CA1177812A - Process for the polymerization of 1-olefins and a catalyst therefor - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

A process for the polymerization of 1-olefins, alone or together with at least one copolymerizable monomer, under polymerization conditions of temperature and pressure with an olefin polymerization catalyst system comprising a mixture of cocatalysts one if which is a halide activated 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.

Description

~77~
This invention relates to intermetallic compounds of -transition metal alkoxides, and processes for their pro-duction. More particularly, the inven-tion affords catalyst precursors for interreaction with halide activators to pro-vide a catalyst component adapted for the polymerization of alpha olefins.
Polyethylene, produced by solution or slurry processes at lower pressures or in autoclave or tubular reactors at higher pressures, has been an object of commer-cial production for many years.
Recent interest has centered on linear low density polyethylene resins characterized by linerarity and short chain branching afforded by alkene comonomers, and offering narrow molecular weight distribution, improved strength properties, higher melt viscosity, higher softening point, improved ESCR (Environmental Stress Crack Resistance) and improved low temperature brittleness. These and related properties provide advantages to the user in such applica-tions as blown film, wire and cable coating, cast film, coextrusion, and injection and rotational molding.
The linear olefin polymers have typically been produced using catalysts of the general type disclosed by Ziegler, thus comprising a transition metal compound, us~ally 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-moter such as an alkyl aluminum halide. Among the improved catalysts of this type are -those incorporating a magnesium component, usually by interaction of magnesium or a compound ~'

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1 thereof with the transition metal component or the organo-metallic component, as by milling or chemical reaction or association.
There is also interest in producing intermediate to high density resins of modified characteristics employing coordination catalysts of this type. In particular, resins of broader molecular weight distribution and higher melt index are sought.
The invention relates to an olefin polymerization catalyst system comprising a mixture of cocatalysts one of which is a halide activated intermetallic compound com-prising the reaction product of a polymeric transition metal oxide alkoxide and a reducing metal of higher oxidation potential than the transition metal.
The invention also relates to a process for the polymerization of 1-olefins, alone or together with at least one copolymerizable monomer, under polymerization conditions of temperature and pressure with an olefin polymerization catalyst system comprising a mixture of cocatalysts one of which is a halide activated intermetallic compound com-prising the reaction product of a polymeric transition metal oxide alkoxide and a reducing metal of higher oxidation potential than the transition metal.

3o 2a ~77~1Z

1 Transition metal-containlng intermetallic compounds are prepared by the reaction of a polymeric transition metal oxide alkoxide with at 1east 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 magnesium meta] to provide a reaction product which may be activated to form an olefin polymerization catalyst element.
The polymeric transition metal oxide alkoxide may be separately prepared by the controlled hydrolysis of the alkoxide; or the polymeric oxoalkoxide may be provided by an in situ reaction, e.g., 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 con-trolled source of water, preferably a hydrated metal salt such as magnesium halide hexahydrate.
Transition metal alkoxides, particularly titanium alkoxides, are knwon for their colligative properties in organic solvents, and their sensitivity to hydrolysis. It is reported that the hydrolysis reaction proceeding from the oligomeric, usually trimeric titanium alkoxides results in polymeric titanium oxide alkoxides, generally expressed as 3o 8~

; 1 Ti(OR) -~ n~ O n( )4-2n ROH
Condensation reactions may also occur especially at elevated temperatures to structures involving primary metal-oxygen-metal bridges such as:
OR IOR
OR - ~i - O - Ti - OR
1R bR
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) mav be repre-sented by the series [Ti3(X~l)04x( )4(x-~3) 1,2,3,..., the structure reflecting the tendency of the metal to expand its coordination beyond its primary valency coupled with the ability of the alkoxide to hridge two or more metal atoms.
Regardless of the particular form which the alkoxide is visualized to adopt, in practice it is sufficient to recognize that the alkoxide oligomers form upon controlled hydrolysis a series of polymeric oxide alkoxides ranging from the dimer through cyclic forms to linear chain polymer of up to infinite chain length. More complete hydrolysis, on the other hand, leads to 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 hydrolysis products. The hydrolysis reaction can be carried 3o out separately, and the products isolated and stored for further use, but this is inconvenient especially in view of the prospect of further hydrolysis, hence the preferred ~778~L~

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 directly by the quantity of water which is supplied to the transition metal alkoxide and the rate of addition. Water must be supplied incrementally or in a staged or sequenced manner: bulk addition does not lead to the desired reaction, effecting excessive hydrolysis, with precipitation of insolubles. Dropwise addition is suitable as is the use of water of reaction, but it is fourld more convenient to provide the water as water of crystalli~ation, sometimes referred to as cation, anion, lattice or zeolitic water.
Thus, common hydrated metal salts are usually employed, where the presence of the salts themselves are not deleterious to the system. It appears that the bonding provided by the coordinated sphere of water in a hydrated salt is adapted to control release and/or availability of water, or water related species to the system as required to effect, engage in or control the reaction.
The overall amount of water employed, as aforesaid, has a direct bearing on the form of polymeric oxide alkoxide which is produced, and thus is selected relative to catalytic performance. ~It is believed without limitation that the stereoconfiguration of the partially hydrolyzed transition metal alkoxide determines, or contri-butes in part to the nature, or result of the catalytic action oE the activated catalyst component.) In general, it has been found sufficient to 3o 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 ~778~Z

1 precipitation of hydrolysis products from the hydrocarbon solvent medium may be avoided. This may be achieved in principle by reducing the ra-te of addltion and ceasing addition upon first evidence of precipitat:ion. While it is believed that -the reaction is essentially equimolar, a certain excess of water is appropriately ernployed in some cases, as i5 customary.
It will be understood that the stereoisomeric form, chain length, etc. of the hydrolysis product may be somewhat al-tered with the elevated temperature required by the ensuing reaction with the reducing metal, and in situ processes likewise will affect equil:ibria through the mass action effect. Likewise, khe cogeneration of alkanol may affect equilibria, reaction rates, etc.
The hydrolysis reaction proceeds under ambient 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 condi-tions, and can be made up to a suitable concentration level as desired, simply by dilution with hydrocarbon solvent.
The polymeric transition metal oxide alkoxides are reacted with a reducing metal having an oxidation potential higher than the transition metal~ Preferably a polymeric titanium oxide alkoxide is employed together with magnesium, calcium, potassium, aluminum or zinc, as the reducing metal.
Combinations of transition metal alkoxide, reducinq 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 preEerred levels of activity for olefin polymerization, magnesium values are ~77~12 1 supplied to the system by approprla-te se:lection of reducing metal/hydrated metal saltA
In the preferred embodimen-t (to which illustrative reference is made in the following text, as a ma-tter of con-venience), titanium tetra-n-bu-toxide (T~l') is reacted with magnesium turnings and hvdrated metal salt, most preferably magnesium chloride hexahydrate, at a temperature of 50-150C., in a reaction vessel under autogenous pressure.
TBT may constitute the reac-tion medium, or a hydrocarbon solvent may be used. Ti/Mg molar ratios may vary from 1:0.1 to 1:1 although for the most homogeneous reaction system a -~ stoichiometric relationship of TiIV to rlgo of 1:1 is pre-ferred, with an amount of hydrated metal salt to supplv during the reaction about 1 mole of water per mole or rlg~.
The hydrocarbon soluble catalyst precursor com-prises predominently Ti values in association with rlg `~ values, in one or more stereoconfiguration comp:Lexes ; believed to constitute principally oxygenated species. Some evidence of mixed oxidation states of the titanium values suggests an interrelated system of integral species of Ti Ti , and Ti values perhaps in a quasi-equilibrium relation at least under dvnamic xeaction conditions. The preferred precursor is believed without limi-tation to incor-porate (Ti-O-Mg) bridging structures.
The intermetallic compounds have special interest as catalyst precursors, in support or unsupported systems, for isomerization, dimerization, oligomerization or polv-; merization of alkenes, alkynes or substitut.ed alkenes in the presence or absence of reducing agents or activators, e.g., organometallic compounds of Group IA, IIA~ IIIA, or IIB
metals.

