SE461100B - PROCEDURES FOR THE PREPARATION OF AN INTERMETAL SOCIETY FOR USE AS A CATALYTIC COMPONENT FOR POLYMERIZATION OF ALFA OLEFINES - 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

461 100. compound, usually a titanium halide mixed with an organometallic compound, such as alkylaluminum. The transition metal component may be activated by reaction with a halide promoter, such as an alkylaluminum halide.

Among the improved catalysts of this type are those which contain a magnesium component, usually by the interaction of magnesium or a compound thereof with the transition metal component or the organometallic component, such as by milling or chemical reaction or association.

There is also interest in the production of intermediates for high density resins with modified properties using coordination catalysts of this type. In particular, resins with a broader molecular weight distribution and a higher melt index are sought.

The present invention thus relates to a process for the preparation of an intermetallic compound for use as a catalytic component in the polymerization of alpha-olefins alone or together with at least one copolymerizable monomer, which process is characterized by the reaction of; (1) a polymeric transition metal oxide alkoxide wherein the transition metal is titanium or zirconium, which polymeric transition metal oxide alkoxide is prepared by partial hydrolysis of a transition metal alkoxide, which hydrolysis is performed with an aquo complex as a water source, the water being provided in hydrated form of salt, iron, magnesium or nickel or in the form of a hydrated oxide, preferably silica gel; and (2) a reducing metal having a higher oxidation potential than the transition metal, which reducing metal is magnesium, calcium, zinc, aluminum or mixtures thereof, the molar ratio of the transition metal to the reducing metal being from about 0.5: 1 to about 3; 1, the reaction being initiated by heating to an elevated temperature, wherein an exothermic reaction is initiated, the heating being continued until the stoichiometric amount of reducing metal is consumed, and optionally further reacting the product with a halide activator.

The polymeric transition metal oxide alkoxide can be prepared separately by controlled hydrolysis of the alkoxide; or the polymeric oxoalkoxide may be provided by an in situ reaction, for example hydrolysis in a reaction medium comprising the reducing metal. For example, titanium or zirconium tetrabutoxide can be reacted with magnesium metal in a hydrocarbon solvent, and in the presence of a controlled source of water, preferably a hydrated metal salt, such as magnesium halide hexahydrate. Transition metal alkoxides, especially titanium alkoxides, are known for their bonding properties in organic solvents and are sensitive to hydrolysis. It is reported that the hydrolysis reaction proceeding from the oligomeric, usually trimeric titanium alkoxides results in polymeric titanium oxide alkoxides, commonly expressed as Ti (oR) 4 + nu o - \ Tionwiußzn + zn Ros 2 Condensation reactions can also occur especially at elevated temperatures to structures primary metal-oxygen-metal bridges such as: 461 100 91 * “BR OR - Ti - O - Ti - OR R OR which in turn may participate in or constitute precursors for hydrolysis reaction.

These polymeric titanium alkoxides or oxoalkoxides (sometimes designated u-oxoalkoxides) can be described by the series [ri3 (x + 1) o4x (oa) 4 (x + 3) _7 wherein x = o, 1,2,3, ..., wherein the structure reflects the tendency of the metal to expand its coordination beyond its primary valence coupled with the ability of the alkoxide to bridge two or more metal atoms.

Irrespective of the particular form which the alkoxide is intended to take, it is in practice sufficient to realize that the alkoxide oligomers in controlled hydrolysis form a series of polymeric oxide alkoxides which vary from the dimer via cyclic forms to linear chain polymer of up to unlimited chain length. More complete hydrolysis on the other hand leads to precipitation of insoluble products, which with completed hydrolysis results in orthotitanic acid.

For simplicity, these materials will be referred to herein as polymeric oxide alkoxides of the respective transition metals representing the partial hydrolysis products. The hydrolysis reaction can be carried out separately, and the products are isolated and stored for further use, but this is inappropriate especially in view of the prospect of further hydrolysis, consequently the preferred application is to generate these materials in the reaction medium. Signs indicate that the same hydrolysis reaction occurs in situ.

The hydrolysis reaction itself can be controlled directly by the amount of water added to the transition metal alkoxide and the rate of addition. Water must be added batchwise or in a stepwise or sequential manner: Lump addition does not lead to the desired reaction but produces excessive hydrolysis with precipitation of insoluble substances. Dropwise addition is suitable in the same way as the use of reaction water, but it proves more convenient to provide the water as crystallization water, sometimes referred to as cation 7 anion jon given or zeolite water. Thus, common hydrated metal salts are usually used where the presence of the salts themselves is not harmful to the system. It turns out that the bond provided by the coordinated sphere of water in a hydrated salt is adapted to control the release and / or availability of water, or water-related parts of the system required to effect, participate in or regulate the reaction.

The total amount of water used has, as just mentioned, a direct significance for the form of polymeric oxide alkoxide produced and is thus selected in relation to catalytic performance. (It is believed without limitation that the stereoconfiguration of the partially hydrolyzed transition metal alkoxide determines, or in part contributes to the character, or the result of the catalytic action of the activated catalyst component.) It has generally been found sufficient to provide as little as 0, 5 moles of water per mole of transition metal. Amounts of up to 1.5 moles are suitable with higher amounts up to 2.0 moles being useful whenever precipitation of hydrolysis products from the hydrocarbon solvent medium can be avoided. This can in principle be achieved by reducing the addition rate and stopping the addition at the first sign of precipitation. Assuming that the reaction is substantially equimolar, a certain excess of water is suitably used in some cases as is customary.

It is to be understood that the stereoisomeric form, chain amount, etc. of the hydrolysis product may be slightly altered with the elevated temperature required by the subsequent reaction with the reducing metal, and in situ processes will likewise affect equilibria through the mass effect. Likewise, the formation of alkanol can affect equilibria, reaction rates, etc.

The hydrolysis reaction proceeds under ambient conditions of pressure and temperature and does not require any special conditions. A hydrocarbon solvent can be used but is not required. Only contact of the materials for a period of time, usually 10-30 minutes to 2 hours is sufficient. The resulting material is stable under normal storage conditions and can be supplemented to the appropriate concentration level as desired, simply by dilution with hydrocarbon solvent. U The polymeric transition metal oxide alkoxides are reacted with a reducing metal having an oxidation potential higher than the transition metal. Preferably, a polymeric titanium oxide alkoxide is used together with magnesium, calcium, potassium, aluminum or zinc as the reducing metal. Combinations of transition metal alkoxide, reducing metal and hydrated metal salt are usually selected with reference to electropotentials for reducing side effects to a minimum, as is known in the art, and to ensure preferred levels of activity for olefin polymerization, magnesium stocks are generally added. the system by appropriate choice of reducing metal / hydrated metal salt.

In the preferred embodiment (for the sake of simplicity, reference is made in the following 7,461,100 text), titanium tetra-n-butoxide (TBT) is reacted with magnesium turnings and hydrated metal salt, preferably magnesium chloride hexahydrate, at a temperature of 50 ° C. 150 ° C, in a reaction vessel under autogenous pressure. TBT can be the reaction medium or a hydrocarbon solvent can be used. Ti / Mg molar ratios can vary from 1: 0.1 to 1: 1, although for the most homogeneous reaction system a stoichiometric ratio of Tiiv to Mg ° of 1: 1 is preferred with an amount of hydrated metal salt to provide during the reaction of about 1 mole of water per mole of Mgo.

The hydrocarbon-soluble catalyst precursor comprises predominantly 'Ti constituents in associativnned Mg constituent alr, in one or fin-stereoconfiguration complexes which are believed to constitute substantially oxygenated types. Some evidence of mixed oxidation states for the titanium values suggests a related system of integrated parts of Tilv, TiIII and Tiïliestandsdelarknskei.a quasi-equilibrium relationship at least under dynamic reaction conditions. The preferred precursor is assumed to incorporate (Ti-O-Mg) bridging structures without limitation.

