NL8105319A - PROCESS FOR POLYMERIZING 1-OLEGINS, AND A CATALYST SYSTEM INTENDED FOR IT. - Google Patents

Abstract

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

Description

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Process for polymerizing 1-olefins and a catalyst system intended for that purpose.

The invention relates to intermetal compounds of transition metal alkoxides and processes for its preparation. More particularly, the invention provides catalyst precursors for interreacting with halide activators to form a catalyst component suitable for the polymerization of <K -olefins,

Polyethylene, prepared by solution or dispersion processes under small pressures or in an autoclave or tubular reactors under higher pressures, has been a subject of commercial preparation for many years.

In the recent past, interest has focused on low density linear polyethylene resins characterized by linearity and short chain olefin-induced branching of olefin comonomers, and which have molecular weight distribution within narrow limits, improved strength properties, greater melt viscosity, exhibit higher softening point, improved ESCR (Environmental Stress Crack Resistance) and improved low temperature brittleness. These and related properties mean benefits to the user in applications such as e.g. blown film, wire and cable sheathing, cast film, coextrusion and injection molding, and rotational molding.

The linear olefin polymers were typically prepared using catalysts of the general type described by Ziegler, thus containing a transition metal compound, usually a titanium halide, mixed with an organometallic compound, such as alkyl aluminum. The transition metal component can be activated by reaction with a halide promoter, such as 8105319 • i - ..... -2-.

as b. v. an alkyl aluminum halide. Among the improved catalysts of this type are those of which a magnesium component forms part, usually by the interaction of magnesium. or a compound thereof with the transition metal component or the organometallic compound, e.g. by milling or chemical conversion or association.

There is also an interest in the preparation of medium to high density resins, with altered properties, using coordination catalysts of this type. In particular, there is a demand for resins with a molecular weight distribution within wider limits and with a greater melt index.

The invention relates to an olefin polymerization catalyst system consisting of a mixture of cocatalysts, one of which is a halide-activated intermetal compound, which consists of the reaction product of a polymer transition with alumina alkoxide and a reducing metal, with a higher oxidation potential than that of 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 temperature and pressure polymerization conditions with an olefin polymerization catalyst system consisting of a mixture of cocatalysts, one of which consists of a halide activated intermetal compound consisting of the reaction product of a polymer transition with alumina alkoxide and a reducing metal with a higher oxidation potential than that of the transition metal.

Transition metal-containing intermetal compounds are prepared by reacting a transition metal polymer oxide alkoxy-30 with at least one reducing metal, i.e., a metal having a higher oxidation potential than that of the transition metal. Thus, a polymeric titanium alkoxide or oxoalkoxide is reacted with magnesium metal to form a reaction product which can be activated to form an olefin polymerization catalyst 8a-2a element.

The polymeric transition metal oxide alkoxide can be prepared separately by controlled hydrolysis of the alkoxide, or the polymeric oxoalkoxide can be obtained by a reaction in situ, e.g. hydrolysis in a reaction medium of which the reducing metal forms part. For example, e.g. titanium or zirconium tetrabutoxide are 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 e.g. magnesium halide-10 'hexahydrate.

Transition metal alkoxides, especially titanium alkoxides, are known for their colligative properties in organic solvents and their sensitivity to hydrolysis. It is noted in the literature that the hydrolysis reaction starting from the oligomeric, usually trimer, titanium alkoxides results in polymeric titanium oxide alkoxides, generally expressed by

TiO2) + + IgO —— * TiO ^ QYY ^ g + 2n HOH

8105319 - '- 3 - Λ' ΐ

Condensation reactions can also occur, especially at elevated temperatures, to form structures to which primary metal-oxygen-metal backs, such as OR OR '

5 OR - Ti - 0 - Ti - OR

I t

OR OR

who, in turn, participate in or are precursors to the hydrolysis reaction.

These polymeric titanium alkoxides or oxoalkoxides (sometimes also referred to as u-oxoalkoxides) can be represented by the series [^ i3 (x + 1) ° 1 ^ 0Ε ^ (χ + 3) "where X = 0, 1, 2, 3, which structure reflects the tendency of the metal to extend its coordination beyond its primary dignity, coupled with the ability of the alkoxide to bridge between two or more metal atoms.

Regardless of the particular form envisioned by assuming the alkoxide, in practice it is sufficient to realize that the controlled hydrolysis of the alkoxide oligomers form a series of polymeric oxide alkoxides from the dimer through cyclic forms to the polymer having a linear chain with a length to infinity. More complete hydrolysis on the other hand leads to. precipitation of insoluble products, which eventually yields, upon complete hydrolysis, orthotitanoic acid.

For convenience, these materials are referred to herein as polymeric oxide alkoxides of the respective transition metals, which represent the partial hydrolysis products. The hydrolysis reaction can be carried out separately and the products can be isolated and stored for further use, but this is unsuitable especially in view of the future further hydrolysis, and therefore the preferred practice is to form these materials in the reaction medium. Observation shows that the same hydrolysis reaction occurs in situ.

The hydrolysis reaction itself can be directly controlled using the amount of water added to the transition metal alkoxide and the rate at which this addition takes place 8 1 0 5 3 1 9 ~ 4. Water must be added in portions or in a series addition. Sudden addition does not lead to the desired reaction since it produces an excessive hydrolysis process with precipitation of insoluble products. Dropwise addition is suitable, as is the utilization of reaction water, but it has been found suitable to introduce the water as crystallization water, sometimes referred to as cation, anion, lattice or zeolytic water. Thus, ordinary hydrated metal salts are usually used when the presence of the salts themselves is not harmful to the system. It has been found that the bond provided by the coordinated scale of water in a hydrated salt is suitable for controlling the release and / or availability of water or water-related materials to the system as is necessary for accomplishment, 15 participating in or controlling the response.

As already stated, the total amount of water used has a direct influence on the shape of the polymeric oxide alkoxide formed and is therefore chosen in connection with the catalytic performance. (It is believed, without limitation, that the stereo configuration of the partially hydrolyzed transition metal alkoxide determines or contributes partly to the nature or result of the catalytic action of the activated catalyst component.)

In general, it has been found to be sufficient to provide only 0.5 mol of water per mol of transition metal. Amounts up to 1.5 moles are suitable, larger amounts up to 2.0 moles being useful when precipitation of hydrolysis products from the hydrocarbon solvent medium can be avoided.

This can in principle be achieved by reducing the rate of addition and interrupting addition at the first occurrence of precipitation. While the reaction is believed to be substantially equimolectural, some excess water is suitably used in some cases, as usual.

It will be appreciated that the stereoxomeric form, chain length, etc. of the hydrolysis product may be slightly modified 8105319>, at the elevated temperature required for subsequent conversion with the reducing metal, and in-situ processes also affect equilibria through the effect of mass action, similarly, the simultaneous formation of alkanol can affect equilibria, reaction rates, etc.

J '-The hydrolysis reaction proceeds under atmospheric pressure and at room temperature and is not required for special conditions. A hydrocarbon solvent can be used, but it is not necessary. Mere and only contact of the materials for a period of time, usually 10-30 minutes to 2 hours, is sufficient. The resulting material is stable when stored under normal conditions and can be brought to an appropriate concentration level if desired by simply diluting with hydrocarbon solvent.

The polymeric transition metal oxide alkoxides are reacted with a reducing metal having a higher oxidation epotential than that of the transition metal. Preferably, use is made of a polymeric titanium oxide alkoxide together with magnesium, calcium, potassium, aluminum or zinc, as the reducing metal. Combinations of the transition metal alkoxide, reducing metal and hydrated metal salt are usefully chosen with respect to the electropotentials, so as to minimize side reactions, in a manner known in the art; and generally, in order to provide preferred olefin polymerization activity levels, magnesium components are added. brought into the system by suitable choice of reducing metal / hydrated metal salt.

In the preferred embodiment (conveniently referred to in the following text for illustrative purposes), titanium-30 tetra-n-butoxide (TBT) is reacted with magnesium shavings and hydrated metal salt, most preferably magnesium chloride hexa-hydrate, at a temperature of 60 - 150 ° C, in a reaction vessel under autogenous pressure. TBT can form the reaction medium, or a hydrocarbon solvent can be used. The Ti / Mg molecular ratio can vary from 1: 0.1 to 1: 1, although 8 1 0 5 3 1 9 “” • ----------- ------- ------— - - Γ - 6 - For the most homogeneous reaction system, a stoichiometric ratio of Ti to Mg of 1: 1 is preferred, with an amount of hydrated metal salt such that during the reaction about 1 mol of water per mol of Mg ^ is introduced.

The hydrocarbon-soluble catalyst precursor predominantly contains Ti materials in combination with Mg materials in one or more stereo configuration complexes believed to represent predominantly oxygen-containing species. Certain indications of mixed oxidation states, from the titanium present, suggest an interrelated system of integra-. IV. III ii.

The types of Ti, Tx and Tx materials may be in a quasi-equilibrium ratio, at least under dynamic reaction conditions. Preferred precursor is believed, without limiting it, to include (Ti-O-Mg) bridge structures.

The intermetal compounds are of particular interest as catalyst precursors, in supported or unsupported systems, for isomerization, dimerization, oligomerization, or polymerization of olefins, alkynes, or substituted olefins, whether or not in the presence of reducing agents or activators, e.g. organic compounds of metals of group ΙΑ, IIA, UIA or IIB.

In the preferred use of these precursors, they are reacted with a halide activator, e.g. an alkyl aluminum halide, and combined with an organometallic compound to form a catalyst system which is particularly suitable for the polymerization of ethylene and comonomers to polyethylene resins.