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1 In the preferred utilization oE such precursors, they are reacted with a halide activator such as an alkyl aluminum halide and combined with an oxqanometallic compound to form a catalyst system adapted particularly to the poly-meriæation of ethylene and comonomers to polyethylene resins.
The transition metal component is an alkoxide, normally a titanium or zirconium alkoxide comprising essentially -OR substituents where R may comprise up to 10 carbon atoms, preferably 2 to 5 carbon atoms, and most preferahly 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 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 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 considerations. Most suitably, as aforesaid, the alkoxide is a titanium or æirconium alkoxide. Suitable titanium compounds include titanium tetraethoxide, as well as the related compounds incorporating one or more alkoxy radicals including n-propoxy/ iso-propoxy, n-butoxy, isobutoxv, secbutoxy, tertbutoxy, n-pentoxy, tertpentoxy, tert-amyloxy, n-hexyloxy, n-heptvloxy, nonyloxy and so forth.

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1 Some evidence suygests that the rate of hydrolysis of the normal derivatives decreases with increasing chain length, and the rate decreases with molecular complexity viz. tertiary, secondary, normal, hence these considerations may be taken into account in selecting a preferred deriva-tive. In general, titanium tetrabu-toxide has been found eminently suitable for the practice of the present inven-tion, and related tetraalkoxides are llkewise preferred. It will be understood that mixed alkoxides are perfectly suit-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 part in the zero oxidation state as a necessary element of the reaction system. A convenient source is the familiar turnings, or ribbon or powder. As supplied comm~rcially, these materials may be in a passivated surface oxidized condition and milling or grinding to provide at least some fresh surface may be desirable, at least to control reaction rate. The reducing metal may be supplied as convenient, in the form of a slurry in the transition metal component and/or hydrocarbon diluent, or may be adcled directly to the reactor.
Whether in the case of the in situ preparation (or for independent preparation of the polymeric transition metal alkoxide), the source of water, or water related species is provided, whereby quantities of water are released or diffused or become accessible, as the case may be, in a delayed rate controlled manner during the reaction.
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 ~177~1Z

1 useable. Thus, calcined silica ge:L free of other active constituents but containin~ con-trolled amounts of bound water may be employed. In ~eneral, 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, cobalt, chromium, iron, magnesium, and the like.
The interaction of these components is conven-iently carried out in an enclosed reactor, preferably coupled with reflux capacity for volatile components at the elevated temperatures produced in the reaction vessel.
Autogenous pressure is employed, as the reaction proceeds smoothly under ambient conditions, with heating to initiate and maintain the reaction. As in any such`reaction stirring is preferred simply to avoid caking or coating of vessel surfaces, to provide intimate admixture of components, and to ensure a homogeneous reaction system.
Usually a hydrocarbon solvent such as hexane, heptane, octane, decalin, mineral spirits and the like is also used to facilitate intermixture of components, heat transfer and maintenance of a homogeneous reaction system.
Saturated hydrocarbons are preferred, having a boiling point in the range of 60 to 190C. The liquid transition metal component also may serve at least in part as the reaction medium, especially where no added solvent is employed. The reaction involves a stage where additional 3o 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 ~77~3~LZ

1 effectuate the reaction through intermediate stages with appropriate reaction times, to return volatiles to the reaction zone. Thus, bu-tanol is generated when the titanium component is titanium tetra n-buto~ide forming an azeotrope with the hydrocarbon solven-t. 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 ex-tent be a matter of choice within a broad range, depending upon the speed of reaction conveniently to be conducted. It has been found that the reaction system (constituted by the liqui~
transition metal component, dissolved hydrated metal salt, reducing metal particles and solvent, where desired) '; 15 evidences visible gas generation at about 60-70C.
suggesting an initiation temperature or activation energy level at ahout 50C. which therefore constitutes the minimum necessary temperature for reaction of the polymeric oxide alkoxide with the reducing metal. The reaction is somewhat exothermic during consumption of the reducing metal hence may be readily driven to the ensuing stage, being the reflux temperature. As the alkanol generated is laryely 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 within a period of as little as 30 minutes to 4 hours or more. Such temperatures may reach 140-190C. and of course higher temperatures might be 3o imposed but without apparent benefit. It is most convenient to operate within the range of 50-150C., preferably 70-140C. In the abser.ce of solvent, the upper limit will ll ~:17~8~Z
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 accompanies commencement of gas evolution. ~here lack of opacity or turbidity of the solution admits observation, evolution of gas ranging from bubbling to vigorous effervescence is most evident at the surface of the metal, and the generally light colored solutions immediately turn greyish, then rapidly darker to blue, sometimes violet, usually blue black, sometimes with a greenish tint.
Analysis 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 temperature, with con-tinuing gas evolution. In this stage, the alkanol corres-ponding 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.
The reaction product is hydrocarbon soluble 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-ray diffraction analysis an essentially amorphous character.
.~ 25 Molar ratios of the components may vary within certain ranges without significantly affecting the perform-ance 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 .

l2 ~77~

1 to 3.0:1.0 or more, preferably 1/0.]-1/1. An insufficient ` level of reducing metal will result in suppression of the reaction temperature such that the reflu~ temperature of the pure solvent remains unattainecl; whereas an excess of reducing metal will be immediately apparent from the uncon-sumed portion thereof, hence the desired amount of this component ls readily ascertained by one skilled in the art.
Within these ranges, a varying proportlon 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 componen-t 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/H2O 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 MgC12 6H2O, 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 H2O 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.

~7t39~Z

l It is nevertheless specifically contemplatecl w.ithout limita-tion, as an operative hypothesis -that the water, or the rate of reaction controlling wa-ter-rela-ted species is activated, released, made accessible to or diffuses in a manner pro-vidinq such species in a regular, sequenced, constant orvariable rate-rel.ated manner. The same molar proportion of free water supplied at -the commencement of the reaction is however wholly ineffective in initiating reaction at this or higher temperature, and results in undesirable complete hydrolysis 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 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 stoichio-metric balance to the transition metal component.
The selection of aquo complexes or hydrated metal salts where employed is essentially a matter of the control-led availability of water it affords to the system. Thus, sodium acetate trihydrate is suitable~ as is magnesium acetate tetrahydrate, magnesium sulphate heptahydrate and magnesium silicon fluoride hexahydrate. A salt of maximum degree of hydration consistently with the controlled release afforded by the coordinate bonding relationship is prefer-red. Most conveniently, a hydrated maqnesium halide such as magnesium chloride hexahydrate or magnesium bromide hexa-3o hydrate is employed. These salts, like other hygroscopicmaterials, even when supplied in commercial anhydrous form contain some sorbed water, e.g., 17 mg/kg (see U.K. Patent ` ~L77812 1 1,401,708) although well below the molar quantities contem-pla-ted in aecordance with this inventlon. Henee, anhydrous ; grade salts unless specially modified for the purpose are not suitable herein.
The reaction system, as def:ined in the above description does not require, 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 partieipate or compete in the reaction system.
No separations are necessary as at least a portion f 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 storage, a workahle reactive slurry ma~ be readilv 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 alky] silicon halide, a titanium halide, or an alkvl boron halide. It has been found that the catalyst precursor may be activated readily~
by merely eombining the product with the halide activator.
The reaction is vigorously exothermic, hence the halide aetivator is typically added gradually to the reaction system. Normally, upon completion of addition, the reaction is also complete and may be terminated. The solid reaction product, or slurry may then be used immediately, or stored ~ for uture use. Usually, for best eontrol over moleeular ; 35 ~5 ~77E~