The intermetallic compounds are of particular interest as catalyst precursors, in supported or unsupported systems, for the isomerization, dimerization, oligomerization or polymerization of olefins, alkynes or substituted olefins in the presence or absence of reducing agents or activators, for example IA, IIA, IIIA or IIB metals.

In the preferred use of such precursors, they are reacted with a halide activator, such as an alkylaluminum halide, and combined with an organometallic compound to produce a catalyst system specifically adapted for the polymerization of ethylene and comonomers to polyethylene resins. the transition metal component is an alkoxide, usually a titanium 461,100 or zirconium alkoxide comprising substantially -OR substituents wherein R may comprise up to 10 carbon atoms, preferably 2-5 carbon atoms and most preferably n-alkyl, such as n-butyl. The selected component is normally liquid under ambient conditions and the reaction temperatures for ease of handling, and is also hydrocarbon soluble for ease of use. It is generally preferred for ease of carrying out the related hydrolysis reaction to use transition metal compounds comprising only alkoxide substituents, although other substituents may be considered where they do not interfere with the reaction in the sense that they significantly modify performance in use. In general, the halide-free n-alkoxides are used. the transition metal component is provided in the highest oxidation state of the transition metal to provide the desired stereoconfiguration structure among other considerations. Most suitable, as just mentioned, as alkoxide is a titanium or zirconium alkoxide. Suitable titanium compounds include titanium tetraethoxide and the related compounds comprising one or more alkoxy groups including n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, tert-pentoxy, tert-amyloxy, tert-amyloxy , n-hexyloxy, n-heptyloxy, nonyloxy, etc.

Some indications are that the rate of hydrolysis of the normal derivatives decreases with increasing chain length and the rate decreases with molecular complexity, namely tertiary, secondary, normal, consequently these considerations can be taken into account when choosing a preferred derivative. In general, titanium tetrabutoxide has been found to be excellently suitable for the practice of the present invention, and related tetraalkoxides are equally preferred. It is to be understood that mixed alkoxides are perfectly suitable and can be used where they are conveniently available. Complex titanium alkoxides which sometimes include »I 9 461 100 other metal components may also be used.

The reducing metal is provided at least in part in the oxidation state zero as a necessary element in the reaction system. A suitable source is the well-known chips, or tape or powder. These materials, as provided commercially, may be in a passivated surface oxidized state and rolling or grinding to provide at least some fresh surface may be desirable at least to control the rate of reaction. The reducing metal may be provided as is convenient, in the form of a slurry in the transition metal component and / or the hydrocarbon diluent or may be added directly to the reactor.

In the case of in situ production (or for the independent production of the polymeric transition metal alkoxide), the source of water, or water-related parts, is provided, whereby amounts of water are released or diffused or become available, as the case may be. in a controlled manner at a delayed rate during the reaction. As just mentioned, the coordination sphere provided by a hydrated metal salt has proved suitable for the purpose; but other sources of water in the same proportions are also useful. Calcined silica gel free from other active components but containing controlled amounts of bound water can thus be used. In general, the preferred source of water is an aqua complex where 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 conveniently carried out in a closed reactor, preferably coupled with reflux capacity 461,100 for volatile components at the elevated temperatures evoked in the reaction vessel. Autogenous pressure is used 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 the vessel surfaces, to provide intimate mixing 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 intermixing of components, heat transfer and maintenance of a homogeneous reaction system.

Saturated hydrocarbons are preferred which have a boiling point in the range of 60-190 ° C. The liquid transition metal component may also serve at least in part as a reaction medium, especially where no added solvent is used.

The reaction involves a step in which additional volatile components form azeotropes with the solvent, or if the components are used pure, constitute the source of reflux but in either case it is preferred, at least for carrying out the reaction by intermediate steps with appropriate reaction times, to return volatiles to the reaction zone.

Butanol is thus generated when the titanium component is titanium tetra-n-butoxide and forms an azeotrope with the hydrocarbon solvent.

The choice of solvent and / or alkoxide in relation to possible suppression of reaction temperature is consequently a consideration as is known to those skilled in the art.

The reaction temperature will to some extent be a matter of choice within a wide range depending on the reaction rate which is convenient to carry out. It has been found that the reaction system (which consists of the liquid transition metal component, dissolved in hydrated metal salt, reducing metal particles and solvent, where desired) shows visible gas generation at about 60-70 ° C, which suggests an initiation temperature or activation energy level at about 50 ° C, which therefore constitutes the minimum necessary temperature for the reaction of the polymeric oxide alkoxide with the reducing metal. The reaction is somewhat exothermic during consumption of the reducing metal and can consequently be easily driven to the next step which is the reflux temperature. Since the generated alkanol is largely consumed during the course of the further reaction (as an independent part), the current system temperature will change and completion of the reaction will be exhibited by consumption of visible metal and / or attainment of the reflux temperature of the pure solvent within a period as short as 30 minutes to 4 hours or longer. Such temperatures can reach the value 140-190 ° C and of course higher temperatures can be imposed without apparent advantage. It is most convenient to work in the range 50-150 ° C, preferably 70-140 ° C. In the absence of solvent, the upper limit will simply be determined by the reflux temperature of the alcohol generated during the course of the reaction.

Reaction of the components is most evident from the clear color change, with exotherm, which accompanies the initiation of gas evolution. When the lack of opacity or turbidity of the solution allows observation, the evolution of gas varying from bubbles to vigorous movement is most evident at the surface of the metal and the usually light colored solutions immediately turn to greyish, then darken rapidly to blue, sometimes violet, usually bluish black. , sometimes with a greenish shift. Analysis of the gas does not show any HCl; and is mainly H2. After the rapid color change, some color darkening occurs during a gradual increase in temperature with concomitant gas evolution. In this step, the alkanol corresponding to the alkoxide moiety is generated in an amount sufficient to suppress the boiling point of the solvent and is found 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 kept in slurry form for ease of further use. The viscous to semi-solid product shows a substantially amorphous character when isolated by X-ray diffraction analysis.

Molar ratios between the components can vary within certain limits without significantly affecting the performance of the catalyst precursor at end use. To avoid competing reactions which render the reaction product unsuitable gelatinous or difficult to treat, the transition metal component is usually provided in at least a molar proportion relative to reducing metal but the transition metal / reducing metal ratio may range from about 0.5 to 1.0 to 3. 0: 1, 0 or more, preferably 1 / 0.1-1 / l. An insufficient level of reducing metal will result in suppression of the reaction temperature so that the reflux temperature of the pure solvent remains unreached; an excess of reducing metal, on the other hand, will be immediately apparent from the unused portion thereof and, consequently, the desired amount of this component is determined with ease by those skilled in the art.

Within these ranges, a varying proportion of the reaction product may constitute a hydrocarbon insoluble component which, however, may and will usually be slurried with the soluble component for use, for example in further reaction with a halide activator to produce an olefin polymerization catalyst. The amount of such an insoluble component can be controlled in part by the use of a solvent with a suitable partition coefficient, but where the use of a common hydrocarbon solvent, such as octane, is preferred for practical reasons having equimolar ratios of, for example, Ti / Mg / H 2 O components. proved most suitable for the preparation of a homogeneous reaction product.

Water, or water-related moiety, is also preferably provided in molar ratio to the transition metal component, for similar reasons regarding homogeneity and lightness pre-reaction. Thus, in the case of MgCl 2 .6H 2 O, an amount of 0.17 moles during the reaction provides about 1 mole of water and this proportion up to about 2 moles of water provides the lightest reactions with one or more moles of transition metal component. More generally, H 2 O can range from about 0.66 to 3 moles per mole of transition metal. The amount of water present at any given stage of reaction is, of course, probably considerably less, varying in catalytic proportions relative to the remaining components depending on the manner and rate at which it participates in the reaction sequence. , currently unknown. It is not less specifically understood without limitation as an operative hypothesis that the water, or the reaction rate-regulating water-related moiety is activated, released, made available to, or diffuses in a manner that provides sâdandahr in a regular, continuous, constant, or variable speed related manner. However, the same molar proportion of free water provided at the start of the reaction is completely ineffective in initiating the reaction at this or higher temperature and results in undesirable completed hydrolysis reactions.

