~ Q ~ -1 Lt') ~9 -1 CO 11'~ CO 1` G
~ h U~
- ~ p~
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a~ h 3 ~l ~ In o o o o o o ~ o~ o ~ In O
cC ~a O t~
~ ~ c~ o In oo ~ Ln 0 C~
~ n o ~ ~ o ~
~rInOOOOOOO1--~OOO
.~ ~ o ~
~ Ln ~ ~ ~ ~ ~
o ~ ~ o\ ~ O r~
a ,~ O ~ a~ ~
o u~ ~ o o G~ u~ ~ O U~ a 3 5 ,~ ~o~ :G~ o 3~3~3 .. ~ O

~,~

~r , ~
~ ~ O O
O
~ ~ ~r CJr~
~ ~ o o . I o co r~
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â ~ _~
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15 o ,, o N -- O
. ~ u~ 5~ ~ n ~ o `_ ~ P~ O I O CO
~ a X 3 ~
~ ~ ~ o m s~ 3 _ ~ ;~ o O ~
20 E~~ m ,~ G
co . . o In oo ~ ~ o ~
~3 2 5 N o O
In O
I O

r~
., U~
~ ~ .
u~ m u~
~- O a) E~
m , a ,1 o E~
~) ~ X 3 ~, ,~ ''~
2 ~ h ~
a a e a ~ x ~2(~5~

l E. In further large scale polymerizations con-ducted in a simila.r manner employing Tr~Mg catalyst (slurry, separated from supernatant liquid and hexane washed~ at molar ratio l/0.75/0.128 (3/1 Al/Ti, EADC), hexene-1 was fed to the reactor as a comonomer with et.hylene, and then butene-l was substituted pro~iding, as followed by off gas analysis, ethylene/butene--1/hexene-1 copolymers and ter-polymers in the course of the operation. Results are set forth in Table XIII, as follows:

-3o ;

~L20~;' r~

;~
H ~ t~
~ tr) ~1 ~ ~ ~ r~7 H ~ ~ ~r N N ~
:~
~ ~ ~ ~ U~ I
t~i ~ N ~ N N N

H
X

~ ~ ~ ~ O O
~ o o o O O

~ ~ ~ I~ C~ 05 In ,~ ~ ~ u~
rn ~ N ~1 ~1 ~I -1 a~
O O O O O O

3o o ~ x x m ;3~3 .

Tr~rlg 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, 170F. reactor temperature, 30-40 psig H2 and TEA to provide 60 ppm Al, with results as follows:

lO Ethylene/3-Methylbutene-1MI MIR Density 1.25 27.4 0.94~8 1.25 28.9 0.9483 1.36 27.9 0.9507 1.55 27.7 0O9497 1.56 27.5 0.9495 1.87 29.9 0.9496 1.63 28.5 O.g455 2.25 28.8 0.9437 1.46 30.0 0.9428 5.01 30.3 0.9411 1.59 31.l9 0.9400 Isobutylene 0.37 32.4 0.9518 1.35 29.6 0.9564 ~.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.

3o l The ~ollowing comparative experiments were also conducted:

COMPARATIVE EXAMPI.ES
A. In the same reaction vessel used in other preparations T~T, 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 anhy~lrous MgCl2 remained undissolved. See also Example IB above.
B. To the same system, an amount of free water equivalent to an Mg~/MgC12 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 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-cing hydrolysis of the titanium compound, but the magnesiumremained unreacted.
E. TBT and MgC12 6H20 were combined in octane at a molar ratio of 1/0.34 and heated to reflux. After the salt had entire]y 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 ltO.128 developed a clear golden yellow liquid with heating to reflux over only 16 minutes. At a molar ratio of 1/1.17 3o foamin~ and formation of a thick cream colored gel termin-ated reaction after 45 minutes. Compare Example VII, above.

Claims (18)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for the preparation of an intermetallic compound which comprises reacting a polymeric transition metal oxide alkoxide with a reducing metal of higher oxidation poten-tial than the transition metal, and wherein the transition metal is titanium or zirconium.

2. Process according to claim 1 wherein the poly-meric transition metal oxide alkoxide is produced by partial hydrolysis of the transition metal alkoxide.

3. Process according to claim 2 wherein the hydro-lysis is effected with an aquo complex as water source.

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

5. Process according to claim 4 wherein the hydrated salt is a hydrate of a salt of aluminum, cobalt, iron, magnesium or nickel.

6. Process according to claim 3, wherein water is provided in the form of a hydrated oxide.

7. Process according to claim 6, wherein the hydrated oxide is silica gel.

8. Process according to claim 3, 4, or 6, wherein the molar ratio of transition metal to water is from about 1:0.5 to about 1:1.5.

9. Process according to claim 1, 2, or 4 wherein the reducing metal is magnesium, calcium, zinc, aluminum, or mixtures.

10. Process according to claim 1 wherein the molar ?tio of transition metal to reducing metal is from about 0.5:1 to about 3:1.

11. Process according to claim 1, wherein the reac-tion time is initiated by heating to an elevated temperature to initiate exothermic reaction.

12. Process according to claim 10, wherein heating is continued until up to the stoichiometric amount of reducing metal is consumed.

13. Process according to claim 1, wherein the product is further reacted with a halide activator.

14. 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, wherein the transition metal is titanium or zirconium.

15. The intermetallic compound of claim 14, wherein the reducing metal is magnesium, calcium, zinc, aluminum or mixtures.

16. The intermetallic compound of claim 14 wherein the polymeric transition metal oxide alkoxide is the product of the controlled partial hydrolysis of a titanium alkoxide.

17. The intermetallic compound of claim 14, 15, or 16, wherein the transition metal and reducing metal are present in a molar ratio of from about 0.5:1 to 3:1.

18. The intermetallic compound of claim 14, 15 or 16, further reacted with a halide activator.