The transition metal component is an alkoxide, usually a titanium or zircon alkoxide, which may contain predominantly -OR substituents, wherein R may contain up to 10 carbon atoms, preferably 2-5 carbon-30 atoms, and more particularly n-alkyl , e.g. n-butyl. The selected component is normally liquid under normal conditions and reaction temperatures for ease of handling and, to facilitate its use, is also soluble in hydrocarbons.

35 In general, for the sake of convenience, the 8105319 -------------------------------- * t. ... -. - Lining of the hydrolysis reaction involved, preferably using transition metal compounds containing only alkoxide substituents, although other substituents may be considered if they do not interfere with the reaction in the sense of a significant change in performance when used. Generally, use is made of the halogen-free n-alkoxides.

The transition metal component is provided in the highest oxidation state of the transition metal to provide the desired stereo configuration structure, among other considerations. As already mentioned, it is most convenient when the alkoxide is a titanium or zirconium alkoxide. Suitable fitane compounds include titanium tetraethoxide as well as the related compounds of which one or more alkoxy radicals, including n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, t-pentoxy, t-pentoxy, t-pentoxy. -amyloxy, n-hexyloxy, n-heptyloxy, nonyloxy, are part.

There are. some indications that the rate of hydrolysis of the normal derivatives decreases as the length of the chain increases, and that this rate decreases as the molecules become more complex, namely, normal, secondary, tertiary, and for this reason these considerations are taken into account when choosing the preferred derivative. In the. Generally, titanium tetrabutoxide has been found to be eminently suitable for the practice of the present invention, and related tetraalkoxides are likewise preferred. It will be understood that mixed alkoxides are entirely suitable and can be used where they are readily available. Complex titanium alkoxides, sometimes including other metal components, can also be used. 30 ..... The reducing metal is supplied, at least in part, in the oxidation state of zero, as a necessary element of the reaction system. A suitable source consists of the known curls or tape or powder. In the form in which they are commercially available, these materials may be in a state in which their surface is passivated by oxidation and milling at 8 1 0 5 3 1 9 ----------- Providing at least some fresh surface may be desirable, at least to control the rate of reaction. The reducing metal, if appropriate, may be fed in a form in which it is dispersed in the transition metal component and / or or the hydrocarbon diluent, or it can be introduced directly into the reactor.

In the case of in situ preparation or for the independent preparation of the polymeric transition metal alkoxide, it provides the source of water or the water-related material, releasing or diffusing or accessing amounts of water, as appropriate, in which manner a delayed rate is controlled during the reaction. As already noted, the coordination scale present with a hydrated metal salt has been found to be suitable for this purpose, but other sources of water in the same proportions are also useful. Thus, e.g. use of other active ingredients free calcined silica gel which, however, contains controlled amounts of bound water. Generally, a preferred source of water is a water complex in which water is coordinated with the base material in a known manner.

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

The interaction of these components is suitably carried out in a closed reactor, preferably provided with reflux agents for volatile components at the elevated temperatures in the reaction vessel. Autogenous pressure is applied as the reaction proceeds smoothly under normal conditions, heating to initiate and sustain the reaction. As with all these reactions, stirring is preferred, simple to avoid crusting or stratification on the walls of the vessel, to ensure intimate mixing of the components, and to ensure a homogeneous reaction system.

- 8105319 ----------------------- "l ΐ _____________" ____ S! - 9 -

Usually use is also made of a hydrocarbon solvent, such as e.g. hexane, heptane, octane, decal, varnish gasoline and the like, to ensure intermixing of the components, heat transfer and maintenance of a homogeneous

J

5 facilitate action system.

Hydrocarbons with a boiling point of βθ to 190 ° C are preferred. The liquid transition metal component can also,. serve at least in part as a reaction medium, especially when no additional solvent is used. The reaction involves a step in which additional volatile components form azeotropes with the solvent or, when the components are used on their own, form the reflux source, but in both cases it is preferred perform the reaction at least through intermediate stages with appropriate reaction times, to return the volatiles to the reaction zone. Thus, butanol is formed when the titanium component consists of titanium tetra-n-butoxide which forms an azeotrope with the hydrocarbon solvent. The choice of a solvent and / or alkoxide with regard to optionally keeping the reaction temperature low is therefore a consideration, as is known in the art.

The reaction temperature is to some extent a matter of choice over a wide range, depending on the reaction temperature for suitable implementation. The reaction system (consisting of the liquid transition metal component, the dissolved hydrated metal salt, particulate reducing metal and, optionally, solvent) was observed to generate visible gas at about 60-70 ° C, indicating an initial temperature or activation energy level at about 50 ° C, thus representing the minimum temperature required for the reaction of the polymeric oxide alkoxide with the reducing metal. The reaction is slightly exothermic during the consumption of the reducing metal and therefore it can be easily continued into the next step, which takes place at the reflux temperature. Since the alkanol formed is largely consumed in the course of the 8 1 0 5 3 1 9 -? * - 10 - progressing reaction (as an independent material), changes the actual temperature of the system and the completion of the reaction "is evidenced by visible metal consumed and / or reflux temperature for the pure solvent being reached within a period of only 30 minutes to b hours or longer, these temperatures can reach 1 ^ 0 - 190 ° C and, of course, one could go to higher temperatures, but this does not yield any obvious advantage. 50-150 ° C, preferably T0 -10 10 ° C. In the absence of solvent, the upper limit is simply determined by the reflux temperature of the alkanol formed in the course of the reaction.

Reaction of the components is most apparent from the marked color change, under exothermic heat development, which accompanies the onset of gas development. "Where the lack of opacity or turbidity of the solution permits perception, the evolution of gas, which can form bubbles into vigorous foaming, is most evident on the surface of the metal and the solutions, which generally have a slight have color, immediately turn grayish, then darken rapidly to blue, sometimes violet, usually blue-black, sometimes with a greenish tint Analysis of the gas shows that no HCl is present and that it mainly consists of Hg. the color slightly darkens during a gradual increase in temperature, whereby gas evolution continues At this stage, the alkoxide corresponding to the alkoxide compound is developed in an amount sufficient to lower the boiling point of the solvent, and the alkanol is gradually consumes in a velocity-related manner along with the remaining reducing metal.

The reaction product is, at least in part, soluble in hydrocarbon and is maintained in a dispersed form suitable for easy future use. The viscous to semi-solid product, when isolated, has been shown to be substantially amorphous in X-ray diffraction analysis; - ii - • i am.

Molecular ratios of the components can vary within certain limits without significantly affecting the performance of the catalyst precursor in its final application. Thus, in order to avoid competing reactions which make the reaction product inappropriately gelatinous to avoid, the transition metal component is usually introduced in at least equimolecular amounts relative to the reducing metal, but the ratio of transition metal to reducing metal may be between about 0.5 · 1.0 and 3.0: 1.0 or greater, preferably 1: 0.1 to 1 1. A

- - I

insufficient reducing metal content results in such a drop in reaction temperature that the reflux temperature of the pure solvent remains out of range; 15 while an excess of reducing metal is immediately apparent from the presence of the unused portion thereof, and the desired amount of this component is therefore readily determined by those skilled in the art.

Within these limits, a varying portion of the reaction product may consist of a hydrocarbon-insoluble component, which may, however, be dispersed with, and usually dispersed with, the soluble component before use, e.g. further reaction with a halide activator to form an olefin polymerization catalyst. The amount of this insoluble component can be controlled in part by using a solvent with a suitable separation coefficient, but when the use of a common hydrocarbon solvent, such as octane, is preferred for practical reasons, equimolecular ratios of e.g. Ti / Mg / HgO components 30 are most suitable for the formation of a homogeneous reaction product.

The water or water-related material is also preferably introduced in an equimolecular ratio to the transition metal component, for similar reasons of homogeneity and ease of the reaction. For example, 8 1 0 5 3 1 9 ----------------------------- - * '-12.- in case of MgCl 2 OH 2 O an amount of 0.17 mole during the reaction about 1 mole of water and this ratio to about 2 mole of water ensures the smoothest reactions, with 1 or more moles of transition metal component. More generally, the amount of water can be from about 0.66 to 3 moles per mole of transition metal. The amount of water present at any given stage of the reaction is, of course, likely to be significantly less, and will be closer to the catalytic ratios with respect to the other components, depending upon the manner and rate at which it participates in the reaction sequence, which data is currently unknown. Nevertheless, without being limiting, the working hypothesis specifically assumes that the water, or the reaction rate controlling water-related material, is activated, released, made accessible to, or diff-15 functions in such a way that it material is made available regularly, sequentially, constantly or in a speed-related manner. However, the same molecular ratio of free water fed at the start of the reaction is completely ineffective to start the reaction at this or higher temperature and this results in undesired complete hydrolysis reactions.

The measured amount of water is mainly in molecular equilibrium or in a molecular excess relative to the reducing metal component and appears to be related to its consumption in the reaction, since an insufficient molecular amount of water invariably results in the remaining an excess of reducing metal. In general, a modest excess of 10 - hQ% is suitable to ensure complete conversion. Larger relative amounts are suitable, without limitation, but should be kept in a relatively stoichiometric equilibrium with the transition metal component.

The choice of water complexes or hydrated metal salts, when used, is primarily a matter of the controlled availability of the water they have introduced into the system. Sodium acetate trihydrate is suitable, for example, as well as magnesium acetate tetrahydrate, magnesium sulfate hept ahydrate and magnesium silicon hydroxide hydrate. A salt with a maximum degree of penetration, consistently combined with the controlled release provided by the coordinate bond ratio, is preferred. Most suitably, use is made of a hydrated magnesium sin halide, such as magnesium chloride hexahydrate. or magnesium bromide hexahydrate. These salts, like other hygroseopic materials, even when supplied - in commercial vessel-free form, contain some sorbed water, e.g. 17 10 mg / kg (see British Patent Specification Νο.ΐΛθ1.7θ8), although significantly less than the molecular amounts of the invention. Therefore, barrels-free salts are not suitable according to the invention unless they are specially modified for the intended purpose.