1 weight characteris-tics, and particularly for production of low density resin, only the hydrocarbon washed solid reaction product is employed as the catalyst.
The halide activator is commonly supplied for interreaction at a molar ratio of 3:1 to 6:1 (aluminum, silicon or boron, relative to the transition metal) although ratios of 2:1 or more have been used successfully.
The resultant catalyst product may he used directly in the polymerization reaction although it is typically diluted, extended or reduced as required to provide in a convenient feed an amount of catalyst equivalent to 80-100 mg/transition metal, based upon a nominal productivity of greater than 200,000 gm polvmer/gm transition metal in continuous polymerizations which the present catalyst ordinarilv exceeds. Ad~ustments are made by the artlsan to reflect reactivity and efficiency, ordin-arily by mere dilution, and control of feed rates.
The transi-tion metal containing-catalyst is com-bined for use in polymerization with an organometallic co-catal~st such as triethyl aluminum or triisobutyl aluminum or a non-metallic compound such as triethylborane.
~ A typical polymerizer feed thus comprises 42 parts of iso-; butane solvent, 25 pts. o ethylene, 0.0002 pts. catalyst (calculated as Ti), and 0.009 pts. co-catalyst (TEA, calcul-ated as Al), to a reactor maintained at 650 psig. and 160F.
In general, the amount of co-catalyst, where employed, is calculated to range from between about 30 to 50 ppm calcul-ated as Al or B, based upon isobutane.
Examples of metallic cocatalysts include trialkyl aluminums, such as triethyl aluminum, triisobutyl aluminum, trinoctyl aluminum, alkyl aluminum halides, alkyl aluminum alkoxides, dialkyl zinc, dialkyl magnesium, and metal boro-l6 ~ 2 1 hydrides including those oE 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 decaborane.
The polymerization reactor is preferably a loop reactor adapted for slurry operation, -thus employinq a solvent such as isobutane from which the polymer separates as a granular solid. The polymeriza-tion reaction is conducted at low pressure, e.g., 200 to 1,000 psi and a temperature in the 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-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 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, 1-heptene, 1-decene, or 1-dodecene may be used, from as little as 0.2~ by weight, especially where monomer admixtures are employed~
The polymerization may nevertheless be conducted at higher pressures, e.g., 20,000 to 40,000 psi, in auto-clave or tubular reactors where desiredO
In referrinq herein to an intermetallic "compound"
3O 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, 7~L2 1 clusters, or other interengagement under the applicable conditions, the in-tegrated reaction in general being evidenced by color change and gas evolution, probably ` reflective of reduction-oxidation, rearrangement and association among the unconsumed elements of -the reaction sys-tem.
The following Examples taken in conjunction with the foregoing description serve to further illustrate the invention, and of the manner and making and using same. All parts are by weight except as otherwise noted. Melt indices are measured under conditions E & F, respectively, of ASTM
D-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 distribution. Other tests are as indicated, or as conventionally conducted in the related arts.

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~ 20 . ,.
i,

3 ~L~77~3~Z
, A. 6. n pts. of Ti(OBu)~ [TBT] and 4.2 pts. of CrC136H2O 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 reaction product free of excess magnesium (which had completely disappeared), was a viscous green liquid, soluble in hexane.
B. In a similar run anhydrous chromium chloride was employed with the titanium alkoxide, but no reaction occurred, with heating a-t greater than 100C. for a half hour. Addition of zinc dust and further heating at greater than 150C. 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.

. .

~L~778~Z

l EXAMPLE II
A. TBT (0.121m), CrCl3 6H2O (0.015m) and M~
(0.0075m) were combined in a stirred reaction vessel ` 5 equipped with an electric heating mantle. The chromium salt was wholly dissolved at about 60C., and reaction with the magnesium shavings was apparent from gas evolution at 85C., which was vigorous at 100C., subsiding at 116C. with some Mg remaining. After dissolution of the remaining Mg, heating was continued, to a total reaction time of 1 hour and 45 minutes. The reaction product at room temperature was a dark green liquid which dissolved readily in hexane.
B. In the same manner, a reaction product was prepared in the proportions 0.116m TBT, 0.029m CrCl3 6H2O
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 TBTI 0.058m CrCl3 6H2O, 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 CrCl3 6H2O, 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 octane. The clear green color of the reaction at 70C. turned muddy with increasing gas evolution and darkened to almost black at 90C. The .

i ~0 ~ ~7 7 B~f~

color returned to green at 119C. and the reaction was terminated at 121C. wi-th complete disappearance oE the magnesium. The reaction product (6.9 wgt.%, Ti, 3.5 wgt.~
Mg, 1.3 wgt.~ Cr) was a dark olive yreen liquid and a solid of darker color (about 50:50/volume) which settled out.
F. In yet another run in octane, -the reactants were provided in the proportions 0.150m TBT, O.nSlm CrC13-6H2O and 0.150m Mg. Again, the muddy green color changed to almost black with vigorous effervescence, forming at 109 a dark blue black reaction product. (5.7 wgt.~ Ti;
2.9~o Mg, 2.1 wgt~ Cr).

;~
,:

3o ~771~z A. The reaction product IIE was combined in a reaction vessel with isobutylaluminum chloride added drop-; 5 wise in proportions to provide a 3:1 Al/Ti molar ratio. Thegreen colored mi~ture changed initially to brown violet at 38C., which upon completion of reactant addition at 39C.
had changed to red brown in appearance. After 30 minutes additional stirring, the reaction was terminated, the pro-duct being a dark red brown liquid and a dark brown precipi-tate.
B. Reaction product IIF was similarly reacted with isobutyl aluminum chloride (3~1 Al/Ti molar ratio).
The peak temperature with complete addition was 48C., but no brown color change was evident. The reaction product was a clear liquid and a dark grey precipitate.

3o 22 ~7E~

l EXAMPLE IV

The catalyst components prepared in Example III
above were employed in the polymeriæation of ethylene (190F., 10 mol% ethylene, 0.0002 pts. catalyst calculated a~s Ti, triethyl aluminum about 45 ppm, calculated as Al, H2 as indicated) with results set forth in Table I, as follows:

' 10 ,:

,~ 20 i 3o , ` 23 ~7~Z

TABLE I

; H Prod. Resin Properties Catalystp2l~ g Pe/g Ti hr ML HLMI HLMI/r1I

IIIA 60 35160 10.1 265 26.3 120 29220 18.9 618 32.6 lO IIIB 60 30380 9.6 264 27 1~0 26880 32.8 g55 26.1 t ;~
,, ~1778~Z

In the following Example, the catalyst component of the invention was prepared from the reactant admixture in the absence of added solvent.

EXA~IPLE V
, A. 0.1212m Ti(OBu)4 [TBTl, 0.121m magnesium turnings and 0.0012m MgCl2 6H2O (TBT/Mg/MgCl2'6H2O =
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 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 MgCl2 6H2O
was increased (TBT/Mg/MgCl2 6H2O = 1:1:0.1 molar). The gold yellow liquid became greyish with gas evolution at 104C., 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. A11 of the magnesium was consumed.

~ 25 ~7781~
,.
;
1 The fo]lowing Example shows the preparation carried out in a hydrocarbon solvent.

EXAMPLE VI

r~ A. 50.2 pts. (0.148m3 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 MgC12 6H2O added with heating over one minute. At 75C. ~20 minutes) the magnesium salt had entirely dissolved, and at 95C. (25 minutes) gas evolution at the surface of the magnesium turnings commenced, the evolution increasing as the solution turned greyish and then deep blue, with refluxing at 117C. (35 minutes). The magnesium metal had entirely reacted within 1 hour (128-129C.) 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 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:

3o ~77~3~Z
1 Ti/Mg/MgCl 6H20 Ti/Mq Mol Rat~o _ (Molar) Motes ! 1. oTo. 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 blue black liquid, 6.6 wgt~ Ti, 3.9 wgt% Mg values (calc) 1/1/0.34 0.75 Dark blue black liquid, 6.7 wqt% Ti, 4.6 wgt% Mg values (calc) 1/1/0.51 0.66 Milk~ 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 qel. Some unreacted Mg 1/2/0.34 0.43 Dark blue black liquid and viscous gel. Some unreacted Mg.
2/1/0.17 1.70 Example IIA
2/1/0.34 1.50 Blue black solution. 7.1 wgt%
Ti, 2.3 wgt% Mg values (calc) 3/1/.51 1.99 Blue black liquid with slight green tint. 6.1 wgt~ Ti, 1.6 wgt~ Mg values (calc) 3o ~l~77E~1Z
1 C. The preparation 1/1/0.34 obtainecl above was repeated except that 63.7 pts. TBT was em~loyed with 67.5 hexane as -the solvent reaction medium. A dark blue black liquid resulted, containing by calcination 8.2 wgt~ Ti and 1.6 wgt% Mq values.

28 ~778iLZ

; 1 The following Example shows the stepwise prepara-tion of the catalyst component.

EXAMPI.E VII
, 5 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 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 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.
~ 20 The reaction product was activated with ethyl ;~ aluminum dichloride at a 3/1 Al/Ti ratio to form a catalyst ' component for olefin polymerization.

:

2,9 ~7812 1 The following Example evidences the significance of level of bound water.