The weighted amount of water is essentially in molar balance or molar excess relative to the reduced metal component and is found to be related to its consumption in the reaction, since a molar insufficiency with water will always result in excess reducing metal remaining. In general, a modest excess of water of 10-40% is suitable to ensure complete reaction. Higher proportions are suitable without limitation but should be kept in relative stoichiometric balance to the transition metal component. 461 100 14 The choice of aquacomplex or hydrated metal salts where used is essentially a matter of the regulated availability of water that it offers to the system. Sodium acetate trihydrate is thus suitable in the same way as magnesium acetate tetrahydrate, magnesium sulfate heptahydrate and magnesium silicon fluoride hexahydrate. A salt with a maximum degree of hydration in accordance with the controlled release offered by the coordinate binding relationship is preferred. A hydrated magnesium halide such as magnesium chloride hexahydrate or magnesium bromide hexahydrate is most suitably used.

These salts, like other hygroscopic materials, when present in commercial anhydrous form also contain some sorbed water, for example 17 mg / kg (see British Pat. No. 1,401,708), although well below the molar amounts contemplated in accordance with the present invention.

Consequently, unless otherwise specifically modified for the purpose, anhydrous salts are not suitable here.

The reaction system as defined in the above description does not require, although it will tolerate, an electron donor or Lewis base, or a solvent which performs some of these functions. As shown in the examples, the reaction in the preferred embodiment is completed with crystallization water and an alcohol component in the system. It is therefore not known with certainty whether proton transfer or electron donor mechanisms participate or compete in the reaction system.

No separations are necessary because at least a portion of the reaction product is soluble in the saturated hydrocarbon where it is used as a solvent or provides a solvating medium so that even when a precipitate also occurs and even after storage, a useful reactive slurry with ease of manufacture.

In a preferred aspect of the invention, the reaction product (catalyst precursor) is further co-reacted with a halide activator, such as an alkylaluminum halide, a silicon halide, an alkylsilicon halide, a titanium halide or an alkylboron halide. It has been found that the catalyst precursor can be easily activated by simply combining the product with the halide activator. The reaction is strongly exothermic and consequently, in typical cases, the halide activator is gradually added to the reaction system. After completion of the addition, the reaction is normally also completed and can be terminated. The solid reaction product, or slurry, can then be used immediately, or stored for future use. Generally, for the best control of molecular weight properties and in particular for the production of low density resin, only the hydrocarbon washed solid reaction product is used as a catalyst.

The halide activator is usually provided for co-reaction in a molar ratio of 3: 1 to 6: 1 (aluminum, silicon or boron, relative to the transition metal) even if the ratio of 2: 1 or more has been used successfully.

The resulting catalyst product can be used directly in the polymerization reaction even if it is typically diluted, extended or reduced as needed to provide in a suitable feed an amount of catalyst equivalent to 80-100 mg / transition metal, based on a nominal productivity of greater than 200,000 grams of polymer / gram of transition metal in continuous polymerizations which the present catalyst usually exceeds. Adjustments are made by those skilled in the art to reflect reactivity and efficiency, usually by dilution alone, and control of feed rates.

The transition metal-containing catalyst is combined for use in polymerization with an organometallic cocatalyst such as triethylaluminum or triisobutylaluminum or a non-metallic compound such as triethylborane. Thus, one typical polymerization feed comprises 42 parts of isobutane solvent, 25 parts of ethylene, 0.0002 parts of catalyst (calculated as Ti) and 0.009 parts of co-catalyst (TEA, calculated as Al) to a reactor maintained. at 47 kp / cm 2 and 71 ° C.

In general, the amount of co-catalyst, where used, is calculated to vary from about 30 to 50 Rpm calculated as Al or B, based on isobutane. Examples of metallic cocatalysts include trialkylaluminum compounds such as triethylaluminum, triisobutylaluminum, tri-n-octylaluminum, alkylaluminum halides, alkylaluminum alkoxides, dialkylzinc, dialkylmagnesium and metal borohydrides including those of the alkali metals, in particular sodium and magnesium. , beryllium and aluminum. The non-metal cocatalysts include boron alkyl compounds such as triethylborane, triisobutylborane and trimethylborane and hydrides of boron such as diborane, pentaborane, hexaborane and decaborane.

The polymerization reactor is preferably a loop reactor adapted for slurry polymerization, thus using a solvent such as isobutane from which the polymer is separated as a granular solid. The polymerization reaction is carried out at low pressure, for example 14-70 kp / cm 2 and a temperature in the range 38-93 ° C with hydrogen applied as desired to control the molecular weight distribution. Other n-alkenes can be fed to the reactor in a smaller proportion to ethylene, for copolymerization therewith. Typically, butene-1 or a mixture thereof with hexene-1 is used in an amount of 3-10 mol%, although other alpha-olefin monomers more / proportions with ease can be used. When using such n-olefin comonomers, it is possible to ensure resin density values over the range from 0.91 to 0.96.

Still other alpha-olefin comonomers, such as 4-methyl-pentene-1,3-methyl-butene-1, isobutylene, 1-heptene, 1-decene or 1-dodacene can be used from such a small amount of SO where monomer mixtures were used. The polymerization can nevertheless be carried out at higher pressures, for example 1400 to 2800 kp / cm 2, in autoclaves or tubular reactors where desired.

When referring here to an intermetallic "compound" or "complex", the intention is to denote any reaction product, either by coordination or association, or in the form of one or more inclusion or occlusion compounds, clusters or other co-engagements. under the applicable conditions, the integrated reaction generally being exhibited by color change and gas evolution, which probably reflects reduction-oxidation, rearrangement and association among the unused elements of the reaction system.

The invention is further illustrated and the method and preparation and use thereof by the following examples together with the foregoing description. All parts are by weight unless otherwise indicated.

Melt index values are determined under conditions E and F respectively according to ASTM D-1238-57 T, for MI and HLMI values, on powder or resin samples as indicated. HLMI / MI or MIR is the melt index ratio, a measure of shear sensitivity that reflects molecular weight distribution. Other tests are as indicated or are conventionally performed in related art.

EXAMPLE Ia A. 6.0 parts of Ti (OBu) 4 [TBT] and 4.2 parts of CrCl 36 H 2 O were combined in a reaction vessel. The chromium salt was partially dissolved and some heat was evolved by stirring. Complete dissolution was performed with gentle heating to 60-70 ° C. An additional 3.3 parts of chromium salt were dissolved with stirring for a period of 20 minutes. To the green solution was added in portions a total of 0.3 parts of magnesium turnings, which caused strong gas evolution.

The cooled reaction product, which was free of excess magnesium (which had completely disappeared), was a viscous green liquid soluble in hexane. 461 10.0 18 B. In a similar experiment anhydrous chromium chloride was used with the titanium alkoxide but no reaction occurred with heating at higher than 100 ° C for half an hour. Addition of zinc dust and further heating at higher than 150 ° C still showed no reaction. Replacement of magnesium chips also did not result in any reaction. It was concluded that the hydrated salt was a necessary component of the reaction system.

EXAMPLE II A. mer was combined in a stirred reaction vessel equipped with an electric heating mantle. The chromium salt completely dissolved at about 60 ° C and reaction with the magnesium turnings was evidenced by gas evolution at BSOC which was strong at 100 ° C, decreased at 116 ° C with some Mg remaining. After dissolving the remaining Mg, heating was continued to a total reaction time of 1 hour and 45 minutes. The reaction product was at room temperature a dark green liquid which was easily dissolved in hexane.