The reaction system, as defined in the foregoing description, does not require an electron donor or Lewis base, or a solvent that partially fulfills its functions, although it tolerates it. As can be seen from the examples, the reaction is effected in the preferred embodiment. -20 was introduced into the system with crystallization water and an alcohol component. It is therefore not known with certainty whether proton transfer or electron donor mechanisms participate or compete in the reaction system.

Separation is not necessary, since at least a portion of the reaction product is soluble in the saturated hydrocarbon when used as a solvent, or provides a solvent medium such that even when a precipitate is formed, and even after storage, a manageable reactive dispersion can be easily formed.

In a preferred aspect of the invention, the reaction product (the catalyst precursor) is further reacted with a halide activator, eg an alkyl aluminum halide, a silicon halide, an alkyl silicon halide, a titanium halide or an alkyl boron halide. It has been found that the catalyst precursor can be easily activated by the 8105319 ......

Product easy to combine with the halide activator. The reaction is vigorously exothermic and therefore the halide asset is typically added gradually to the reaction system. normally, after completion of the addition, the reaction is also complete and can be stopped. The solid reaction product or dispersion can then be used immediately or saved for future use. Usually, for the best control of the molecular weight properties, and in particular for the preparation of low density resin, only the hydrocarbon-washed solid reaction. product used as a catalyst.

The halide activator is usually introduced for mutual reaction in a molecular ratio of 3: 1 to 6: 1 (aluminum, silicon or boron, with respect to the transition metal) although ratios of 2: 1 or greater have been successfully used .

The resulting catalyst product can be used directly in the polymerization reaction, although it is typically dilute or reduced, as necessary for providing an appropriate starting material with an amount of catalyst equivalent to 80-100 mg of transition metal based on a nominal productivity greater than 200,000 g polymer / g transition metal in continuous polymerization, which value is determined by the catalyst according to the. invention is usually surpassed. Adjustments can be made by the person skilled in the art in order to respond to reactivity and efficiency, usually by simple dilution, and control of feed rates.

The transition metal-containing catalyst is combined with an organometallic cocatalyst, e.g. triethyl aluminum (TEA) or triisobutyl aluminum or a non-metal compound such as triethyl borane. Thus, a typical polymerization starting material contains h2 parts of isobutane solvent, 25 parts of ethylene, 0.0002 parts of catalyst (calculated as 35 Ti), and 0.009 parts of cocatalyst (TEA, calculated as Al), which yields 8105319 -15-

<I

starting material is intended for a reactor maintained under a pressure of 82 kPa and at a temperature of 71.1 ° C. Generally, the amount of cocatalyst when used is calculated to be between about 30 and 50 mg / kg, calculated as Al or B on isobutane.

Examples of metal cocatalysts include trialkyl aluminum, such as triethyl aluminum, triisobutyl aluminum, tri-n-octyl aluminum, alkyl aluminum halides, alkyl aluminum alkoxides, dialkyl zinc, dialkyl magnesium, and metal borohydrides, including those of the alkali metals, especially sodium and lithium potassium, and of magnesium, beryllium and aluminum. The non-metal cocatalysts include boron alkyl, such as triethyl borane, trilobutyl borane and trimethyl borane, and boron hydrides, such as diborane, pentaborane, hexaborane and decaborane.

The polymerization reactor is preferably a loop reactor suitable for working with dispersions using a solvent, such as isobutane, from which the polymer separates as a granular solid. The polymerization reaction is carried out under low pressure, e.g. 1380 to 206895 kPa, and at a temperature of 31.8 to 93.3 ° C, using hydrogen as desired to control the molecular weight distribution. Other n-olefins can be introduced into the reactor in minor relative amounts to ethylene for copolymerization. For example, e.g.

Butene-1 or a mixture thereof with hexene-1 in an amount of 3 to 10 mol%, although other α-olefin comonomers and other ratios can be readily used. Resin densities from 0.91 to 0.96 can be obtained by using such n-olefin comonomers.

Still other olefin comonomers such as U-methyl-pentene-1, 3-methyl-butene-1, isobufcylene, 1-heptene, 1-decene, or 1-dead-cene can be used in amounts as low as 0.2 wt%, especially when monomer mixtures are used.

The polymerization can nevertheless be carried out under higher pressures, e.g. 137,895 to 275 * 790 kPa in an autoclave; or tubular reactors, if desired.

8 1 0 5 3 1 9 "" * * ____________________ - ^ · - IS -

When reference is made herein to an intermetal "compound" or "complex", it is intended to mean any reaction product, whether it be a coordination or association product, or the form of one or more inclusion or occlusion compounds, "" clusters "or other forms of mutual engagement under the applicable conditions, the integrated reaction generally being evidenced by change of clay and gas evolution, likely to reflect reduction oxidation, rearrangement and association among the unused elements of the reaction system.

The following examples, together with the foregoing description, are intended to further illustrate the invention and the method of its preparation and use. All parts are parts by weight unless otherwise indicated. Melt indices are measured under conditions Ξ resp. F from ASTM D-1238-57T, for ΜΓ and HIMI values, on powder or resin samples, as directed. KLM / MI or MIR is the melt index ratio, a measure of the shear sensitivity and a reflection of the molecular weight distribution. Other tests are as indicated or as usually performed in the related techniques.

Example I

A. 6.0 parts of Ti (OBu) ^ [TST J and k, 2 parts of CrCl2 OHH O were combined in a reaction vessel. The chromium salt was partially dissolved and a little heat was generated with stirring. Complete solution was obtained by gentle heating at 60-70 ° C. A further 3.3 parts of chromium salt was dissolved with stirring over 20 minutes. A total of 0.3 parts of magnesium shavings was added in portions to the green solution, causing vigorous gas evolution. The cooled reaction product, free of excess magnesium (which had completely disappeared), was a viscous green hexane-soluble liquid.

B. In a similar run, vat-free chromium chloride was used with the titanium alkoxide, however, no reaction occurred when heated to temperatures higher than 100 ° C for 8105319 1/2 hours. When zinc powder was added and further heating above 150 DEG C. still no reaction occurred. Replacement of the magnesium curls did not produce a reaction either. The conclusion from this is that the hydrated salt is a necessary component in the reaction system.

Example II

A. TBT (0.121 mol), CrCl 4 SHgO (0.015 mol) and Mg ° (0.0075 mol) were combined in a reaction vessel equipped with an electric heating jacket and stirrer. The chromium salt was completely dissolved at about 60 ° C and reaction with the magnesium curls. was evidenced by gas evolution at 85 ° C, which was powerful at 100 ° C and decreased at 16 ° C, leaving a little Mg. After dissolution of the remaining Mg, heating was continued to a total reaction time of 1.75 hours. The reaction product at room temperature was a dark green liquid that readily dissolved in hexane. B. In the same manner, a reaction product was prepared from the reactants in the following relative amounts; 0.16 moles of TBT, 0.029 moles of CrCl 4 -gIgO and 0.029 moles of Mg. The reaction product had a cloudy green color at 18 ° C and it took on a distinct bluish color at 120 ° C with continued gas evolution.

The reaction was stopped after the disappearance of magnesium in 1.25 hours. The reaction product was soluble in hexane.

C. The foregoing experiments were repeated again with reaction participants in the following amounts: 0.16 mole TBT, 0.058 mole CrClyOHgO and 0.01¼ mole Mg. The reaction was completed in 115 minutes and as a result a hexane soluble product was obtained.

D. The ratio of the reactants was again changed in a further test in 0.115 mole TBT, 0.028 mole

CrClgjéHgO and 0.01¼ mol Mg. A cloudy green material occurred at 11U0C and turned blue on the Mg surface. The reaction product recovered was soluble in hexane.

E. In a similar run, 0.176 moles TBT, 0.30 moles 35 CrCl 4 .HgO and 0.176 moles Mg 4 were converted to octane. The bright green color of the reaction mixture at 70 ° C became cloudy with increasing 18105319. Gas evolution and darkened to nearly black at 90 ° C. The color returned to green at 119 ° C and the reaction was stopped at 121 ° C with the magnesium completely disappeared. The reaction product (6.9 wt. # Ti, 3.5 wt. # Mg, 1.3 wt. # Cr) consisted of a dark olive green liquid and a solid with a darker clamp * (volume ratio approx. 50:50 ) who deposed.

F. In yet another octane test, the reactants were introduced in the following ratio: 0.150 moles TBT, 0.051 moles CrCl3.6H 2 O, and 0.150 moles Mig. Federom changed a cloudy green color to almost black with vigorous foaming, where a dark blue-black reaction product was formed at 109 ° C (5.7 parts # Ti; 2.9 parts # Mig, 2.1 parts # Cr ).

Example III

A. Isobutyl aluminum chloride was added dropwise to the reaction product IIE in a reaction vessel in such a ratio that a molecular ratio of AL / Ti of 3: 1 was obtained. The green color of the mixture initially changed to brown violet at 3 ° C and after completion of the addition of the reactant at 39 ° C to red brown. After stirring for another 30 minutes, the reaction was terminated, the product consisting of a dark reddish brown liquid and a dark brown precipitate.

B. The reaction product IIF was similarly reacted with isobutyl aluminum chloride (Al / Ti 3: 1 molecular ratio).

The temperature peak at the completion of the addition was 88 ° C, but no change in color to brown was observed.

The reaction product consisted of a clear liquid and a dark gray precipitate.