EX~IPLE VIII

A series of identical runs were performed at the molar ratio 1/0.75/0.128 (TBT/Mg/MgC12 6~2O) except that the degree of hydration of the magnesium salt was modified.
When MgC12'4H2O was employed (H2o/rqg = .68/1 as compared to 1:1 for MgC12 6H2O), only 89.1~ of the magnesium metal reacted. Use of MgC12 2H2O at the same overall molar ratio (H2O/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 H2O/Mg ratio. All of the magnesium metal reacted. It was also ohserved that the amount of insoluble reaction product increased with increasing salt levels.

3o ~L~77~
.

1 The following Example illustra-tes the use of other titanium compounds.

EXA~IPI,E IX

A. 45.35 pts. (0.1595m) Ti(OPrl)4, 0.1595m ~g and 50.85 pts. octane added to a stirrecl reaction flask fitted with an electric heating mantle, and 0.027m of ~qC12 6H2O were added. The milky yellow mixture became grev with reflux, at about 88C., and turned blue at 90C. with gas effervescence. Based upon magnes:ium remaining, it was concluded that the reaction was partially suppressed by the oc-tane/isopropanol azeotrope present.
B. The reaction described in A was repeated, at a reactant mol ratio of 1/0.75/0.]28 using decalin (b.p 185-189C) 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-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, providin~ a blue black liquid and dark preci-pitate. About 50% of the magnesium reacted.
~. Titanium tetranon~late was similarly employed, with magnesium and r~gcl2 6H2O, at a mole ratio of 1/0.75/
0.128. A blue liquid was formedr 45% of the magnesium having been consumed.
E. The reaction product of titanium tetrachloride 3o and butanol, (believed to be dibutox~y titanium dichloride) was reacted with magnesium and magnesium chloride hexa-hydrate at a molar ratio of 1/0.75/0.]28 under conditions `:

. 31 ~177B12 1 simi.lar 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 recov-ered.

-: 15 :`~

. .

, ~
: 25 ~ 30 32 ~1~77~2 l The following Example employs a zirconium metal alkoxide.

ExArlp-I~E X

A. 12.83 parts of Zr(~Bu)4 BuOM (0.028m); 0.34 pts. Mg(0.14m) in the form of commercially 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 reaction. 0.97 pts. of MgCl2 6H2O
(0.005m) was added whereupon vigorous effervescence was noted, and the reaction mixture became milky in appearance.
~ . 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 ptso mineral spirits (bp 170-195C.) and 4.79 pts. MgC12 6H2O (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 ~rom the surface of the magnesium metal was evident when the temperature had attained 85C., at 8 minutes reaction time.
Gas evo]ution 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, containing 6.8 wgt~ Zr and 2.4% Mg (2.8:1 Zr/Mg by weight; 0.75 Zr/Mg molar ratio) which was soluble in hydrocarbons.
The reaction product may be activated in known manner with, e.g., an alkyl aluminum halide by reaction 1 therewith conveniently at a molar rati.o of about 3/1 to 6/1 Al/Zr to provide, in combination with an organic or organo-metallic reducing agent, an olefin polymeri.za-tion catalyst system adapted to the formatlon of polyethylene resin.

3o 34 ~L778~Z

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

EXAMPLE XI

A. 0.074m Ti(oBu)4; 0.074m Ca (thick turnings supplied commercially, mechanically cut into smaller pieces) and 0.0125m MgCl2 6~2O were combined in octane in a stirred reaction vessel equipped with an electric heating mantle.
Upon attaining 105C., the solution darkened in color, and at 108C., with gas evolution, the solution took on a dark grey appearance. At 110.5C. rapid qas evolution was evidenced, followed by formation of a dark blue liquid. At sn minutes, the reaction was terminated and a reaction product comprising a dark blue black liquid with a greenish tint isolated.
The run was repeated at the same molar ratio. 50%
of the calcium reacted to provide a dark blue liquid and grey solid containing 6.2 wgt% Ti, 2.6 wgt% Ca, and 1.1 wgt%
r~g (molar ratio 1/0.5/0.34) (XI A1).
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. he reaction product (molar ratio 1/0.47/0.128) contained 6.6 wgt~ Ti, 2.6 wg-t~ Ca and 0.4 wgt% Mg (XI A2).
B. The reaction product XI A1 were further reacted with ethyl aluminum chloride at a 3/I and 6/1 Al/Ti molar ratio. The reaction products were diluted with hexane and the halide activator added slowly to control the highly 3o exothermic reaction. In the 3/1 run the off white slurry initially formed resolved upon completion of the reaction to 3s ~ ~778~Z

1 a pink liquid and a white precipitate. At 6/1 A1/Ti ratio, the slurry changed in color to grey, and then lime green.
Reaction product ~I 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 polymeri~ation, with results as indi-cated in the following Table.

3o 36 ~77~1Z

~ o~ ~, ~ o H ~ ~ N Ul o ~D
~1 ~ ~
o o H ~1 1-- ~) O ~1 ~D
,:~ ~ 'r r` N N ~1 ., O
P~
~ ~r ~'7 ~ L
H ¦ 00 0 1` 0 ~) 1`
1-- 0 ~1 15 , ~ '~ o o o o o o Q~
U ~ cn C!:) 1~ N ~r O
~;~ - o ~ o ~ t~ ~ ~
HO ~1 ~ ~r ~ ~ ('`i ~)~) 1:'1 ~1 ~ ::~
~ ~4-- Q
~:
E~

~,1 o o o o o o -E~
~ V~
o o .
~rl u ~ r~
C) P~ ~a a),~
o; ~ ~ ~ u~
o 0 ~ 0~ a ~J a) ~ u h s0~ o :: O ~ 1 0~
5~N_ ~ ~0 1 U~ I O O
~ O a~ . U~ 0 ~ ~D
r-l 0 NQ) I ~ -1 1 ~ r-l ~1 ~ r-l O O
0~ 0 a . o U ~ S~ ~ ~ a) ,~
1 0 O u~ a) a~ o 0 ,-~
d ~ _I~ ~ ~ h ~ o o ~ ~ ~ a I ~: ~
Em o O u ~ E~ V ¢11~

37 ~7~812 1 The runs evidenced a somewhat broader molecular weight distribution in the resi.n as compared to the use of magnesium as the reducing me-tal.

.: 5 ':

3o .

~L~77812 1 The substitution of zinc as ~he reducing metal is shown in the following Example.

EXAMPLE XII

A. 0.204m TBT, 0.153m of Zn granules, and 0.026m of MqC12 6H2O were combined in octane in a stirred enclosed system equipped with reflux, and externally heated. Within 13 minutes (85C.) a rapid color change to hlue 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, 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 10-13C. (XII ~1).
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 B1 prepared above was washed thoroughly in hexane and employed in the preparation of low density polyethylene resin. The reactor was preloaded with sufficient butene-l to secure target density, and the reaction conducted (with incremental addition of butene-1 along with the ethylene) 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, HLMI 52.1 and MIR 31.

' 39 ~ 7~Z

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

_AMPLE XIII
,, 5 62.7m mol of TBT, 47m mol of fresh potassium metal (scraped clean of its oxide/hydroxide coating under octarle!, and 8.Om mol of MgC12'6H20 were combined in octane ;n an enclosed system equipped with reflux, and externally heated.
Within 2 minutes at 35C. the color changed to blue hlack, 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 precipita,te was recovered.

'~ ~5 , 3o ~7~8~

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

EXAMPLE ~TV

A. 112.31 pts. of Ti(OBu~4 (0.33m), 8.91 pts. of Al (Alfa Inorganicspherical aluminum powder, -45 mesh~ and 11.4 pts. of MgCl2 6H2O (0.056m) [molar ratio 1:1:0.171 were admixed in a reaction vessel wi-th stirrinq, and heat applied, employing an electric mant]e.
When 100C. was attained in about 10 minutes, the yellow color deepened, and at 118C. vigorous effervescence commenced, with gas evolution. At 122C. 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 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 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. 9ol0 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 3o ethyl aluminum dichloride was added gradually, the temperature being maintained at 15-20C. The admi~ture, ~77~

l stirred for 30 minutes provided a dark red brown slurry and an intractable solid. (B1).
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 ~ 7131Z

l _XAMPLE XV

The reaction products of Example X:[V were employed as catalysts in the polymerization of ethylene under standard conditi.ons (190F., 60 psig E12~ employing triethyl aluminum as a co-catalyst, with results as follows:

MI HLMI MIR
Bl 0.14 6.45 46.1 B2 0.38 17.4 45.7 ., 3o 43 ~ Z

l _XAMPLE XVI

A. In a similar manner to the forecJoing, 0.133m TBT, O.lOOm Al, and 0.017m AlC13'6H2~ were comblned in octane and reacted over 7 hours and 15 minutes -to provi~e a dark blue black liquid and a small amoun-t of a grey solid.
About 40 per cent of the aluminum reacted to provide a reaetion product comprised of 6.6 wgt% Ti and 1.6% al.
(XVI Al).
In the same manner, the same reactants were combined in a l/l/0.17m ratio. About 53% of the Al reacted, to provide a reaction product containing 6.5 wgt% Ti and 2.7 wgt% Al. (XVI A2).
B. The reaetion produets (XVI Al) and (XVI A2) were aetivated 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 170F., 15 psig H2 to produce resin character-ized by MI .02, HI.MI 1.01, MIR 50.5 and in a second run MI.02, HJ.MI .45 and MIR 22.5.