B. In the same manner, a reaction product was prepared in the proportions 0.16m TBT, 0.029m CrCl 3 .6H 2 O and 0.029m Mg. A cloudy green reaction product at 18 ° C assumed a definite bluish color at 120 ° C with continued gas evolution. The reaction was terminated by the disappearance of magnesium in 1 hour and 15 minutes. The reaction product was soluble in hexane.

C. The experiments described above were repeated again in the reactant amounts of 0.16m TBT, 0.058m CrCl 3 .6H 2 O, 0.0l45m Mg. The reaction was completed in 115 minutes and a hexane soluble product was obtained as a result.

D. The ratio of the reactants was again modified in a further experiment to 0.15m TBT, 0.0287m CrCl 3 .6H 2 O and 0.0l44m Mg. A cloudy green material visible at 114 ° C turned blue at the Mg surface. The recovered reaction product 461,100 was hexane soluble.

E. In a similar experiment, 0.76m TBT, 0.30m crclenzo and 0.176m Mg ° 1 octane were reacted. clear the green color of the reaction at 70 ° C became cloudy with increasing gas evolution and darkened to almost black at 90 ° C. The color returned to green via 119 ° C and the reaction was cerninated at 21 ° C with complete disappearance of the magnesium. The reaction product (6.9% by weight Ti, 3.5% by weight Mg, 1.3% by weight Cr) was a dark olive green liquid and a solid with a darker color (approximately 50: 50 / volume) which settled out.

F. In a further octane run, the reactants were provided in the proportions 0.150m TBT, 0.05lm CrCl 3 -6H 2 O and 0.1m Mg. Again, the cloudy green color changed to almost black with vigorous movement and formed at 1090 a dark blue-black reaction product (5.7% by weight Ti; 2.9% Mg, 2.1% by weight Cr).

EXAMPLE I I I A. The reaction product IIE was combined in a reaction vessel with isobutylaluminum chloride added dropwise in proportions to provide a 3: 1 Al / Ti molar ratio. The green colored mixture was initially changed to brown-violet at 38 ° C, which upon completion of reactant addition at 39 ° C had changed to reddish-brown in appearance. After further stirring for 30 minutes, the reaction was terminated, the product being a dark red-brown liquid and a dark brown precipitate.

B. The reaction product IIF was also reacted with isobutylaluminum chloride (molar ratio 3.1 Al / Ti). The peak temperature with complete addition was 48 ° C but no brown color change was seen. The reaction product was a clear liquid and a dark gray precipitate. EXAMPLE IV The catalyst components prepared in Example III above were used in the polymerization of ethylene (8800, 10 mole percent ethylene, 0.0002 parts of catalyst calculated as Ti, triethylaluminum about 45 ppm, calculated as A1, H2 as indicated). ) with results given in Table I as follows: TABLE I 2 Prod. Resin properties Catalyst H2 kp / cm g Pe / g Ten hours. MI HLMI HLMI / MI IIIA 5.2 35160 10.1 265 26.3 9.4 29220 18.9 618 32.6 IIIB 5.2 30380 9.6 264 27 9.4 26880 32.8 855 26.1 I In the following example, the catalyst component of the invention was prepared from the reactant mixture in the absence of added solvent.

EXAMPLE V A. 0.212m Ti (OBu) 4 [TBT], 0.1lm magnesium shavings and 0.00lm MgCl2.6H2O (TBT / Mg / MgCl2. 6H2O = 1: 0.0l molar) were combined in a stirred reaction vessel. equipped with an electric heating jacket. The magnesium salt completely dissolved at room temperature to form a homogeneous reaction mixture.

The mixture was gradually heated and at 95 ° C gas evolution began on the surface of the magnesium chips. At 140 ° C with reflux, the bubbling had become strong. The solution darkened in color and the bubbling ceased at 170 ° C after which the reaction was terminated. The reaction product contained excess ammonia - only about 8.5% charged had reacted - and was soluble in hexane.

B. In another experiment, the molar ratio of MgCl 2 .6H 2 O (TBT / Mg / MgCl 2 .6H 2 O = 1: 1: 0.1 mol) was increased. The golden yellow liquid became greyish with gas evolution at 104 ° C and darkened with further heating to 1668 ° C. After 125 minutes of reaction time, the reaction product contained some excess magnesium - about 63 percent had reacted.

C. In a further experiment, the molar ratio used was 1: 1: 0.17. The dark blue reaction product was very viscous and did not dilute easily with hexane. All magnesium was consumed.

The following examples show the preparation carried out in a hydrocarbon solvent.

EXAMPLE VI A. 50.2 parts (0.148m) of TBT were added to a stirred reaction vessel equipped with an electric heating mantle and 58.6 parts of octane. The magnesium turban (0.074m) was added, stirring was started and then 0.0l25m MgCl 2 .6H 2 O was added with heating for one minute. At 75 ° C (20 minutes) the magnesium salt had completely dissolved and at 95 ° C (25 minutes) gas evolution began at the surface of the magnesium chips, with evolution increasing as the solution became greyish and then dark blue with refluxing at 117 ° C (35 minutes). minutes). The magnesium metal had completely reacted within one hour (128-129 ° C) and the reaction was terminated. The dark blue reaction product, solubilized in octane (a small amount of a greenish precipitate remained) was estimated to contain 6.8% by weight of Ti and 2.0% by weight of Mg constituents (Ti / Mg 3.4 to 1 by weight, 1.7 to 1 molar).

B. Previous experiments were essentially repeated except that the molar ratios of the reactants were modified with the following results: 461 100 22 Ti / Mg / MgCl 2 .6H O Ti / Mg molar ratio (Molar) Remarks 1.0 / 0.65 / 0, 11 1.32 Dark blue-black liquid and green precipitate. 6.6% by weight Ti, 2.6% by weight of Mg constituents (calculated). 1.0 / 0.75 / 0.128 l, l4 Blue solution with a greenish tint. 6.5% by weight Ti, 2.8% by weight of Mg constituents (calculated). 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 °. l / l / 0.17 0.85 Dark blue-black liquid, 6.6% by weight Ti, 3.9% by weight Mg constituents (calculated). l / l / 0.34 0.75 Dark blue-black liquid, 6.7% by weight Ti, 4.6% by weight Mg constituents (calculated). l / l / 0.51 0.66 Milky blue liquid. 3.7% by weight Ti, 2.9% by weight of Mg constituents (calculated). l / 2 / 0.17 0.46 Dark blue-black liquid and viscous green gel. Some unreacted Mg °. l / 2 / 0.34 0.43 Dark blue-black liquid and viscous gel. Some non-traded Mg. 2 / l / 0.17 1.70 Example IIA. 2 / l / 0.34 1.50 Blue-black solution. 7.1% by weight Ti, 2.3% by weight Mg constituents (calculated). 3/1 / 0.51 1.99 Blue-black liquid with a light green tint. 6.1% by weight of Ti, 1.6% by weight of Mg constituents (calculated).

C. The 1/1 / 0.34 preparation obtained above was repeated except that 63.7 parts of TBT were used with 67.5 hexane as the solvent reaction medium. A dark blue-black liquid was obtained which by calcination contained 8.2% by weight of Ti and 1.6% by weight of Mg constituents.

The following example shows the stepwise preparation of the catalyst component. EXAMPLE VI 2.61 parts of MgCl 2 .6H 2 O and 34.2 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. Prolonged stirring resulted in bleaching of the turbidity and gave a clear yellow liquid within 2 hours (in a second experiment carried out in octane, the salt had completely dissolved within 30 minutes and gave a yellow liquid without any intermediate precipitation or opacity).