Example IV

The catalysts prepared in Example III and used in the polymerization of ethylene (87, S ° CY 10 mol- ethylene, 0.0002 parts of catalyst calculated as Ti, triethylaluminum ca. if-5 mg / kg , calculated as Al, as indicated), with the results reported in Table A: 8105319 4 * _____ _ _________ __ ^ _.........__ ·· ·.

\; - 19 -

Table A

Cataly- Hg Product Resin Properties

sator kPa transfer g Pe / g Tl · h MI HLMI HLMI / MI

IIIA UlU 35 160 10.1 265 26.3 5 82T 29 220 18.9 6l8 32.6 IIIB lalt- 30 380 9.6 26 ^ 27 '827 26 880 32.8 855 26.1 • * t 10 In the following example, the catalyst component of the invention prepared from the reaction mixture in the absence of added solvent.

Example V

A. 0.1212 mole Ti (OBu) / / TBT J, 0.121 mole magnesium shavings and 0.0012 mole MgClg.OHgO (TBT / Mg / MgClg.OH ^ O = 1: 1: 0.01 (mol)) united in an electric heating jacket provided with a stirred reaction vessel. The magnesium salt dissolved completely at room temperature to form a homogeneous reaction mixture.

The mixture was heated gradually and gas evolution started at 95 ° C; occur on the surface of the magnesium shavings. At li + 0 ° C, the reflux gas evolution became lively. The color of the solution darkened and gas evolution ceased at 170 ° C, after which the reaction was stopped. The reaction product contained excess magnesium, only about 8.5% of the metal introduced had reacted, and it was soluble in hexane.

. B. In another experiment, the molecular ratio of MgCl2.6H2O was increased (TBT / Mg / MgClg.OHgO = 1: 1: 0.1 (mol)). The golden yellow liquid turned greyish under gas evolution at 10 ° C and darkened with further heating at 168 ° C. After 125 minutes of reaction time, the reaction product contained a little excess of magnesium, about 30% had been converted.

C. In a further test, a molecular ratio of 1: 1: 0.17 was used. The dark blue reaction product was very viscous and could not easily be diluted with hexane. All the magnesium was consumed.

8105319 i »- 20 -

The following example describes the preparation carried out in a hydrocarbon solvent.

Example VI

A. 50.2 parts (0.1½ moles) of TBT was charged into an electric heating jacket, stirred reaction vessel, followed by 58.6 parts of octane. The magnesium curls (0.074 mol) were added. was added and stirring was started, after which 0.0125 mol of MgCl2.6e ^ 0 was added under heating for 1 minute. The magnesium salt had completely dissolved at 75 ° C (20 minutes) and gas evolution started at 10 - 95 ° C (25 minutes). the surface of the magnesium curls to appear, which development increased as the solution turned greyish and then dark blue, boiling at 117 ° C (35 minutes). The magnesium metal was completely reacted within 1 hour (128-129 ° C) and the reaction had ended. The dark blue reaction product, dissolved in octane (a small amount of greenish precipitate remained), was found to be 6.8 wt. 5? Ti and 2.0 wt% Mg (Ti / Mg weight ratio 3.4: 1, molecular ratio 1.7: 1) · B. The previous experiment was essentially repeated, except that the molecular ratios of the reactants were changed modified to obtain the following results: Ti / Mg / MgClg.eHgO Ti / Mg Remarks: mole ratio (mole ratio) 25 _ _ 1.0 / 0.65 / 0.11 1.32 dark -blue black liquid and green precipitate. 6.6 wt. # Ti, 2.6 wt. # Mg (annealed) 1.0 / 0.75 / 0.128 1.14 blue solution with a greenish tint. 6.5 wt. # Ti, 2.8 wt. # Mg (calcined) 1.0 / 1.0 / 0.085 0.92 blue-black liquid with a light green precipitate (insoluble in acetone, alkane and methylene chloride). A whey 0.35 mg unconverted 1%.

λ j Λ c 7 4 Π - 21 -> *

Table A (continued) 1/1 / 0.17 0.8? dark blue liquid, 6.6 weight% Ti, 3.9 weight Mg (annealed) 1/1 / 0.3 ^ 0.75 dark blue liquid, 6.7 weight% Ti, 5 ^ 6 weight%. $ Mg (annealed) 1/1 / 0.5 0.66 milky blue liquid, 3.7 wt. $

Ti, 2.9 wt, $ Mg (annealed) 1/2 / 0.17 0.14-6 dark blue-black liquid and viscous green gel. A little unconverted Mg. 10 1/2 / 0.3 ^ 0, Λ3 dark blue-black liquid and viscous;

gel. A little reed-converted Mg. 2/1 / 0.17 1.70 Example IIA

2/1 / 0.3 ^ 1.50 blue-black solution- 7S1 wt% Ti, 2.3 wt% Mg (annealed) 15 · 3/1 / 0.51 1.99 blue-black liquid with a weak green tint . 6.1% by weight Ti, 1.6% by weight Mg (calcined) C. The above preparation with 1/1 / 0.3b was repeated, except that 63.7 parts TBT was used with 67.5 parts hexane. 20 as the solvent for the reaction medium. A dark blue-black liquid resulted, which after annealing generated 8.2% by weight Ti and 1.6% by weight.

Mg contained.

The following example concerns the stepwise preparation of the catalyst component.

Example VII

2.6 parts of MgCl 2 · ïOgO and 3 · 2 parts of TBT were combined with stirring. Within 30 minutes, the yellow liquid / crystalline salt mixture was replaced with a milky yellow, opaque viscous liquid. Stirring for a long time resulted in a reduction of the turbidity and the formation of a clear yellow liquid within 2 hours. (In a second run, run in octane, the salt was completely dissolved within 30 minutes to form a yellow liquid without any precipitation or opacity occurring.) 8105319 "- 22 - \

A TM-Mg reaction product was prepared in the same manner as in the previous examples, using the clear yellow liquid prepared above, and 1.83 dia Mg ^, at a molecular ratio of the components in the octane of 1 / 0.75 / 5 0.128. The reaction proceeded smoothly and a dark blue-black liquid with a green precipitate formed in the same manner as in the other reactions described.

* The reaction product was activated with ethylaluminum dichloride at an Al / Ti ratio of 3: 1 to form a catalyst component for olefin polymerization.

The following example shows how important the bound water content is.

Example VIII

A series of identical experiments were performed at a molecular ratio of 1 / 0.75 / Q, 128 (TBT / Mg / MgClg 6η ^ 0) except that the degree of hydration of the magnesium salt was changed.

When MgClg.tO2 was used (H 2 O / Mg = 0.68 / 1 compared to 1: 1 for MgClg 3 H 2 O), only 89 µg of the magnesium reacted. Use of MgCl 2 .2Η ^ 0 at the same total molecular ratio (H 2 O / Mg 0.3Vl) resulted in that only 62.1% of the Mg had reacted.

In repeated runs, the amount of the added hydrated salt was increased to give a ratio of 25 1/1 H 2 O / Mg. All the magnesium metal was converted. It was also observed that the amount of insoluble reaction product increased as the salt content increased.

The following example concerns the use of other titanium-30 compounds.

Example IX

A. ^ 5.25 parts (0.1595 mol) Ti (OPr ^) ^, 0.1595 mol Mg ° were placed in a reaction flask equipped with an electric heating jacket and stirrer, after which 0.027 mol MgCl2. . The milky yellow mixture turned gray under boiling reflux at about 88 ° C and turned "blue" at 90 ° C under foaming gas evolution. Based on residual magnesium, it was concluded that the reaction was partially suppressed by the presence of the octane / isopropanol azeotrope.

B. The reaction described under A above was repeated with a molecular ratio of the reactants of 1 / 0.75 / 0.128 using deealien (Kp. 185-189 ° C) as diluent. After 6 hours, the reflux temperature had reached 100 DEG C. and the reaction was terminated. A dark blue-black liquid with a small amount of dark precipitate was obtained. Only 8.8 $ of the magnesium had been converted.

C. Similarly, the reaction was carried out with tetra-iso-butyl titanate at a molecular ratio of 1 / 0.75 / 0.128, yielding a blue-black liquid and a dark precipitate.

Approx. 50 $ of the magnesium had been converted.

D. Titanium tetranonylate was similarly used, with magnesium and MgC 2 OH 2 O at a molecular ratio of 1 / 0.75 / 0.128. A blue liquid was formed; k5% of the magnesium 20 was consumed.

E. The reaction product of titanium tetrachloride and butanol (believed to be dibutozytitane dichloride) was reacted with magnesium and magnesium chloride hexahydrate at a molecular ratio of 1 / 0.75 / 0.128 under similar conditions to those in the above examples. About half of the magnesium was consumed in about 3 hours, after which a dark blue-black liquid and an olive green precipitate (50; 50 by volume) were recovered. In the following example, a zircon alkoxide is used.

Example X.

A. 12.83 parts of Zr (QBu). BuOH (0.028 mol); 0.3¼ din Mg ° (0.1¼ mol) in the form of commercially available curls, and 8.8 µl of ethylene were placed in a reaction vessel and refluxed at 125 ° C with stirring for 15 minutes, without 8 1 0 5 3 1 9; - 2h - some reaction "was found to occur. 0.97 parts of MgCl 2 .HGg (0.005 mol) was added, after which vigorous gas evolution was observed and the reaction mixture took on a milky appearance.