3o ~L~L77~3~Z

1 The followin~ Examples are drawn to catalyst com-ponents prepared employlng other aquo complexes.

EXAMP~.E XVI I

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 heatinq to 65~C. A grey color developed with gas effervescence, and the solution turned blue, then blue black with a greenlsh 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 reaction product was pre-15 pared at a mole ratio of ~Ti/Mg/MgBr2 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 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 precipitate. (IV
B-1) The 6/1 product (IV B-2) was prepared in similar manner with the same results.
In a separate run, the reaction product (XVII A) was combined with SiC14 in the same manner. The reaction product of a 30 minute reaction at a 3/1 Si/Ti ratio was a light yellow liquid and a brown precipitate. A similar run provided a 6/1 Si/Ti reaction product.

~7781~

1 C. The activated reaction products XVII B~1 and XVII B-2 (1% Ti by wei.ght) were employed in -the polymeri~ation of ethylene (10 mol % in isobutane) at 190F., with hydrogen modifier and triethyl aluminum cocatal~7st ~45 ppm Al) and compared to an identical run using magnesium chloride hydrate, with results set forth in Table III as follows:

3o ~6 ~ 78~2 , 1 .~ ~ c~
I~ H
h ~1 N N I~ ~'7 p::
~ H I , coco I,~ a~
~rl ~ ~ ~ I~ D
P~ m S I r` N ~) oo ~5 ~1 3 ~ r~ ~ c r N [`
o ,~ N O~I r1 `:

. ~ s .
: ~-rl O O O O O O
rl E-l t- O ~ ~co u~
~ O~ rl r ~ ~ O
u ~
,~ ~ ~ ~ ~ r~ ~r 1-~ W cr c~r o t--H P~ ~ I
H P~ t~
H
W
20 ~
,_ ,~ o o o o oo 5.; U~ V ) N ~N ~ N
Q~ ,~

: 25 ~ ~ ,~
E~r~
O ~ ~ ~D
,¢ ~

3o '¢ O O
l tr: X
b~ ~
N N
~ c r ,~
r-~_ U
tJ~
~O
~., E~

47 ~.3L77~Z

1 EXAMPLE XVI:[I

A. 42.23 pts. o~ TBT (0.124m) were combined with 3.02 pts. Mg (0.124m) in octane (~2.8 pts.) in the presence of 5.7 pts. FeC13 6H~O (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 65C. gas evolution began. The muddy yellow color turned dark brown at 80C. (7 minutes) and gas evolution increased. In about 30 minlltes gas e~olution had slowed and then ceased with consumption 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.
Diluticn with hexane caused no precipitate or deposition of residue. (XVIII 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 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 liquid and grey precipitate contained lh Mg Ti/g.
C. Activated reaction product XVIII Bl was employed in the polymerization of ethylene at 190F., 60 psi ~2. 11~,320 g PE/g Ti/hr were recovered, exhibiting the following properties: ~I 5.1, ~ILMI 155.3, MIR 30.3.

48 ~.'77812 .

A. l. 0.160m Ti (Ohu)~, 0.160m maqnesium turnings and 0.027m CoCl~ 6H?O were comhined 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 app~ars at 58C., increasing to vigorous effervescence at 107C. within 12 minutes. The clear b]ue 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 pr~cipitate upon standing The run was repeated, with essentially identical results.
B. The reaction product of the foregoing prepara-tion was shaken, and 0.011lm (Ti) was combined with isobutvl aluminum chloride (0.0333m A1) supplied dropwise to a reaction vessel. The temperature peaked at 40C., with formation of a greyish precipitate, which upon further addition of ~uAlC12 turned brown. After s-tirring for an additional 30 minutes the reaction was terminated, pro-25 vidiny a dark red brown liquid and a brown precipitate.
C. The catalyst component prepared in Example XIXabove was employed in the polymerization of ethylene (190F., 10 mol % ethylene, 0.0002 pts. catalyst calculated as Ti, triethyl aluminum about 45 ppm calc as Al, ~ as 3O indicated) with the results set forth in Table IV, as follows:

'19 ~L~77~Z

1 TABI,E IV

H Prod Resin Properties Catalyst ~g PE/g Ti/hr MI HLMI HLMI/MI
XIX B 60105,1806.2 206 33.6 12075,29033.9 950 28.1 ` 10 ;

';

: 15 i~-. .

-3o so ~ 12 ,.
: lEXAMPLE XX

A. 0.169m Ti(~Bu)4 [TBT], 0.169m magnesium turnin~s, and 0.029m AlCl3 6H2O in octane as a diluent were combined in a stirred reaction vessel equipped with an elec-tric heating mantle. The hydrated aluminum salt partly dis-solved and at 111C. the solution rapidly darkened to a black liquid with vigorous effervescence originating with ; gas evolution at the surface of the magnesium. The solution took on a blue coloration and, with smooth refluxing to 122C. formed a dark blue-black liquid with some remaining magnesium. At 125C., 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-cipitate recovered, in a volume ratio of about 95/5.
B. The reaction product described above was com-bined 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 v~ssel containing the titanium material. In the first reaction (3:1), the alkvl chloride was added at a rate of 1 drop/2-3 seconds until a peak temperature of 42C. 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 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-3o merization of ethylene (10 mol ~) with isobutane diluent at190F. and hydrogen as indicated. The runs were terminated ~778~L2 , ,. ~., .. l 1 after 60 minutes, with results indicated :in Table V, as follows:

:

3o ~77~
.
.`........ 1 ~` TABLE V
,,_ H PEProd Resin ProPerties Catalyst p~ig mole g PE/g Ti/hr MI HLMI HLMI/MI
~
XX B 60 40684,580 17.2 517 30.1 120 54275,280 54.9 1413 25.7 XX C 60245 54,440 4.11 129 31.4 120 18334,860 26.2 801 30.5 ;

3o ` 53 ~7~z l EXAMPLE XXI

A. 0.153m Ti(OBu)4 [I'BT], 0.153m Mg turnings and 0.026m NiCl2 6H~O were combined with 61.75 pts. of octane in a stirred reaction vessel equipped with an electric heating mantle. With heating to 4~C. the yellow solution deepened in color, and gas evolution on the magnesium metal surface became observable at about 57C. Wi-th continued heating, the gas evolution increased until at 102C. (15 minutes reaction) the reaction system turned a light muddy brown color. Vigorous effervescence continued wi-th darkening of the brown color until at 126C. l75 minutes) all the maqnes-ium had disappeared, and the reaction was terminated. The reaction product (XXIA-1) was a hydrocarbon soluble dark brown liquid and a small amount of a fine precipitate.
In a second run 0.149m TBT, 0.149m Mq, and 0.05lm NiCl2-6H2O 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 soluble liquid, which resolved on standing to a very fine dark precipitate and a yellow liquid, about 50/50 by volume (XXIA-2).
B. Reaction product IA-l was sha]cen, and a por-tion (0.0137m Ti) was placed in a reaction vessel with hexane diluent, to which iBuAlC12 (0.0~llm A]) 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 comple~ion 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/l 54 ~ 1~7 8~ ~

l Al/Ti molar ratio. The reaction product was a dark red brown liquid and a dark yrey solid. (XXIB-2).
In an essentially identical manner, reaction produc-t XXIA-2 (Ti/My/Ni molar ratio 1/1/0.34) was combined with iBuAlC12 at a 3:1 Al/T1 ratio, with the same results, except that the superna-tant liquid was a pale red brown color. (XXIB-3).
In a further run, reaction product XXIA-2 was reacted in the same manner with iBuAlCl2 at a 6:1 Al:Ti 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 li~uid and a dark grey solid. (XXIB-5).