A TM Mg reaction product was prepared in the same manner as in the previous example using the clear yellow liquid prepared above and 1.83 parts of MgO with 1 / 0.75 / 0.128 molar ratio of components in octane. The reaction proceeded evenly to a dark blue-black liquid and green precipitate in the same manner as other reported reactions.

The reaction product was activated with ethylaluminum dichloride at a 3 / L Al / Ti ratio to produce a catalyst component for olefin polymerization.

The following example shows the importance of the content of bound water.

EXAMPLE VIII A series of identical experiments were performed at the molar ratio l / 0.75 / 0.128 (TBT / Mg / MgCl 2 .6H 2 O) except that the degree of hydration of the magnesium salt was modified.

When MgCl 2 .4H 2 O was used (H 2 O / Mg = 0.68 / 1 compared to 1: 1 for MgCl 2 .6H 2 O) only 89.1% of the magnesium metal reacted. Use of MgCl 2 .2H 2 O at the same total molar ratio (H 2 O / Mg 0.34 / l) resulted in only 62.1% reaction of MgO.

In repeated experiments, the amount of hydrated added salt was increased to provide a 1 / L H 2 O / Mg ratio. All magnesium metal reacted. It was also found that the amount of insoluble reaction product increased with increasing salinity. 461 100 24 The following examples illustrate the use of other titanium compounds.

EXAMPLE IX 'A. 45.35 parts (0.195m) Ti (OPRI) 4.0, 19595m MgO and 50.85 parts octane were added to a stirred reaction flask equipped with an electric heating mantle, and 0.027m MgCl 2 .6H 2 O was added. . The milky yellow mixture turned gray at reflux, at about 88 ° C, and turned blue at 90 ° C with gas movement. Based on the residual magnesium, it could be concluded that the reaction was partially suppressed by the octane / isopropanol azeotrope present.

B. The reaction described in A was repeated at a reactant molar ratio of 1 / 0.75 / 0.128 using decalin (b.p. 185-1890) as diluent. After six hours, the reflux temperature was 1400 and the reaction was terminated. A dark blue-black liquid was obtained with a small amount of dark precipitate.

Only 8.8% of the magnesium had reacted.

C. In a similar manner, reaction was carried out with tetraisobutyl titanate at a molar ratio of 1 / 0.75 / 0.128 to give a blue-black liquid and dark precipitate. Approximately 50% of the magnesium had reacted.

D. Titanium tetranonylate was also used with magnesium and MgCl 2 .6H 2 O in a molar ratio of 1 / 0.75 / 0.128. A blue liquid formed and 45% of the magnesium had been consumed.

E. The reaction product of titanium tetrachloride and butanol (which was assumed to be dibutoxytitanium dichloride) was reacted with magnesium and magnesium chloride hexahydrate in a molar ratio of 1 / 0.75 / 0.128 under similar conditions as 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 v / v) were recovered. In the following example, a zirconium metal alkoxide was used.

EXAMPLE X A. 12.83 parts of zr (oßu) 4.ßuon (mozsm), 0.34 parts of Mg ° (0.4m) in the form of commercially available chips and 8.8 parts of octane were placed in a reaction vessel and heated to reflux at 125 ° C with stirring for 15 minutes without any sign of reaction. 0.97 parts of MgCl 2 .6H 2 O (0.005 m) were added, after which vigorous movement was observed and the mixture became milky in appearance.

B. In a second experiment, 31.7 parts of the zirconium compound (0.069m) were combined with the magnesium metal shavings (0.069m) and 57.6 parts of mineral spirits (b.p. 170-195 ° C) and 4.79 parts of MgCl 2 .6H 2 O (0.0235m) was added with stirring. Heat was supplied to the reaction vessel via an electric jacket. Within 5 minutes, the reaction mixture had become opaque in appearance and gas evolution from the surface of the magnesium metal appeared when the temperature had reached 85 ° C, at 8 minutes reaction time.

Gas evolution continued with strong movement, with the temperature rising to 108 ° C when a whitish solid appeared. With continued heating to 133 ° C (1 hour reaction time), all magnesium metal had disappeared, the reactor containing a milky white liquid and a white solid. The reaction mixture was cooled and 92 parts of a mixture were collected which contained 6.8% by weight of Zr and 2.4% by weight of Mg (2.8: 1 Zr / Mg by weight; 0.75 Zr / Mg molar ratio) which was soluble in hydrocarbons. .

The reaction product can be activated in a known manner with, for example, an alkylaluminum halide by reaction therewith suitably in a molar ratio of about 3 / l to 6/1 Al / Zr to provide, in combination with an organic or metal-organic reducing agent, an olefin polymerization catalyst. lysator system adapted for the production of polyethylene resin.

The following example shows the use of calcium instead of 461 1ÛÛ N magnesium as the reducing metal.

EXAMPLE XI A. o, o74m Ti (osu) 4; about 74m approx. ° (thick chips provided commercially, mechanically cut into smaller pieces) and 0.0l25m MgCl2.6H2O were combined in octane in a stirred reaction vessel equipped with an electric heating mantle. When the temperature reached 105 ° C, the solution darkened in color and at 105 ° C, with gas evolution, the solution assumed a dark gray appearance. At 110 ° C, rapid gas evolution occurred, followed by the formation of a dark blue liquid. At 90 minutes, the reaction was terminated and a reaction product comprising a dark bluish black liquid with a greenish tint was isolated.

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

In another experiment, the same reactants were combined in a molar ratio of 0.75 / 0.128. 63% of the calcium reacted with a blue-black liquid and a green solid.

The reaction product (molar ratio l / 0.47 / 0.128) contained 6.6% by weight of Ti, 2.6% by weight of Ca and 0.4% by weight of Mg (XI A2) B. The reaction product XI A1 was further reacted with ethylaluminum chloride at a molar ratio of 3/1 and 6/1 Al / Ti. The reaction products were diluted with hexane and the halide activator was added slowly to control the highly exothermic reaction. In the 3/1 experiment, the dirty white slurry that was initially formed upon completion of the reaction was dissolved into a cutting liquid and a white precipitate. At the 6 / l Al / Ti ratio, the slurry changed in color to gray and then lime-green. The reaction product XI A2 was also treated with EtAlCl2 in the molar ratio of 3 / l and 6 / l Al / Ti. The reactions were even and gave in 3 / l a dark brown slurry and in 6 / l a reddish-brown liquid with a brown precipitate.

C. Reaction products prepared in Part B were used in ethylene polymerization with the results given in the following table. 28 461 100 o ~ w @ fi_ ° @> _m «@. ~ <M_ @« H_ «m m fi z w fifl o_H ~ Q ~ m> _m>> _>« AMA Hzqm HUSDGHE om ucwooum fl oog o fi H4 Emm mv uwmwwn fl w A fl dmßv Es m v m m> .H m ~ .o o. ~ m> _H mo_H «wm Q ummøxm: wmmuw> Hømwuumm mwucm Eowwm uoww: musnom fl .l U fl vmxßmnmh Gwßü u0ummæHmumx | Emm wum> usumuwmëwa HmWMUMHH HUvUMWMH. ~ «.> ~ ~ .M H \ wo@~.HH« _m o ~ m. ° ~ ~ .m H \ mw ~ Ho \ »«. Q \ H oHm.m «-m H \ @ = ømm. Q «~ .m H \ m« m_o \ mo \ H .e fl u fi @@ \ m @ m. eu \ mx, wuum fifi wnuwu Awøq flflfl wnußw fi oev »w» fl> fi ~ x: @o »@ = | m = o fl px« wm if @. ~ umz | «u | ama HH Q fl mmdä 461 100 The experiments showed a slightly broader molecular weight distribution in resin use of magnesium as the reducing metal.

The use of zinc as a reducing metal is shown in the following examples.