B. In a second run, 31.7 parts of the zirconium compound (0.069 mol) was combined with the magnesium shavings (0.069 mol), and 57.6 parts of petroleum ether (bp 170-195 ° C) and h, J9 parts MgClg. 1HgO (0.0235 mol) were added with stirring. The reaction vessel was heated by means of an electric heating jacket. Within 5 minutes, the reaction mixture had become opaque, and gas evolution from the surface of the magnesium metal "appeared to occur when the temperature reached 85 ° C after a reaction time of 8 minutes. Gas evolution continued with vigorous foaming, temperature rose to 108 ° C with a whitish solid occurring With continued heating to 133 ° S (1 hour reaction time), all the magnesium metal had disappeared, and the reactor contained a milky white liquid and a white solid. cooled to give 92 parts of a mixture containing 6.8 wt% Zr and 2.1 wt% Mg (weight ratio Zr / Mg 2.8: 1, molecular ratio Zr / Mg 0.75), which mixture was soluble wax in hydrocarbons.

The reaction product can be activated in known manner with e.g. an alkyl aluminum halide by reaction therewith, suitable at an Al / Zr molecular ratio of from about 3: 1 to 6: 1, to form, in combination with an organic or metalorganic reducing agent, an olefin polymerization catalyst system suitable for the formation of polyethylene resin.

The following example concerns the replacement of magnesium with calcium as a reducing metal.

Example XI

A. 0.07¼ mol Ti (OBu) ^; 0.07 moles Ca ^ (commercially available thick curls, which are mechanically cut into small pieces) and 0.0125 moles MgCl 4 .HgO were combined in octane in one of an electric heating mantle and stirrer. reaction vessel. When the temperature reached 105 ° C, the color of the solution darkened and at 108 ° C the solution turned dark gray under gas evolution. Rapid gas on winding occurred at 110.5 ° C, followed by the formation of a dark blue liquid.

After 90 minutes, the reaction was stopped and a reaction product consisting of a dark blue-black liquid of a greenish color was isolated.

The test was repeated at the same molecular ratio.

50% of the calcium reacted to form a dark blue liquid and a gray solid containing 6.2% by weight Ti, 2.6% by weight 10 Ca and 1.1% by weight Mg (molecular ratio 1: 0.5 : 0.3 ^).

(ΧΓΑ1).

In a further experiment, the same reactants were united in a molecular ratio of 0.75 · 0.128. 63% of the calcium reacted to form a blue-black liquid and a green solid. The reaction product (molecular ratio 1 r. 0, U7: 0.128) contained 6.6 wt.% Ti. 2.6% by weight Ca and 0.1 wt. $ Mg (XI A2).

B. The reaction product XI A1 was further reacted with ethylaluminum chloride in molecular ratios of 3: 1. and 6: 1. The reaction products were diluted with hexane and the halide activator was slow to control the highly exothermic reaction , added. In the 3: 1 test, the. dispersion initially formed upon completion of the reaction, which was an off-white color, formed to form a pink liquid and a white precipitate. At the Al / Ti ratio of 6: 1, the color of the dispersion changed to gray and then to light green.

The reaction product XI A2 was likewise treated with EtAlCl 2 with a Al / Ti molecular ratio of 3: 1 and 6: 1. The reactions proceeded smoothly and at 3: 1 a dark brown dispersion was obtained, and at 6: 1 a reddish brown liquid with a brown precipitate.

C. The bottom. B reaction products prepared were used in ethylene polymerization to give the results listed in the table below: 8105319 - 26 - h 0 Η 0 o 9t 0 S4

sj W H CO vo C— H O

H t J A A A A A A

SH-VOCiLAOVO

4J co -a · -3 · * = t vo vo 0 Λ § t— o r · H "" *

2 H C— CO O H VO

pjHcO-rfC— CViCVlH

-0 W Η H

& • & · 'Λ

O

m j- co co ia öHcoot-ocnt · - "0 S» ** «« »« Ό

bO COHHT-OH P

Rf £

rvr O

w> 0

bC

-P

P H

<<p rj · 0 A!

-PH bO

03 raEHOOOOOO H g bfl ca H CO VO CV1 A 0 H pbCO \ coG \ ej-3-o0 · £ aj <n * ··· »* iC - *

o ^ 0OCOOHC “H1 O

os HfeH-H-caHcvicnra * pj a. g 83 B o be 3 h 1 5 13 p

P 0 H

HHHCUHOJCÖ g

C'JCÜ-S'-S'H'CO-S'CO Η H

w a a ~

° ö B

0 0 -H

• H> 0 40 0 · Η bO 0 bC g 1 .5 0 be H Ö 0 η p 0 0 ® 0 • HP HHH H oi

o, ¾ CO VO CO VO H-PO OHS

dJij, ΡΟΛ -ΡΟ · Η 0 0 S Π co H: 0 g g pHr *> 3 0 Λ 5 "H _ _ c w f— Ο ρ ο o

a * ri CO M -p H VO

u 0 · * ’· ....... · *

0'-1 0 H

CVI bC E * 0 0 w s _ 2 2

VO -H P · Ρ, S

• (0 0 * H? -4 Pi CU P CO Ό g 9 ΛΙ HO 03 0 0¾¾.¾ ΟΛ-3--3-Η O bO p 0 Ό bO t! CO CO «bCPP ^ jM.

S Φ «« Ο · Η · Η-Ρθ ^ Μ 5 1 t> ο σ \ ^ η p 0 -p h 0

Pl '^.' ^. C- flGfHCQPPrOHAA-3-

| 0ΛΛΛ -p'UftdJCÖOH

& 4SOOO CQ U S -P ^ Λ 3 S i 5> S3.

fi 1 n R 3 1 Q __ * * - 27. -

These experiments showed a slightly wider molecular weight distribution in the resin than that obtained when magnesium is used as the reducing metal.

The use of zinc as the reducing metal is described in the example below.

• Example XII

A. 0.20¼ moles of TBT, 0.153 moles of Zn4 in the form of granules, and 0.026 moles of MgClg.OHgO were combined in octane in one of 10 reflux dating. and rudder access provided, externally heated system. Within 13 minutes (85 ° C), a rapid color change to blue-black occurred with increasing gas evolution. to vigorous foaming. The reaction product, a blue-black liquid (no precipitate) containing 7 * 0.9% Zn and 0.5 | Contained 15 Mg, faded to yellow when exposed to air.

B, The reaction product, TiZnMg (molecular ratio '1; 0.86 0.128), was reacted with isobutyl aluminum chloride at a molecular ratio of Al / Ti of 3: 1, in hexane at 10-13 ° C (XII B1).

C. The preparation of the reaction product TiZnMg (XIIA) was repeated using Zn powder to give similar results. In a further trial, with mossy. (English: mossy) zinc only J% of the zinc was consumed and. the formation of a green layer on the surface 25 hereby occurred.

; D. Reaction product XIIB1 prepared above was thoroughly washed in hexane and used to prepare low density polyethylene resin. A sufficient amount of butene-1 was previously introduced into the reactor to ensure the target density, and the reaction was carried out (under the stepwise addition of butene-1 together with the ethylene) at 76.7 ° C and under a hydrogen pressure of 2l + 1kPa in the presence of triethyl aluminum as a cocatalyst. The resulting resin had the following properties: density 0.9105, MI 1.68, KIMT 52.1 and 35 MIR 31.

81 0 5 3 1 9 --------------------- »λ - 28 -

The following example "concerns the use of potassium as the reducing metal.

Example XIII

62.7 mmole TBT, UT nmol fresh potassium metal (freed from its oxide / hydroxide skin under octane by deletion 5) and 8.0 mmole

MgCl 2 .OHgO were combined in octane in a refluxed, externally heated, closed system. steem. Within 2 minutes at 35 ° C, the color changed to blue black and bubbles appeared. Powerful gas evolution and 10 foams followed. After the disappearance of the potassium metal, the reaction was terminated (after 5 hours). A dark blue-black liquid with a small amount of dark blue precipitate was obtained.

Examples XIV and XV describe the use of aluminum 15 as the reducing metal.

Example XIV

A. 112.31 parts TiiOBu) ^ (0.33 mol), 8.19 parts Al ° ("Alfa Inorganicspherical" aluminum powder, finer than mesh) and 11.1 parts MgClg. ratio 1: 1: Q, 17) were mixed with stirring in a reaction vessel and heat was applied using an electric heating mantle.

When 100 ° C was reached in about 10 minutes, the yellow color deepened and at 118 ° C, vigorous foaming occurred under gas evolution. At 122 ° C, the refluxing liquid turned greyish and the temperature stabilized as the color of the reaction mixture changed from a deep gray with a bluish tint to dark blue and then blue-black after a reaction time under heating for 27 minutes. The temperature was maintained, rising to 1 * 5 ° C within 1 hour and 20 minutes, after which the gas evolution had substantially ended and the reaction was terminated.

The reaction product was a viscous liquid at room temperature, in which unreacted aluminum particles were found to be present. The unreacted aluminum was separated, washed, and weighed to find that 6.7 parts of Al had reacted 7 λ Λ C 7 Λ Π ______. -29-. The reaction product contained 7.9 wt.% Ti, 3.5 wt.% Al and 0.7 wt.% 1% (molecular ratio 1: 0.75: 0.17).

B. 9.10 parts of the reaction product prepared "above" (0.719 parts Ti, or 0.015 mole Ti) was placed in a cooling bath in hexane (13.0 parts) in a reaction vessel. 0.05 mole of ethyl aluminum dichloride was added gradually, maintaining the temperature at 15-20 ° C. After stirring for 30 minutes, the mixture yielded a dark reddish brown dispersion and an unmanageable solid (B1).

A second experiment was run (0.175 mole Ti / 0.0525 mole

A1) without cooling, reaching a peak temperature of 38 ° C, and again a reddish brown dispersion with an unmanageable solid (B2) was formed.