3o ` 55 1~'7~B~

, .
.
, 1 EXAMPLE XXII

A. Example XXIA was repeated, with the reactants supplied in the molar ratio Ti:Mg:Ni of 1:0.65:0.11. The color change was from deep brown yellow to dark brown with gas evolution, and thence through a grey brown to dark blue black upon consumption of magnesium, in a reaction occurring :~ over a period of 6 hours. (XXIIA).
B. Reaction product XXIIA was combined with ethyl aluminum chloride in the manner of Example XXIB at a 3:1 Al/Ti molar ratio. A red brown liquid and red brown preci-pitate was recovered. (XXIIB).

3o Example XXIIA was repeated, with the reactants supplied in the molar ratio 1/0.75/0.128. The dark brown reaction product contained 5.9~ Ti, 2.2~ Mg and 0.97~ Ni.
The reaction product was then treated with isobutyl aluminum chloride at an Al/Ti molar ratio of 3/1.

3o ~ 71~Z

l EXAMPLE XXIV

A series of TMgNi catalysts, prepared as set forth in Examples XXIB and XXIIB, were emploved as catalyst com-ponents in the polymerlzation oE ethylene (190F., 10 molethylene, triethyl aluminum about 45 ppm calc as Al, H2 as indicated) with the results set forth in Tahle VI, as follows:

3o ~'77~3~2 l TABLE VI
HProductivity Resin Properties Catalyst ~gg PE/g Ti Hr MI HLMI HLMI/MJ.
. __ XXIB-3 6090,750 9.55 270 28 120104,980 24.6 683 27.8 601]1,940 0.29 10.7 36.8 120112,260 3.1 119 38.9 XXIB~4 6059,790 0.25 10.9 43.6 12062,720 1.0 43.6 43.6 XXIIB 6057,890 1.66 54.9 33.1 12064,740 6.13 183 29.8 XXIB-2 60238,670 0.65 19.5 30.2 ; 15 120271,560 6.7 188 28.1 XXIB-5 3011?5,000 Low .
Runs at higher levels of hydrogen were extremely rapid, resulting in polymer buildup requiring termination of runs.

3o ~.778~Z

1 E~AMPLE XXV

A. T~T, 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 ]/1/0.34 and 1/0.75/0.128, respectively.
R. The latter reaction product was activated by reaction with ethyl aluminum chloride at a ratio of 3/1 Al/Ti.
C. The resulting ~rown 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 (190F, 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 he~ane and employed with TEA in a polyethylene polymerization reactor preloaded with butene-1 to provide resin of targeted densitv at 170F., 30 psi H~ from the ethylene/butene-1 feed. The resulting resin had a density of .9193, MI 1.91, HLMI 60.8 and MIR 31.8.

3o .

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

EXAMPLE XXVI
_ A. In the following runs, T~Mg reaction products were reacted with the halide component added gradually thereto, usually dropwise -to control the exothermic reaction. The reaction was conducted under ambient conditions for a period of time sufficient to 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:

' ,; .

6 1 ~77~

1 Catalyst Component, mol ratio Ti/Mg/MgCl 6H~O (H O) Halide Activator Mol Ratio -- 2 ~ _ _ 1/0.65/0.11(0.66) Bu AlCl2 2/1 Al/Ti 1/0.65/0.11(0.66) Bu AlCl2 3/1 1/0.65/0.11(0.66) Bu AlCl2 4/1 1/0.65/0.11(0.66) Bu AlC12 6/1 1/0.65/0.11(0.66) EtAlCl~ 3/1 ; 1/0.65/0.11(0.66) EtBCl2 1.25/l(B/Ti) 1/0.65/0.11(0.66~ EtBCl2 3/1 (B/Ti) 1/0.65/0.11(0.66) SiC14 3/1 (Si/Ti) 1/0.65/0.11(0.66) SiCl4 6/1 (Si/Ti) 1/0.75/0.128(.768) EtAlCl2 3/1 1/0.75/0.128(.768) Et~Al2Cl3 3/1 1/0.75/0.128(.768) Bu AlC12 3/1 1/0.75/0.128(.768) Bu AlC12 6/1 1/0.75/0.128(.768) EtBCl2 3/1 (B/Ti) 1/0.75/0.128(.768) (C~3)2SiC12 6/1 (Si/Ti) 1/0.75/0.128(.768) (Ch3)3SiCl 6/1 (Si/Ti) 1/0.75/0.128(.768) (ch3)2siHC1 6/1 (Si/Ti) 1/0.75/0.128(.768) SiC14 3/1 lSi/Ti) 1/0.75/0.128(.768) SiCl4 6/1 (Si/Ti) 1/0.75/0.128(.768) TiC14 1.5/1 (Ti/Ti) 1/0.75/0.128(.768) TilC14 3/1 (Ti/Ti~
1/1/.17(1.02) Bu AlC12 3/1 1/1/.17(1.02) EtAlCl2 3/1 1/1/.34(2.04) Bu AlC12 3/1 1/1/.34(2.04) BulAlC12 6/1 1/1/0.51(3.06) Bu AlC12 3/1 1/1/0.51(3.06J Bu AlCl2 6/1 30 2/1/0.17(1.02) Bu AlC12 3/1 2/1/0,17(1.02) Bu AlC12 6/1 2/1/0.34(2.04) Bu AlC12 3/1 2/1/0.34(2.04~ Bu AlCl2 6/1 3tl/0.51(3.06) Bu AlC12 3/1 35 3/1/0.51(3.06) Bu AlC12 6/1 62 ~ Z

A. Catalyst samples activated with Bu AlC12 (3:1 A]/Ti) were employed in a series of polymerization runs, with results set forth in Table VII as follows:

3o 7~

H
a) ~~ 'n m o ~) N ~ N
rl HLn COLn ~ N ~ 0 I cr~
(1) ~~') N~ ~)~r) ~~ ~r) ~1 ~ ~`~ N ~I
~ 'E~
S-l H~1 00Lt~1 N a~ Oa~ O Ln O
~1~ ~ L Lnco ~ i~ ~~r o .
~:C~).-1 Ln ~ ~r .-1 ~IN ~
3 .~

N CC 1- Ln Ln ~ N ~ L ~I Ln -1 N (~1 Ln N N N ~ Ln N CO ~r N 1`
m . 3 C C ~ Ln Ln o o Ln o o o Ln o o o rl E-l~ CCO Ln~10 ~ CO Ln N O
~co ,~ n ~i~ Ln ~ ~r~ Ln ~o ~ -,~
,. HH~; ~ ~ rLn LnLn U~ N

ro E~ h ~ o o o o o o o o o oo oo o ~ , Ul ~ N~D N~D N ~ N ~0 NLD ~1 ~) N }~
Q -1 -J .-1 -J -1.-1 ~-I &
~1 Ln ~ O

2 5 LD ~ ~ N
N~ L~ U
U L Ln N Ln Ln 1` Ci~
:~ ~ .

u, ~ o -1 a ~ t~ O ~ rJ
o ~ h m o~,l -1 Q ,1 ~ O i~ E~
O . O I ~ I --1 o o .,1 N ~1 ~ H a) ~) ~) ~ -1 0 ~1 1 U~ I I I
.-~ ~ ~ Ln ~ ~ -1 h . . . . Ln Ln ~ o td O O O o 1~ LD O ~) ID a) O
o ` ` .` ~ o o ~ ~ ~ a I $~
~_ ~--i N ~ ~ 1 N ~; ~ E~ U ~

6~ 7~1~Z

1 A~; may be seen from a comparison of Ti/M~Cl~'6H~0 molar ratio, peak melt index is observecl at a 9:1 ratio (1.5:1 Ti/ll~0).