EXAMPLE XII A. 0.204m TBT, 0.53m Zno granules and 0.026m MgCl 2 .6H 2 O were combined in octane in a stirred closed system equipped with reflux and externally heated. Within 13 minutes (85 ° C) a rapid color change to bluish black occurred with increasing gas evolution to vigorous movement and foaming. The reaction product, a blue-black liquid (no precipitate) comprising 7.7% by weight Ti, 0.9% by weight Zn and 0.5% by weight Mg fades to yellow on exposure to air.

B. The reaction product TiZnMg (molar ratio l / 0.86 / 0.128) was reacted with isobutylaluminum chloride in a molar ratio 3 / l Al / Ti in hexane at io-13 ° c (XII si).

C. Preparation of the TiZnMg reaction product (XII A) was repeated using Zn dust, with similar results.

A further experiment with granulated zinc used only 7% of the zinc and showed the formation of a green layer on the zinc surface.

D. The activated reaction product XII B1 prepared above was carefully washed in hexane and used in the preparation of low density polyethylene resin. The reactor was pre-filled with sufficient butene-1 to ensure the desired density and the reaction was carried out (with batch addition of butene-1 together with the ethylene) at 77 ° C and 3.45 kp / cm 2 H 2 in the presence of triethylaluminum as cocatalyst. The recovered resin had the following properties: density 0.1956, MI 1.68, HLMI 52.1 and MIR 31. 461 100 3Û The following examples include the use of potassium as the reducing metal.

EXAMPLE XIII 62.7 m moles of TBT, 47 m moles of fresh potassium metal (scraped from its oxide / hydroxide coating under octane) and 8.0 mmol MgCl 2 .6H 2 O were combined in octane in a closed system equipped with reflux and externally heated. Within 2 minutes at 35 ° C the color changed to blue-black and bubbles appeared.

Strong gas development and movement followed. Upon disappearance of the potassium metal, the reaction was terminated (at 5 hours).

A dark blue-black liquid with a small amount of dark blue precipitate was recovered.

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

EXAMPLE XIV A. 112.31 parts Tl (osu) 4 (0.33 m), 8.91 parts Al ° (Alpha Inorganicspherical aluminum powder, -45 mesh) and 11.4 parts MgCl 2 .6H 2 O (0.056 m) [molar ratio 1: 1: 0, 17] was mixed in a reaction vessel with stirring and heat was applied using an electric jacket.

When 10 ° C was reached in about 10 minutes, the yellow color deepened and at 18 ° C strong movement began with gas evolution. At 222 ° C, the refluxing liquid assumed a gray shift and the temperature stabilized when the reaction mixture changed color from deep gray to bluish hue to dark blue then bluish black at 27 minutes reaction time. The temperature was maintained, rising to 145 ° C within 1 hour and 20 minutes, after which the evolution of gas was substantially complete and the reaction was terminated.

The reaction product was at room temperature a viscous liquid which showed unreacted aluminum particles. The unreacted aluminum separated, washed and weighed, showing H 461 100 that 6.7 parts of Alo had reacted. The reaction product contained 7.9% by weight of Ti, 3.4% by weight of Al and 0.7% by weight of Mg (molar ratio 1: 0.75; 0.77).

B. 9.10 parts of the reaction product prepared above (0.719 parts of Ti or 0.015 m of Ti) were added in hexane (1.3.0 parts) to a reaction vessel in a cooling bath. 0.045 m of ethylaluminum dichloride was added gradually, keeping the temperature at 15 DEG-10 DEG. The mixture, which was stirred for 30 minutes, gave a dark red-brown slurry and a rigid solid (B1).

A second experiment was performed (0.175 m Ti / 0.0525 m Al) without cooling to a peak temperature of 38 ° C and a reddish brown slurry was formed again with a stiff solid deposit (B2).

EXAMPLE XV The reaction products of Example XIV were used as catalysts in the polymerization of ethylene under standard conditions (88 ° C, 5.2 kp / cm 2 H 2) using triethylaluminum as a cocatalyst with the following results: _19; HLMI MIR B1 0.14 6.45 46.1 B2 0.38 17.4 45.7 EXAMPLE XVI A. In a similar manner as before, 0.13 m TBT, 0.1 m A10, and 0.017 m AlCl 3 .6H 2 O were combined. in octane and reacted for 7 hours and 15 minutes to provide a dark blue-black liquid and a small amount of a gray solid. About 40% of the aluminum reacted to provide a reaction product composed of 6.6% by weight of Ti and 1.6% of Al. (XVI A1).

In the same way, the same reactants were combined in a ratio of 1 / l / 0.1m. Approximately 58% of the aluminum reacted to provide a reaction product containing 6.5% by weight of Ti and 2.7% by weight of Al. (XVI A2). 461 100 az B. The reaction products (XVI A1) and (XVI A2) were activated with ethylaluminum chloride in 3/1 Al / Ti.

C. The solid portion of the activated reaction product (XVI A2) was isolated from the supernatant and used with TEA as a co-catalyst in the polymerization of ethylene, via 77%, 2.05 kp / cm 2 H 2 to produce narcotics. drawn by MI 0.02, HLMI 1.01, MIR 50.5 and in a second experiment MI 0.02, HLMI 0.45 and MIR 22.5.

The following examples focus on catalyst components prepared using other acuo complexes.

EXAMPLE XVII A. 0.0335 moles of TBT and 0.0335 moles of MgO were stirred in octane in a heated reaction vessel to which was added 0.005? mol MgBr2. 6H2O. (Reaction molar ratio 1/1 / 0.17). The salt was dissolved in 6 minutes with heating to GSOC. A gray color developed with gas movement and the solution changed to blue, then bluish black with a greenish tint. The reaction was terminated at 112 ° C (approximately 10% unreacted Mg) after a reaction time of 4 hours and 10 minutes (XVII A).

In a similar manner, a reaction product was prepared in a molar ratio of (Ti / Mg / MgBR 2 .6H 2 O = 1 / 0.65 / 0.11) which was a blue-black liquid and a dark green precipitate (6.5% by weight Ti, 2.5 weight percent Mg (calculated)).

B. The edged reaction product (XVII A) was combined with isobutylaluminum dichloride in Al / Ti amounts of 3/1 and 6/1 by gradual addition of the alkylaluminum halide. In the first experiment (3/1 Al / Ti) a peak temperature of 42 ° C was reached with addition at a rate of 1 drop / 2-3 seconds, after which the green liquid turned to brown. The reaction product consisted of a reddish-brown liquid and a brown precipitate.

(IV B-1). The 6 / l product (IV B-2) was prepared in a similar manner with the same result. 461,100 LO (IJ) In a separate experiment, the reaction product (XVII A) was combined with SiCl 4 in the same manner. The reaction product after a 30 minute reaction at a 3 / l Si / Ti ratio was a light yellow liquid and a brown precipitate. tried to provide: kept a 6 / l Si / Ti reaction product.

C. The activated reaction products XVII B1 and XVII B-2 (1% by weight Ti) were used in the polymerization of ethylene (10 mole percent in isobutane) at 88 ° C with water modifier and triethylaluminum cocatalyst (45 ppm Al) and compared with an identical experiment using magnesium chloride hydrate, with the result given in Table III: 461 100 34 m.mm wm mm m.æ ~ m.mm Hz Hzqm mmm fl ßm wmw ævm fl w HEQI m_> H ~. ° H wo fi vw ~. ~ fl ß.H mm uwmwxm: wmwmuum: nw> fi: m om °.> m «_ @ ow>. <~ ~ .m ~ \ wo @ m. >>« _m omH.m ° H ~ .m H \ mo ~ mm. ~ umm: °° Hm «« ~ m °> @. ~ «~ .m H \ ~ o ~ m @. ~ Høwz u 4 ^ ~: | fi a w \ mm wv ~ eu \ mx Aum fi osv <« m: | « ^: mo. fl a »m» fl> H »g = @ o» m Nm + fl a \ H <Ho »~ m> H ~» mx HHH qqmm 461 100 35 EXAMPLE XVIII A. 42.33 parts of TBT (0, 1224m) was combined with 3.02 parts of Mg (Q, 1224m) in octane (42.8 parts) in the presence of 5.7 parts of FeCl 3 H 2 O (0.02m) (TMgFe = 1 / l / 0.17 molar) in an enclosed stirred reaction vessel equipped with reflux and an electric heating mantle. Heating was started and within 6 minutes a gas evolution began at 65 ° C. The cloudy yellow color turned dark brown at 80 ° C (7 minutes) and gas evolution increased. In about 30 minutes, the gas evolution had slowed down and then stopped with the consumption of Mgo and the reaction was terminated. The very dark liquid showed no residue (XVIII A1).