Example XV "The reaction product and from Example XIV were used as catalysts in the polymerization of ethylene under standard conditions (87.8 ° C, water pressure kCl kPa) using triethyl aluminum as a cocatalyst, yielding the following results: MI HLMI MIR.

B1 0.1¾ 6, k5 ¾β, l B2 0.38 17, ¾

Example XVT

A. In a manner similar to the above, 0.133 moles TBT, 0.100 moles Al 2 Cl and 0.017 moles AlCl 2 .HgO were combined in octane and reacted for 7.25 hours, using a dark blue liquid and. a small amount of gray solid were formed. Approx. K% of the aluminum reacted to form a reaction product containing 6.6 wt% Ti and 1.6 wt% Al (XVI Al).

In the same manner, the same reactants were pooled in a molecular ratio of 1: 1: 0.17. Approx. 58% of the aluminum reacted to form a reaction product containing 6.5 wt% Ti and 2.7 wt% Al (X7 A2).

B. The reaction products (XVT A1) and (XVI A2) were activated with ethyl aluminum chloride in an Al / Ti ratio of 3: 1.

Q. The solid portion of the activated reaction product 8105319-30 - (XVX A2) was separated from the supernatant and used with TEA as a cocatalyst in the polymerization of ethylene at 675 ° C and under a hydrogen pressure of 103 kPa. forming a resin characterized by MI 0.02, HLMI 1.01, 5 MIH 50.5 and in a second run MI 0.02, HLMI Q, k5 and MIR 22.5.

The following examples concern catalyst component and were prepared using other water complexes.

Example XVII

10. A. 0.0335 mole TBT and 0.0335 mole Mg ° were stirred in octane in a heated reaction vessel, to which 0.0057 mole MgBr6.66 ^ 0 was added. (Molecular ratio in the reaction: 1: 1: 0.17.) The salt dissolved in 6 minutes under heating at 65 ° C. The mixture took on a gray color and gas-evolved foaming occurred, the solution turned blue, then blue-black with a greenish color. The reaction was terminated at 123 ° C (about 10% unreacted Mg) after a reaction period of k hours and 10 minutes (XVII A).

Similarly, a reaction product was prepared at a molecular ratio of Ti / Mg / MgBr2.OH2O of 1: 0.65: 0.11), which consisted of a blue-black liquid and a dark green precipitate (6.5 wt. $ Ti, 2.5 wt. $ Mg (annealed)).

B. The decanted reaction product (XVII A) was combined with isobutylaluminum dichloride at an Al / Ti ratio of 3! 1 and 6: 1 by gradual addition of the alkyl aluminum halide. In the first run (Al / Ti 3: 1), a peak temperature of U2 ° C was reached when added at a rate of 1 drop every 2-3 seconds, after which the green liquid turned brown.

The reaction product consisted of a reddish brown liquid and a brown precipitate (IV B1). The 6: 1 product (B27 B2) was prepared in a similar manner and the same results were obtained.

In a separate run, the reaction product (XVII A) was combined with SiCl 2 in the same manner. The reaction product after a reaction time of 30 minutes at a Si / Ti ratio of 3: 1 consisted of a pale yellow liquid and a brown precipitate. A similar test gave the reaction product of Si / Ti 6: 1.

8 1 0 5 3 1 9 ___ · "t * ______" ΒΙΟ. The activated reaction products XVII B1 and XVII B2 (1 wt% Ti) were used in the polymerization of etben (10 mol- in isobutane) at 87.8 ° C, with hydrogen as modifier and triethyl aluminum as cocatalyst (^ 5 mg / kg Al) and compared to 5. an identical test using magnesium chloride hydrate, the test results of which are summarized in Table C: 8105319 - 32 - ca Ρ Η C \ ΙΛ cö S Λ * JS \ ιη «σ \ I νο ιτ \ μ cn cm evil on on * PJ§ a) a

Λ W

. §

^ H

Ö S H CO 00 t d Si qj 3 vo j σ \ I t- on p, S on vo on vo ft, aj ft m U C- CM ^ c <U H "**".

<D Ό 2 H CM -T ft 2 t— fcO <U H CM Ο H 1-i

.HO H

H ft ft "

, ρ · Η 0> O OO Ο O

ocnEHi-OCTv ^ 'aLrv GO r4 η CO t— O

H Ö bO * · * - * * * 0) 0) ^ h <MC \ 7n rn p PW - = r - = r o * “mon

3 ft ft H

Eh ft O so § js · c— nr c— nr c—

3 H CM "-'CM H

hj- oo nr co nr oo CM ed ** Ö b 0

S H ft H

+ 9> • h> 'T: · *

ÉH I SC

s H fl n on vo H Q · ri ^ 310

O O

“F JM« w

1 ►Μ M

P 60 VO MO

O 2

• p I CM CM

cd no H U

cn - o ft p so so 3 ft a s

ce O

-P - II II

aJ · Η. , W Eh <<i 8 1 0 5 3 1 9 --------------------- - - 33 / 3b - * t \

Pre-XVIII

A. 1 * 2.23 din TBT (0.12 ** mol) were added to 3.02 parts Mg (0.12 ** mol) in octane. 1 * 2.8 parts) In the presence of 5, 7 parts of FeClg. (0.02 mol) · (molecular ratio Ti / Mg / Fe = 1: 1: 0.17) in a closed reaction vessel equipped with a reflux device, a stirrer and an electric heating jacket.

One started to heat and within 6 minutes, at 65 ° C, gas started to develop. The cloudy yellow color turned dark brown at 80 ° C (7 minutes) and gas evolution increased. In about 10 minutes, the gas evolution slowed and then ceased when the Mg0 was consumed, after which the reaction was terminated.

No residue was found to be present in the very dark liquid (XVIII At).

In a second run, the same reactants were combined in a Ti / Mg / Fe = 1: 1: 0.3 ** molecular ratio to give similar results. Dilution with hexane did not precipitate or deposit a residue (XVIII A2).

B. Reaction product XVTII A1 was activated by reacting with a 50 wt.% Solution of ethyl aluminum chloride in hexane at an Al / Ti ratio of 3 * 1. A brown liquid and solid were collected, which contained 16.5 mg Ti / g (XVTII B1).

Similarly, the reaction product (XVTII A2) was activated. The dark brown liquid turned into a violet dispersion and then into a dark gray dispersion. The resulting clear liquid and the gray precipitate contained 16 mg Ti / g.

C. The activated reaction product XVIII B1 was used in the polymerization of ethylene at 87.8 ° C and under a hydrogen pressure of 11 * kPa. 11U.320 g Pe / g Ti h was obtained, having the following properties: MI 5.1, HLMI 155.3, MIR 30.3.

Example XIX

A. 1. 0.160 moles TiO4u), 0.10 mole magnesium shavings and 0.027 moles CoCl2 HgO were combined in a stirred reaction vessel with 6 1.2 parts octane. The purple cobalt salt crystals yield a dark blue solution after dissolution. The mixture is heated using an electric heating mantle, and gas evolution on the magnesium surface occurs at 58 ° C and increases to vigorous foaming at 107 ° C within 12 minutes. The light blue color turns grayish on further heating and turns almost black at 123-125 ° C when all the magnesium has disappeared and the reaction is terminated after 90 minutes. The milky blue reaction product was soluble in hydrocarbon and separated on standing in a dark blue liquid and a dark precipitate.

The experiment was repeated, yielding essentially identical results.

B. The reaction product from the previous preparation was shaken and 0.0111 mol Ti was combined with isobutylaluminum chloride (0.0333 mol Al) and placed dropwise into a reaction vessel. The temperature peaked at 0 ° C to form a greyish precipitate which turned brown after further addition of BuAlClg. After stirring for a further 30 minutes, the reaction was terminated, thereby obtaining a dark reddish brown liquid and a brown precipitate.

C. The catalyst component prepared in Example XIX was used in the polymerization of ethylene (87.8 ° C, 10 mol- ethylene, 0.0002 parts of catalyst calculated as Ti, triethyl aluminum ca.

k5 mg / kg calculated as Al, H 2 as indicated), the following results were obtained in Table D:

Table D

Catalyst H ^ Yield Properties of the resin

kPa g PE / g Ti h MI HLMI ELMI / MI

XIX B click IO5.I8O 6.2 206 33.6 30 827 75.290 33.9 950 28.1

Example XX

A. 0. 99 mole Ti (OBu) ((TBT), 0.169 mole magnesium curls and 0.029 mole AlCl 6 H 2 O in diluent in octane were combined in an electric jacketed stirred reaction vessel. The hydrated aluminum salt dissolved part- 8105319: - 36 - * <.

look like and. During 11 ° C, the color of the solution darkened rapidly until a black liquid was obtained with lively foaming due to gaseous formation on the surface of the magnesium. The solution took on a blue color and, while boiling smoothly at reflux to 122 ° C, a dark blue-black liquid was formed with a little magnesium remaining. Bee. All the magnesium metal had disappeared and the solution had a faint green color. The reaction was stopped and a dark blue-black liquid and a green precipitate were recovered in a 10 volume ratio of about 95'5B. The reaction product described above was combined with isobutylaluminum chloride in an Al / Ti molecular ratio of 3: 1 and 6: 1 by dropwise introduction of the chloride into a reaction vessel containing the titanium material. In the first reaction, (3: 1), the alkyl chloride was added at a rate of 1 drop / 2 - 3 seconds until a peak temperature of 1 + 2 ° C was reached, changing the color from blue-green to brown. After stirring for an additional 30 minutes, the reaction product, a reddish brown liquid and a brown precipitate, were isolated (XXB).