B. In the followinq additiona]. run.s the effe~t. of Al/Ti ratio in the activated T~ (mol.ar ratio 1./O.fiS/n.ll) catalvsts was e~plored in the polymerization of ethy].ene.
.Results are set forth in Table Vlll as follow.s:

3o 65 ~:~l77E~
U~
.~ ~
H r-~ ~ N ~r 11 a~ co o I ~ ~ ~ ~ o I ~ o ~
~1 ~1 ~1 N ~) I ~ t`l ~) ~1 ~) I ~) N ~) ~1 Sl H ~ D Ut I 1~ a~ Ul U~ ~ I CO ~D u~ O
~I) ~ co ~ ~r I u~ ~--1 o a~ ~ I N r-~ O ~D
3 ~ ~r ~r N N ~ 1 ~ N r~l ~0 ~1 U') H ~ 1 U~ 1~ Ul 1-- 0 0 1` 11~) U~
K ~ u~ ~ N U 1~ 5~ ~

Q
:~
~ u~ O u~ o o Ln o o o o u~ O O O a~
rl E~ co ~ ~o ~ ~ u~ ~ I` a~ ~ u~ ~ O a~
.) ~ N ~ u~ ~r N OD ~ I` ~) ~ 1 t~ N ~5 ,~ ~ U~ ~ ~' O 1~
:: 15 o p~ u~ D ~o ~r ~r ~o ~ o~ u~ ~ ~ v H _, oo oo oo oo oo c~o oo ~ O
:~ ~ &v U

~ ~ ~ ~ ~ ~ ~ E ~D

o o ~ ~ U~ ~ ~ ~ U~

U~ ~ o ~ ~ O
3 ~ o ~ ~
. ~ o, U~ ~ .,, o o In ~ O H ~ l I
rl ~ r l r~l ~ ~ U ~J
~ O r l r l r-l r~l C~ l r-l ~ a) Q) O 11~ r1 r~
rl C~ ~ l r~ t) o .rl rl rl rl l¢ ~ m r~ ~ I ~ S

` 66 ~7~2 .

l C. In a further series of experiments, employing a TM~lg catalyst at 1/0.75/0.128 molar xatio, the effect of activating agent was analyzed, with results set forth in Table VIX as follows:
. 5 :

, . 20 ~.~'77~

U~
a.) H~
00 ~D ~ O CS~
Sl H .. . .. .. . . .. .. ..
P~ 1~1 ~ ~ ~ I N ~
~0 ~
s~ u~ r- o r-~U H
o ~ I oo ~ ~r o .~ c~ o .
3 ~1 ~ ~ o I
O X

~ ~r Ln ~ a~ ~9 o~ ~
U~ H .. .. .. .. .. .. .. ..
a) ~ u~ ~ ~ ~ ~ O ~ 00 In o r~ .1 CO

rC
o o o o o o Ir, o o o o ~ o o o In N r1 ~ 00 N N ~ Nl t`~ r-l ~ Lt~ ~r 1~ ~7 N
~ .~
X ~ ~
H

~ _ r~

Nrl O O O O O O O O O O O O O O O O
X U~ ~ N ~D N ~ N ~D N ~ N ~D N ~D N ~D N E;
Q ~-1 r-t r-l r-l r~~ r~l r~

,0~
~ E~
~--1 ~D ~D N ~t~ ~D N ~r ~D r-l ~ rl r-l N ~ ,a O r-l a~
o U~
~ ~ O r~ rl r~ ~

0 ~ h 0~, ~1 O I U~ I o o a ~ H ~U
rl N N r-l ~ ~C r-l h ~ ~
C~ ~ o ~ rl ::~ ~) r-l rl rl rl r~ ~r ~ ~ ~ Q) a~ 0 11~ rl E-~ u ~ u ~
,1 m N 1'~) N ~ r~ e ~, JJ ~ ~ ~ '1 ,1 ~ o ~ ,~

` ` 6~ ~77~
.

lD. Larger sale polymerization runs were con-: ducted at 160~F. witll the TMMg 1/0.75/0.128 catalys-t (slurry, separated from supernatant l.iquid, and washed with hexane) and T~A co-catalys-t employing ethylene and butene-l as a comonomer, utili~ing varvlng butene-l ~eed, activators and activator ratios. Results are set forth in Table X as Eollows:

3o 69 ~3 ~7812 ~ ~ ,, o ~
.
~ ~ ~ Z ~ Z ~ Z Z Z ~
~ ~ ~ ~ ~ ~ ,, ~ ~ ~
~D ~o ~ ~ ~ ~ ~ ~ ~ ~D

~ oooooooooo H ¦
H O O ~1 0 00 '1 0 .
tc ~

~I H I
a) x~ ~ ~ o o o n ~
.~ x m ~J ~
o o I I o o I o ` 20 ~o ~ _ " EL~
i In ~
0 U~ Ln ~D r~ oo 25~:: 3 ~o 1~ ,~ ,, ~ I I ~ In I ~

a~ --o ~
o 30~4 ~ ~ cr~
~r ~ o ~r I, I ~ ~ I ~
I-J ~J! ~ ') ~ N ~

z I ~ m c) c~ H 1 .

~177t~12 l The resin bat~hes col].ecte~l as noted above were stabili.zed with lO0 pprn calc.ium st.earate and lO00 ppm Irganox 107~ ; characterized by conventiona~ te~sts; and converted into blown film in a l l/2" ~arti~ extrllder ~6~rpm screw; 3" die at 0.082" d.ie ~ap; cooling air 37-40F.) ar)-l further tested, all as set forth below i.n Table.s XT an~l XII:

3o 71 ~i~781z In m o o o r C~ o ~ ~\l 1~ rl ~D ~1 11~ r I ~ O r~ In r~ O~ O 0'~ r r~
~ r-l t~l 1~1 ~
a~ ~ o o o ~ ~D a~ ~ ~
co ~r ~D r~ O ~ O r~ In r rl I O O O GO O O ~D ~D ~) ~ o ~ ~ r ~ r~ In r~
X ,. ~ ~r r~
o r~ ~ ~ ~ c :' cr ~ O
~ r~
o o o ~ ; I r~ o rLI I ~ o~ In . r-~ ~ In r~~ r r- ~ r ~ r L~
O ~ N ~ ~ l O
.: O ~ r~
. ~
N

4 1 0 0 O In r t`J ~O r r1 ~' I n ~ r Ll') ~;
LO ~ ~D r~ a~ ~) ~1 1 r-l ~ ~ ~ ~ r~
.
~ ~ o n o o o o o ~ D CO h U~ ~ ¦ ~1 ~ O ~C~ r ~ r` L~
L . .-1 r~ CO ~! ~ ~ r~l ~rl 1~ r ~ l r r~
u~ a) a) a~
L~ Ul ID t~J O O O r-l ~ In ~ L~
a) a In In r I t~ r~ u~
1-1 ,~ ~ ~) ~ ) Ll x ul a~ ~
~ ~ ~ I o o o ~ c> ~
a) O~ ~ ~r) r~ CO . ~ r~ r~ Ln r a ~ U ~ co r ~ ~ r~
~i ~ r~
~0 ~~
~ , r ~r o o o o ~ In ~ co ~ ~; m ~ r Ln s~
Q) ~ rl r~ ~ r-l ~ eJ~ r I
L. IYI r--l ~ Ln O~

:' r~
~1 ~D ~D o I o ~ r~ Ln ~D r-~ h - ,¢ Ln ~r ~ I o . . ,~ r~ u7 ~
. rl ~ ~ ~ r~ r1 r~) ~ r-l 2 5 ~ a~
', ~ L~ aj .rl `'' ~ '~ E~ u O r O ~ ~ u~ h N: O N
O r~ 1: ~ X
~ rJ U~
X
a) ~
O Ul ~ rl r-l r-l al -1~ 0~ ~rl ~
~u o~n o ~ ~ a ~ ~
r~ U
J ~ ~ u~ h ~ O ~ ~ .,LJ o~P r-l U U~ I:4 0 a) ~ _~ ~ a) ;~
C5!~ h L~ ` ~ Q
x ~ a~ ~ o ~
,~ u~ h O :~ H U h ,~
o ,~ o .
o o a) ~ ~ a) a) t~ ~q 350 3 r~ ~a r-l r~ ~ o r1 v~ r~ r~ ~ rJ r m u~ h o ~ a) o ~ ~ u m o ~1 a) ~ a) a) ,~
a 72 1177BlZ
o ~ ~ ~ ~
.
co r o o o o o o Ln ~ o o o ~ ~ o o CO ~ o U~ ~ o o ~ a~ ,` oo .
o o o o o o ~ ~ o o o o r~ n o o ~
~ ~r ~ ~ u) I~
In ~D
C~
~r er O ~
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:~ C~ ~ o o o o o o ~ I~ o o o o o ~r ~ r-Ul O