In a second experiment, the same reactants in the molar ratio TMgFe = 1/1 / 0.34 were combined with similar results. Dilution with hexane did not cause any precipitation or precipitation of residue (XVIII A2).

B. Reaction product XVIII A1 was activated by reaction with a SO% by weight solution of ethylaluminum chloride in hexane at a 3 / L Al / Ti ratio. A brown liquid and solid was recovered containing 16.5 mg of Ti / g. (XVIII Bl).

Similarly, the reaction product (XVIII A2) was activated.

The dark brown liquid changed to a violet slurry and then to a dark gray slurry. The resulting clear liquid and gray precipitate contained 16 Mg Ti / g.

C. The activated reaction product XVIII B1 was used in the polymerization of ethylene at 88 ° C, 4.2 kp / cm 2 H 2. 114,320 g PE / g Ti / hour were recovered which exhibited the following properties: MI 5.1, HLMI 155.3, MIR 30.3.

EXAMPLE XIX A. 1. 160 m Ti (OBu) 4, 160 m magnesium turnings and 0.027 m CoCl 2 .6H 2 O were combined in a stirred reaction vessel with 61.2 parts of octane. The violet cobalt salt crystals gave a dark blue solution at 461,100 solution. The mixture is heated using an electric jacket and gas evolution on the magnesium surfaces appears at 58 ° C and increases to vigorous agitation at 107 ° C within 12 minutes. The clear blue color becomes greyish on further heating and becomes almost black at 123-12500 when all magnesium has disappeared and the reaction is terminated at 90 minutes. The milky blue reaction product was hydrocarbon soluble and redissolved to a dark blue liquid and a dark precipitate when allowed to stand.

The experiment was repeated with essentially identical results.

B. The reaction product of the previous preparation was shaken and 0.0 μl (Ti) was combined with isobutylaluminum chloride (0.0333 m Al) which was added dropwise to a reaction vessel. The temperature reached a peak at 40 ° C with the formation of a grayish precipitate, which upon further addition of BuAlCl2 turned brown. After stirring for an additional 30 minutes, the reaction was terminated to provide a dark red-brown liquid and a brown precipitate.

C. The catalyst component prepared in Example XIX above was used in the polymerization of ethylene (88 ° C, 10 mole percent ethylene, 0.0002 parts of catalyst calculated Ti, triethylaluminum about 45 ppm calculated as A1, H2 as indicated) with the results given in the following Table IV: TABLE IV ~ Catalyst H 2 Prod. _ _ Resin properties kp / cm g PE / g Ti / hr gl EEE; HLMI: MI XIX B 5.2 105.180 6.2 206 33.6 9.4 75.290 33.9 950 28.1 EXAMPLE XX A. 0.69m Ti (OBu) 4 [TBT], 0.69m magnesium span and 0.029m nlCl 3 .6H 2 O in octane as diluent was combined in a stirred reaction vessel equipped with an electric heating mantle. The hydrated aluminum salt partially dissolved and at 11 ° C the solution rapidly darkened to a black liquid with vigorous agitation beginning with gas evolution at the surface of the magnesia. The solution assumed a blue coloration and formed with a uniform reflux to 122 DEG C. a dark blue-black liquid with some residual magnesium. At 125 ° C, all magnesium metal had disappeared, the solution showed a light green tint. The reaction was terminated and a dark blue-black liquid and green precipitate were recovered, in a volume ratio of about 95/5.

B. The reaction product described above was combined with isobutylaluminum chloride in a molar ratio of 3: 1 and 6: 1 Al / Ti by dropwise addition of the chloride to a reaction vessel containing the titanium material. In the first reaction (3: 1), the alkyl chloride was added at a rate of 1 drop / 2-3 seconds until a peak temperature of 42 ° C was reached, 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 (XX B) were isolated.

C. A 6: 1 Al / Ti product with the same result (XX C) was similarly ensured.

D. Reaction products XX B and XX C were used with triethylaluminum co-catalyst (45 ppm Al) in the polymerization of ethylene (10 mole percent) with isobutane diluent at 88 ° C and hydrogen as indicated. The experiments were terminated after 60 minutes with the results given in the following Table V: TABLE V Catalyst H2 2 PB Prod _ _ Resin properties kp / cm mol g PE / g Ti / hr MI HLMI HLMI MI XX B 5.2 406 84.580 17.2 517 30.1 9.4 542 75.280 54.9 1413 25.7 XX C 5.2 245 54.440 4.11 129 31.4 9.4 183 34.860 26.2 801 30.5 461 100 38 EXAMPLE XXI A. 0 , 153m Ti (OBu) 4 [TBT], 0.13m Mgo on and 0.026m NiCl2. 6H 2 O was combined with 61.75 parts of octane in a stirred reaction vessel equipped with an electric heating mantle. Upon heating to 44 ° C, the yellow solution darkened in color and gas evolution was observed on the magnesium metal surface at about 57 ° C. With continued heating, gas evolution increased until at 102 ° C (15 minutes reaction) the reaction system changed to a slightly cloudy brown color. Vigorous stirring continued with dark staining of the brown color until at 120 ° C (75 minutes) all the magnesium had disappeared and the reaction was terminated. The reaction product (XXIA-1) was a hydrocarbon-soluble dark brown liquid and an equal amount of a fine precipitate.

In a second experiment, 0.149m TBT, 0.149m Mg and 0.05lm NiCl2-6H2O in octane were combined in the same way. Mg metal disappeared at 115 ° C, 120 minutes, and the reaction resulted in a dark tan black hydrocarbon soluble liquid, which was redissolved when allowed to stand to a very fine dark precipitate and a yellow liquid, about 50/50 volume (XXIA-2). ).

B. Reaction product IA-1 was shaken and an aliquot (0,013 m / Ti) was placed in a reaction vessel with hexane diluent to which was added dropwise Bu 2 AlCl 2 (0.04 μm Al) at a rate of 1 drop / 2-3 seconds to 28 ° C and a 1 drop / second to a peak temperature of 39 ° C. After completion of the addition, the vessel contents were stirred for 30 minutes and the reaction product, a dark red-brown liquid and a dark gray precipitate were isolated (XXIB ~ I).

The same reaction product (XXIA-1) was combined with ethylaluminum chloride in the same manner in a molar ratio of 3 / l Al / Ti. The reaction product was a dark red-brown liquid and a dark gray solid (XXIB-2).

In a substantially identical manner, the reaction product XXIA-2 (Ti / Mg / Ni molar ratio 1/1 / 0.34) was combined with iBuAlCl 2 39 461 100 in a 3: 1 Al / Ti ratio, with the same result except that the supernatant had a pale reddish-brown color (XXIB ~ 3). o; | In a further experiment, reaction product XXIA-2 was reacted in the same manner with iBuAlCl 2 in a 6: 1 Al: Ti molar ratio to likewise form a dark liquid and a dark precipitate (XXIB-4).