20 C .. Similarly, an Al / Ti product 6: 1 was obtained, with the same results (XX C).

D. The reaction products XXB and XXC were used with triethylaluminum cocatalyst (1 + 5mg / kg Al) in the polymerization of ethylene (10mol%) with isobutane as a diluent at 8T, 8 ° C and under the stated hydrogen pressure. The tests were terminated after 60 minutes to give the results listed in Table E:

Table E

Catalyst yield Properties of the resin

30 Sat ° r kPa mol g PE / g Ti h MI HLMI HIMI / MI

XXB UlU 1 + 0 6 81 ;. 580 17.2 517 30.1 827 5k2 75,280 5b, 9 ll + 13 25.7 XX C bik 2k5 5I4..I4.I1.O 1 +, 11 129 31.1+ 35 827 183 3 ^ .860 26, 2 801 30.5 8105319 ......

- 37 -

Example XXI

A. 0.153 mole Ti (OBu) ((TBT), 0.153 mole Mg curls and 0.026 mole HiCl 3 .H 2 O 2 were combined with 61.75 µl 11 octane in an electric heating jacket and agitator. When heated to H ° C, the color of the yellow solution darkened and gas evolution on the surface of the magnesium metal could be observed at about 57 ° C. With continued heating, gas evolution increased to 102 ° C (15 minutes reaction time) to give the reaction system a light, cloudy brown color. Strong foaming continued as the brown color darkened, until 126 ° C (75 minutes) all the magnesium had disappeared and the reaction was terminated. The reaction product (XXI A1) was a hydrocarbon-soluble dark brown liquid and a small amount of a fine precipitate.

In a second run, 0.19 moles of TBT, 0.11 * 9 moles of Mg and 0.051 moles of HiClg.eHgO were combined in octane in the same manner. The magnesium metal disappeared at 115 ° C after 120 minutes and the reaction yielded a dark brown-black hydrocarbon-soluble liquid which separated on standing into a very fine dark precipitate and a yellow liquid in a volume ratio of ca. 50:50 (XXI A2).

B. Reaction product I Al was shaken and an amount (0.0137 mole Ti) was charged to a reaction vessel with hexane diluent to which iBuAlCl 2 (0.011 mole Al) was added dropwise at a rate of 1 drop / 2 - 3 seconds to 28 ° C and from 1 drop / second to a peak temperature of 39 ° C. After completion of the addition, the contents of the vessel were stirred for 30 minutes and the reaction product, a dark reddish brown liquid and a dark gray precipitate, were isolated.

30 (XXI BI).

The same reaction product (XXI A1) was combined with ethyl aluminum chloride in the same manner at a Al / Ti molecular ratio of 3: 1. The reaction product consisted of a dark reddish brown liquid and a dark gray solid (XXI B2).

In a substantially identical manner, reaction product 8 1 0 5 3 1 9 *. __________ ________ _____; - 38 - XXI A2 (Ti / Mg / Ni molecular ratio of 1: 1: 0.3 * 0 combined with xBuAlClg At an Al / Ti ratio of 3 ': 1, giving the same results except that the top liquid- layer had a pale reddish brown color (XXI B3).

In a further test, reaction product XXI A2 was reacted in the same manner with iBuAlClg at: a molar ratio Al / Ti of --6: 1 », correspondingly resulting in a dark liquid and ··" a dark precipitate (XXI B * 0.

The same reaction product XXI A2 was combined with ethylaluminum 10-chloride in the same manner, leaving a dark reddish brown

liquid and a dark gray solid were formed (XXI B5). Example XXII

A. Example XXI A was repeated, introducing the reactants in a Ti / Mg / MiTi ratio of 1: 0.65 15: 0.11. The color change was from deep brownish yellow to dark brown under gas evolution, and then again via gray-brown to dark blue-black after the magnesium had been consumed, in a reaction taking place over 6 hours (XXII A).

B. Reaction product XXII A was combined with ethyl aluminum chloride in the manner described in Example XXI B at a Al / Ti molecular ratio of 3: 1. A reddish brown liquid and a reddish brown precipitate (XXII B) were obtained.

Example XXIII

Example XXII A was repeated using the reactants in a molecular ratio of 1: 0.75: 0 ^ 128,

The dark brown reaction product contained 5% by weight Ti, 2.2% by weight

Mg and 0.97 wt.% Ni.

The reaction product was then treated with isobutylaluminum chloride at an Al / Ti molecular ratio of. 3: 1.

30 Example XXXV

A series of TMg catalysts prepared according to Examples XXI B and XXII B were used as catalyst component in the polymerization of ethylene (87.8 ° C, 10 mol% ethylene, triethylaluminum ca. mg / kg calculated as Al , Hg as indicated), where-35. The results shown in Table F were obtained: 8 1 0 5 3 1 9 ----------------- - 39 -

Table F

Cataly- Yield Properties of the resin

Sator kPa g PE / g Ti h MI HLMI HLMI / MI

XXI B3 JüU 90,750 9.55 270 28 5 827 10k.980 2k, 6 683 27.8 kik 111.9 ^ 0 0.29 10.7 36.8 827 II2.260 3.1 H9 38.9 10 XXI Bk. kik 59,790 0.25 10.9 Yy-3.6 827 62,720 1.0 k3.6 bl, 6 XXII B ivlU 57 * 890 1.66 5k, 9 33.1 827 6k.7kO 6.13 183 29.8 15 · * ·. * XXI B2 Kik 238,670 0.65 19.5 30.2 827 271,560 6.7 188 28.1 XXI B5 207 ^ 175,000 low - 20 ^ The tests under greater hydrogen pressures proceeded extremely quickly, resulting in a polymer formation such that the tests had to be terminated.

Example XXV

25. A. TBT, · Mg ^ and MgSiFg.OH ^ O were combined in octane in a refluxed heated reaction vessel, as described in the previous examples, to yield reaction products with 1: 1 molecular ratios : 0.3k resp. 1: 0.75: 0.128.

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

C. The resulting brown precipitate was separated from the reddish brown liquid superimposed, and used with TEA to form about k5 mg / kg Al under standard conditions for polyethylene polymerization (87.8 ° C, hydrogen pressure kik kPa), 8 1 0 5 3 1 9 ------------------- * «» * <- 4o - where resin was formed in a yield of 107,500 Pe / g Ti h and characterized by Mi 2.85, HLMI 84.5 and MIE 29.6.

D. The reaction product obtained according to the foregoing 1: 1: 0.34 was similarly activated with isobutylaluminum-5 chloride at an Al / Ti ratio of 3: 1. The solid reaction product was washed several times with hexane and used with TEA in a polyethylene polymerization reactor, which had previously been introduced into Bu-1, so as to provide a resin with a target density at 76.7 ° C and. obtain a material pressure of 207 kPa from the ethylene / butene-1 used as starting material. The resulting resin had a density of 0.9193, MI 1.91, HLMI 60.8 and MIR 31.8.

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

Example XXVI

A. In the following experiments, TMMg reaction products were reacted with the halide component, which was added gradually, usually dropwise, to contain the exotic reaction. The reaction was carried out under the ambient conditions for a sufficiently long period of time to complete the addition with stirring of the reaction mixture 10 to 30 minutes after the peak temperature occurred (where 6 t was applicable, the solid and liquid TMMg components mixed into a dispersion and used in that form).

The reaction participants and the reactions of the reaction participants can be found below:

Catalyst Component, Molecular Halide Molecular Ratio Ti / Mg / MgClg .6 (Hg) Activator Thing 30. 1 / 0.65 / 0.11 (0.66) Bu1A1C12 2: 1 (Al / Ti) 1 / 0.65 / 0.11 (0.66) Bu1A1C12 3: 1 1 / 0.65 / 0., 11 (0.66) Bu1A1C12 4: 1 1 / 0.65 / 0.11 (0.66) Bu1A1C12 6: 1 1 / 0.65 / 0.11 (0.66) Et A1Cl2 3: 1 35 1 / 0.65 / 0.11 (0.66) EtBCl2 1.25: 1 (B / Ti) 8105319 ' -. - kl - 1 / 0.65 / 0.11 (0.66) EtBClg 3: 1 (B / Ti) 1 / 0.65 / 0.11 (0.66) SiCl ^ 3: 1 (Si / Ti) 1 / 0.65 / 0.11 (0.66) SiCl ^ 6: 1 (si / Ti) 1 / 0.75 / 0.128 (0.768) EtAlClg 3: 1 5 1 / 0.75 / 0.128 (0.768) Et ^ C ^ 3: 1 1 / 0.75 / 0.128 (0.768) Bu1A1C12 3: 1 1 / 0.76 / 0.128 (0.768) Bu1A1C12 6: 1 1 / 0.75 / 0.128 (0.768) EtBCl2 3: 1 (B / Ti) 1 / 0.75 / 0.128 (0.768) (CH3) 2SiCl2 6 t 1 (Si / Ti) 10 1 / 0.75 / 0.128 (0.768) (CH3) 3SiCl 6: 1 (Si / Ti) 1 / 0.75 / 0.128 (0.768) (CH JgSiHCl 6: 1 (Si / Ti) 1 / 0.75 / 0.128 (0.768) SiCl 3: 1 (Si / Ti) 1 / 0.75 / 0.128 (0.768) SiCl ^ 6/1 (Si / Ti) 1 / 0.75 / 0.128 (0.768) TiCl ^ 1.5: 1 (Ti / Ti) 15.1 / 0.75 / 0.128 (0.768) TiCl ^ 3: 1 (Ti / Ti) 1/1 / 0.17 (1.02) Bu1A1C12 3 ": 1 1/1 / 0.17 (1.02) EtAlCl 3: 1 1/1 / 0.3¾ (2.0¾) Bu ' AlCl 3: 1 1/1 / 0.3¾ (2.0¾) Bu1A1C12 6: 1 20 1/1 / 0.51 (3.06) Bu1A1C12 3: 1 1 / - / 0.51 (3.06) Bu1A1C12 6: 1 2/1 / 0.17 (1.02) Bu1A1C12 3: 1 2/1 / 0.17 (1.02) Bu1A1C12 6: 1 2/1 / 0.3¾ (2.0¾) 'Bu1A1C12 3 : 1 25 2/1 / 0.3¾ (2.0¾) Bu1A1C12 6: 1 3/1 / 0.51 (3.06) Bu1A1C12 3: 1 3/1 / 0.51 (3.06) Bu1A1C12 6: 1