~ . ~ O o~ ~ ~
,~oerOOOOOO~D~OOO
~1 1~ ~ ~ ~ r~ ~ o o u~ ~ In ~ ~ ~r o~
~ 3 ~ ~ ~ ~ ~ ~ ,~
E~ ~ ~ ~D CO
,~ 3 m Q) ~
~m r 1`
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~ ... ..
~ u~ ~ o o o o o o ~ r~ ~ o o o :- ~ ~ ~ ~ ~ r I~ o~
: 25 . .. , u~ ~ ,C h oP (d o ~1 ~:: o~ ~ o U~
3 5 ,, N O ~: a) 0 o 73 ~ '77~31Z
~D
_ . I
r~ t ) O 01 >
co c m r~l ~r ~
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n ~1 o ~ o a~
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a .` ~(I) rl a~ ~ o

5 ~~. aJ o Z~ Q~
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E~ o ~ ~
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a ~ rl 3 5 s~ ~ rO
a a ~ a ~ ~ u -7'1- ~1177~

~Do o o o o~ C~
~/ o ~9 o o o o o o cr ~ o o ~D r`
t`l o~ ~ ~) ~ ~1 ~9 ~ o ~1 l~
~ o 1 0 o In o co co ; ~r~ooooooo~DOOL~
~ ~ O O;) . , U~ U~
, C: O ~ ~1 ~ ~1 . . . . . o u~ o ,~ 9 o o o o o o ~1 ~ r-l ~1 a) rl ~ O ~~
_ K ~ I-- o o o Lr~ 1 o E~ ~ )~
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''` 20 ~ 3 rl - - o o .' ~ 0 14 ~ O O O O O O O t~ ~1 0 0 C5 . ~ ~ ~1 )~ 3 u~
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2 5 ~i r~ o o o o o o ~ ~ o ~i 0 ~ ~ C~ O U~
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o o . ~U~ooooooo~1oo~

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~I N O
_ ~ ~ o O
. . U~ ~ O
~ ~r ~ o ~ ~ ~r 1~

Il~ N
N N ~
-- ~D
In . ~ O
.~ Cl~

~ O
:; _ .
O ~1 10.
,- ~r o _ ~ In o :` . I O Cl~ I~
r~ I ~ ~r ~C
~n ~rl : ~ ~ ~\ ~1 ~
15 Z ~ o' ~ o o C~ U~ s~ ~ Ln ~ o _ ~ ~ O . ~ O ~ I~
H ~ ~ r-l ~ I ~r ~r ~) X 3 ''~
O
~ ~ ~ O
~ h o3 ~
20 E~ ~ - o ,~ _ ,J ~ In o co . . o In ~0 ~ ~ ~ o N
2 5 ~ m u~ o o I o In C~
I ~

o ~rl ~

o h O -- 3 a) S~ b~
a , a ~ e a 76 ~:1'7~ Z

1 ~ E. In further l.arge sca]e polymerixa~ )n.s corl-ducted in a similar manner emp].oyin~ MMg catalyst (slurry, separated from supernatant liquid and hexane washed) a~.
molar ratlo 1/0.75/0.1~ /l A]/Ti, EADC~, hexene-l w~s ferl : 5 to the reactor as a comonomer with ethy].ene, and then butene-l was substituted providing, as fol.lowetl hy off-~a~;
analysis, ethylene/butene-l/hexene-l copolymers and ter-polymers in the course of the operation. Results art-~ set forth in Tab].e XIII, as fo]lows:

3o 77 ~ 78~Z

:
H
.: ~
H
.,, ~C

H a~ o~ ~ ~1 ~`J cs~.
:F
~_1 ~ ~ ~ ~ u~ a~
. 15 ,, ` H
:, H
~:1 '~ ~ ~ ~ ~r o o ~r O O O O o O

a~ ~ I` ~ co u 2 5 ,1 ~ a~
~ 3~ a~ ~ ~ ~ ~
a o O O O c O

3o h ~ ~a o o ~ x x ~ -c) ~ x ~

78 ~L177~Z

l EXA~PLE XXVIII

TMM~ catalyst prepared in accordance with the Examples and activated with isobutyl aluminum chloricle (3/1 Al/Tl) wa~s also employed to produce other copolyme~5 at varying comonomer preload, isobutane diluen~, ]70F. reactor temperature, 30-40 psig 11~ and TEA -to provide 60 ppm ~], with results as follows:
.:
lO Ethylene/3-Methy]butene-1MI MIR Density l.25 27.4 0.9488 1.25 28.9 n. 9483 1.36 27.9 0.9507 1.55 27.7 0.9497 1o56 ~7.5 0.9495 1.87 ~9.9 0.9496 1.63 28.5 0-9455 2.25 28.8 0.9437 1.46 30.0 0.9~28 5.01 30.3 0.9411 1.59 31.9 0.9400 Isobutylene 0.37 32.4 0.9518 1.35 29.6 0.9~64 1.79 3l.1 0.954~
1.17 31.7 0.9567 4.~0 30.1 0.9582 3.30 32.9 O.g557 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 79 ~ Z

l The following comparative experiments were also ; conducted:
.,';
COMPARATIVE EXAMPLES
,; 5 A. In the same reaction vessel used in other preparations TBT, Mg and anhydrous MgC12 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 TB above.
'` 10 B. To the same s,vstem, an amount of free water equivalent to an Mg/MgCl2 6H2O 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 6H~O 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 6H2O 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 qolden yellow liquid with heating to reflux over only 16 minutes. At a molar ratio of 1/1.17 3o foaming and formation of a thick cream colored gel termin-ated reaction after 45 minutes. Compare Example VII, above.

Claims (19)

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

1. A process for the polymerization of 1-olefins, alone or together with at least one copolymerizable monomer, under polymerization conditions of temperature and pressure with an olefin polymerization catalyst system comprising a mixture of catalysts including a halide activated intermetallic compound comprising the reaction product of a polymeric trans-ition metal oxide alkoxide and a reducing metal of higher oxidation potential than the transition metal, wherein said transition metal is selected from the group consisting of titanium and zirconium.

2. Process according to claim 1, wherein the polymeric transition metal oxide alkoxide is produced by partial hydrolysis of the transition metal alkoxide.

3. Process according to claim 2, wherein the hydrolysis 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 selected from a hydrate of a salt of aluminum, cobalt, iron, magnesium or nickel.

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

6. Process according to claim 5, wherein the hydrated oxide is silica gel.

7. Process according to claim 2, 4, or 5, wherein the molar ratio of transition metal to water is from about 1:0.5 to about 1:1.5.

8. Process according to claim 1, 4, or 5, wherein the reducing metal is magnesium, calcium, zinc, aluminum or mixtures.

9. Process according to claim 1, wherein during the formation of said reaction product the transition metal and reducing metal are present in a molar ratio of from about 0.5:1 to about 3:1.

10. Process according to claim 1, wherein said catalyst, as reducing metal, and said reaction product as transition metal are present in a molar ratio of from about 3:1 to about 25:1.

11. Process according to claim 1, 9, or 10, wherein the halide activator compound is at least one of an alkyl aluminum halide, a silicon halide, an alkyl silicon halide, a titanium halide and an alkyl boron halide.

12. Process according to claim 1, 9 or 10, wherein the catalyst mixture includes an organo aluminum or organo boron compound.

13. Process according to claim 1, 9 or 10, wherein the catalyst mixture includes triethyl aluminum or triethyl borane.

14. An olefin polymerization catalyst system com-prising a mixture of catalysts including a halide activated 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 said transition metal is selected from the group con-sisting of titanium and zirconium.

15. The catalyst system of claim 14 wherein the halide activator is at least one of an alkyl aluminum halide, a silicon halide, an alkyl silicon halide, a titanium halide or an alkyl boron halide.

16. The catalyst system of claim 14, wherein the reducing metal is magnesium, calcium, zinc, aluminum or mixtures.

17. The catalyst system of claim 14, wherein the polymeric transition metal oxide alkoxide is the product of the controlled partial hydrolysis of a titanium alkoxide.

18. The catalyst system of claim 14, 16, or 17, wherein during the formation of said reaction product the transition metal and reducing metal are present in a molar ratio of from about 0.5:1 to about 3:1.

19. The catalyst system of claim 14, 16, or 17, wherein said catalyst, as reducing metal, and said reaction product as transition metal are present in a molar ratio of from about 3:1 to about 25:1.

-