Example XXVII

A. Catalyst (3: 1 Al / Ti) Activated Catalyst 30-Star Were Used in a Series of Polymerization Tests to Obtain Results in Table G: 8105319-1) -2-

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Reaction conditions Diluent: isobutane temperature: 8TS8 ° C

hydrogen: as indicated cocatalyst: triethylaluminum (U5 mg / kg Al) catalyst: reaction product of Ti (OBu) ^ - Mg-MgClg .OHgO, activated with Bu1A1C12 (Al / Ti = 3: 1) ethylene: 10 mol # duration of the test: 60 minutes. As can be seen by comparing the molecular ratio of Ti / MgClg.OHgO, a maximum in the melt index is observed at a ratio of 9: 1 (Ti / II 1.5: 1). In the following further experiments, the effect of the SI / Ti ratio in the activated TMMg catalysts (molecular ratio 1: 0.65 * 0.11) was examined in the polymerization of ethylene. The results are shown in Table H: ^ 8 1 0 5 3 1 9 ------------------ -. . - Ml - J-4

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Beaction conditions:

Diluent: isobutane "temperature: 8j, 8 ° C

hydrogen: as indicated cocatalyst: triethylaluminum (1 <-5 mg / kg Al) catalyst: reaction product of Ti (OBu) - Mg-MgClg-6 · 20, activated as indicated above ethylene: 10 mol length of test: 60 minutes.

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The resin portions obtained in the foregoing were stabilized with 100 mg / kg calcium stearate and 1000 mg / kg "Irganox 1076" and the properties were determined by conventional tests. The material was converted into blown film in a 38.1 mm "HartigT extruder (60 rpm rotating screw; 76.2 mm die with 2.08 mm die gap; 2.8 air cooling. - U, l) ° C) and further investigated as shown in the following tables K and L:! 8 1 0 5 3 1 9 --------------------- ---- - t * - 51 - on π- o cm 'ir \ vo cn * "Η H m H HO H o O ^ ö« .vo cn -3-H on σ \ o t- w ¢ 3

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8105319 ---------------- - 56 - * · * «/ I. t E. In further large-scale polymerizations using TMMg catalyst (dispersion, separated from the supernatant and washed with hexane) in a similar manner at a molecular ratio of 5 1: 0.75 0.128 (EADC, Al / Ti = 3: 1), hexene-1 was charged to the reactor as a comonomer with ethylene and then butene-1 was used instead, as shown by analysis of the waste gas, ethylene / butene-1 / hexene-1 copolymers and terpolymers during processing were obtained. The results are found in the following table M:

Table M

Comonomer Density MI HIM ΗΤ, ΜΙ / ΜΓ hexene 0.9339 0.83 26.9 32 hexene 0.9293 0.73 23.9 33 15 hexene / butene 0.9175 0.9 ** 31, ** 33 butene 0 .91 ** 8 0.70 25.2 ^ 3β butene 0.91 ** 8 0.70 25.2 36 butene 0.9135 0.9k 29.9 32

Example XXVIII

TMMg catalyst, which was prepared according to the examples and activated with isobutyl aluminum chloride (Al / Ti = 3: 1) was also used for the preparation of other eopolymers with varying pre-introduced comonomers, with isobutane as diluent, a reactor temperature of 76.7 ° C, a hydrogen pressure of 25 207 - 276 kPa and enough TEA to introduce 60 mg / kg Al, yielding the following results: ethylene / 3-methylbutene-1 MI MR Density 1.25 27 Λ. 0.9 ** 88 1.25 28.9 0.9 * 183 30 1.36 27.9 0.9507 1.55 27.7 0.9 ** 97 1.56 27.5 0.9-1 * 95 .1.87 29.9 0.9 ^ 96 1.63 28.5 0.9 U55 35 2.25 28.8 0.9 ** 37 8105319 ...... .............

- 57 - ï ϊ 1, ½ 30.0 0.9 ^ 28 5.01 30.3 0.9 ^ 11 1.59 31.9 0.9 ^ 00 5 isobutene 0.37 32., b 0.9518 1.35 29.6 0.956b 1.79 31.1 0.95½ 1.17 31.7 0.9567 1 ^, 20 3σ, 1 0.9582 10. 3.30 32.9 0.9555

The polymerization or copolymerization of other olefin monomers, such as propylene, i) methyl pentene-1, alkyl etherylates and methaciylates and alkyl esters, can be accomplished in a similar manner.

15

The following comparison tests were also carried out:

Comparative Examples A. In the same reaction vessel used for other preparations, TBT, Mg ^ and anhydrous MgCl2 were combined in octane 20 in a molecular ratio of 2: 1: 0.3¾ and refluxed for 5 minutes with no indication was that the reaction occurred. Set anhydrous MgClg remained undissolved. See also example I B.

B. To the same system, an amount of free water, responding to a ratio of Mg 1 / MgCl 2 .OH 2 O of 1: 0.3 ¾ in one portion, was added, but no change was found to occur.

C. TBT and Mg 2 were combined in a molecular ratio of 2: 1 in octane and refluxed. While the 30. yellow color became slightly more intensive, no reaction appeared to occur.

D. To the previous system C, an amount of free water corresponding to a ratio of Mg / MgCl 2 .OHgO of 1: 0.3¾ was added. A small amount of pale yellow precipitate formed, indicating hydrolysis of the titanium compound, but the magnesium remained unconverted.

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- 58 -! / ι! Ε. ΤΒΤ and MgCl 2 .OH 2 O were combined in octane in a 1: 0.3 mole ratio and boiled under reflux. After the salt was completely dissolved, the solution became cloudy and slightly viscous with continued boiling under reflux for 3 hours, but 5 became clear and a cloudy yellow liquid and a whitish precipitate overnight. In a further test at a molecular ratio of 1: 0.128, a clear golden yellow liquid was formed; reflux for only 16 minutes. At a molecular ratio of 1: 1.17, foaming and the formation of a thick cream gel resulted in the reaction after 25 minutes. Compare the above example VII. ; \ 8105319 Γ

Claims (15)

A process for the polymerization of 1-olefins, alone or together with at least one copolymerizable monomer, under polymerization conditions in temperature and pressure with an olefin polymerization catalyst system, characterized in that this system consists of a mixture of cocatalysts, one of which is a halide-activated intermetal compound consisting of the reaction product of a polymer transition metal oxide alkoxide and a reducing metal having a higher oxidation potential than that of the transition metal. 2. A process according to claim 1, characterized in that the polymeric transition metal oxide alkoxide is prepared by partial hydrolysis of the transition metal alkoxide. 3. Process according to claim 2, characterized in that the hydrolysis is effected with a water complex as a source of water. H. Process according to claim 3, characterized in that the water is provided in the form of a hydrated salt, e.g. a hydrate of an aluminum, cobalt, iron, magnesium or nickel salt. Process according to claim 3, characterized in that the water is provided in the form of a hydrated oxide, preferably silica gel. Process according to any one of claims 3-5, characterized in that the transition metal to water molecular ratio is from about 1:25 to about 1: 1.5. A method according to any one of claims 1-6, characterized in that the reducing metal consists of magnesium, calcium, zinc, aluminum or mixtures thereof. 8. A method according to any one of claims 1-7, characterized in that the transition metal is titanium or zircon. Method according to claim 8, characterized in that the transition metal and the reducing metal are contained in a 8 1 0 5 3 1 9 ------------ - Vj1>,. i t * * (molecular ratio of about 0.5 to 1 to about 3: 1. 10. Process according to claim 9S, characterized in that the transition metal and the reducing metal are present in a molecular ratio of about 1: 0.1 to about 1: 1. Process according to any one of claims 1 to 10, characterized in that the halide activator is at least one of the following: an alkyl aluminum halide, a silicon halide, an alkyl, silicon halide, a titanium halide or an alkyl boron halide. Process according to any one of claims 11 to 11, characterized in that the cocatalyst is an organo-aluminum or organo-boron compound, preferably triethyl aluminum or triethylhorane. 13. Alkene polymerization catalyst system, characterized in that it consists of a mixture of cocatalysts, one of which is a halide-activated intermetal compound consisting of the reaction product of a polymer transition metal oxide alkoxide and a reducing metal with a higher oxidation potential than that of the transition metal. The catalyst system according to claim 13, characterized in that the halide activator is at least one of the following: an alkyl aluminum halide, a silicon halide, an alkyl silicon halide, a titanium halide or an alkyl boron halide. Catalyst system according to claim 13 or 1, characterized in that the transition metal is titanium or zircon. Catalyst system according to any one of claims 13-15, characterized in that the reducing metal consists of magnesium, calcium, zinc, aluminum or mixtures thereof. Catalyst system according to any one of claims 3 - β, characterized in that the polymeric transition metal oxide alkoxide is the product of controlled partial hydrolysis of a titanium alkoxide. Catalyst system according to any one of claims 13-17, characterized in that the transition metal and the reducing metal are present in a molecular ratio of about 0.5: 1 to 3: 1. Catalyst system according to claim 18, characterized in that the ratio mentioned there is about 1: 0.1 to about 1: 1. 8105319 -----------