The same reaction product XXIA-2 was combined with ethylaluminum chloride in the same manner to give a dark red-brown liquid and a dark gray solid (XXIB-5).

EXAMPLE XXII A. Example XXIA was repeated with reactants added in the molar ratio Ti: Mg: Ni of 1: 0.65: 0.1l. The color change was from deep brownish yellow to dark brown with gas evolution and then via a gray-brown to dark blue-black when consuming magnesium in a reaction that occurred over a period of 6 hours (XXIIA).

B. The reaction product XXIIA was fused with ethylaluminum chloride in the same manner as in Example XXIB in a molar ratio of 3: 1 Al / Ti. A reddish-brown liquid and a reddish-brown precipitate were recovered (XXIIB).

EXAMPLE XXIII Example XXIIA was repeated to provide the reactants in a molar ratio of 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 isobutylaluminum chloride in an Al / Ti molar ratio of 3/1.

EXAMPLE XXIV A series of TMgNi catalysts, prepared as set forth in Examples XXIB and XXIIB, were used as catalyst components in the polymerization of ethylene (88 ° C, 10 mole percent ethylene, triethylaluminum about 45 ppm calculated as A1, H2 as indicated). with the results given in the following Table VI: TABLE VI Catalyst H2 Productivity Resin properties Kp / Cm q PE / g Ten hours gi HLMI HLMI / ML xxxß-3 5.2 90.750 9.55 270 28 9.4 104.980 24.6 683 27.8 5.2 111,940 0.29 10.7 36.8 9.4 112.260 3.1 119 38.9 xxza-4 5.2 59.790 0.25 10.9 43.6 9.4 62.720 1.0 43.6 43.6 xxzla 5.2 57,890 1.66 54.9 33.1 9.4 64.740 6.13 183 29.8 xxrß-2 5.2 238.670 0.65 19.5 30.2 9.4 271,560 6.7 188 28.1 xxrß-5 3.11 175.000 159 --- - 1 Experiments at higher hydrogen levels were extremely fast and resulted in polymer build-up which required termination of experiments.

EXAMPLE XXV A. TBT, Mgo and MgSiF6.6H2O were combined in octane in a heated reaction vessel equipped with reflux in the same manner as in the previous example to provide reaction products in molar ratios of 1 / l / 0.34 and 1/0, respectively. , 75 / 0.128.

B. The latter reaction product was activated by reaction with ethylaluminum chloride in a ratio of 3/1 Al / Ti.

C. The resulting brown precipitate was separated from the supernatant and used with TEA to provide approximately 45 ppm Al under standard conditions for ethylene polymerization (88 ° C, 5.2 kp / cm 2 H 2) to give resin in 107,500 g PE / gTi / hour characterized by MI 2.85, HLMI 84.5 and MIR 29.6.

D. The 1 / l / 0.34 reaction product prepared above was also activated with isobutylaluminum chloride at 3 / l Al / Ti. The solid reaction product was washed several times with hexane and used with TEA in a polyethylene polymerization reactor pre-filled with butene-1 to provide the desired density resin at 77 ° C, 2.1 kp / cm 2 H 2 from ethylene / the butene-1 feed. The resulting resin had a density of 0.9l93, 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 are reacted with the halide component added gradually, usually dropwise to control the exothermic reaction. The reaction was carried out under ambient conditions for a period of time sufficient to complete the addition with stirring of reactant for 10-30 minutes after the onset of peak temperature (where applicable, TMMg solid and liquid components were mixed into a slurry and used in this form). . Reactants and reactant proportions are as follows: 461 100 42 Catalyst component, molar ratio Ti'r MGCIZÄZO (H 2 O) Halide activator Molar ratio 1 / o, 6s / o.11 1 / n, 6s / o, 11 (o, 66) Bu1A1c1, 3/1 1 / 0.65 / o, 11 (o, 66) nu1A1c1å 4/1 1 / 0.65 / o, 11 (o, 661 ßu1A1c12 6/1 1 / 0.65 / o, 11 (o, 661 EtA1c12 3 / 1 1 / 0.65 / o, 11 1 / 0.65 / o, 11 1 / 0.65 / o, 11 (o, 66) sic14 3/1 (si / Ti) 1 / 0.65 / o, 11 (o, 661 s1c14 6/1 (si / Ti) 1 / o, 1s / o, 12ß (, 76e) ßtA1c1, 3/1 ¶1 / o, 1s / o, 12s (.76a1 ßt§A12E13 3 / 1 1 / 0.76 / o, 12s (, 76s1 su A1c12 3/1 1 / 0.75 / o, 1zs (, v6s) su1A1c12 6/1 1 / 0.15 / o, 1zs (, 76s) stsc12 3 / 1 <3 / Ti) 1 / 0.75 / o, 12a (, v6s) (cH312s1c12 6/1 (si / Ti) 1 / 0.75 / o, 12a (, 16s1 (cn313sic1 6/1 (si / Ti) 1 / 0.76 / o, 12s (, v6ß1 (ch312sinc1 6/1 (si / Ti) 1 / 0.75 / o, 12s (, 16a) sic14 3/1 (si / Ti) 1/0, 75 / 0.12a (, 766) sic14 6/1 (si / Ti) 1 / 0.75 / o, 12s (, 16s1 T1c14 1.5 / 1 (Ti / Ti) 1 / 0.75 / o, 12s (, 76s) Tic14 3/1 (Ti / Ti) 1/1 /, 17 (1, o21 au1A1c12 3/1 1/1 /, 17 (1, o2) Etzlxlclz 3/1 1/1 /, 34 (2, o4 ) nu A1c12 3/1 1/1 /, 34 «z, o4) Bu1A1c12 6/1 1/1 / o, s1 (3, o61 Bu1A1c12 3/1 1/1 / o, s1 <3, o61 Bu1A1c12 6 / 1 g / 1 / 0.17 (1,02) 5111111012 3/1 2/1 / o, 1v «1, o2) ßu1A1c12 6/1 2/1 / o, 34 (2, o4) nu1A1c12 3/1 2/1 / o, 34 (2 , o4) Bu1A1c12 6/1 3/1 / o, s1 (3, o61 ßu1A1c12 3/1 3/1 / o, s1 (3, o6) nu1A1c12 6/1 461 100 J> b: EXEZ-IPEL XXVII A. Catalyst samples activated with ßuiAlCl 2 (3zl Al / Ti) were used in a series of polymerization experiments with the results given in the following Table VII: Å fi @ \ H <H "~, ~ fi uHm ¶o 461 100 44 Am flfl .mvUE ÜNHN> MUMÛ PMSUO mm.~Humz|mz|@^=movHa 1 ~ .w ~ a_m ~ ~ _om w_> ~ æ.mm w_- ~ _> m ~ _ @ ~ m. ~ m o_ ~ mm \ mm m ~ w ~ m_m ~ Hzw fi zqm ame m ~ ßw oom fl mww omm mßa omv mm Nmw Hm mam mm fl ævm Hw Hz fl m um mxmcw wmuumm .mwmcm Eomww I mum> «.> H m ~. ~ M_« «« _m w.- mm ~ _mH «. ~ m.NH m_ ~> .mH w_m ~ _ ~ H> .H wa .nwuäü fl š cm w fl wwxmmnmm ummco fl uxmmu uouømæ fl mumz _.fl «smmm« v es fl a fi sø fi m fl æuw fl np | .uoææ I u fl umummëwu ~: musnow fi I fi wøwëmmc fi cømmmun .ucwuoum fi oog o fl 1 cøum uoummæ fi mumxlšmm uwm fi w c fl umnuouxømm QQm.mæ «_m o ~ æ.wm ~ ~ _m H \ ~ H @ om @ H. . @> ~ _m Hm HH.o \ m @. ° \ H omm. @ HH «.m Qmm.« - ~ _m @_> @ ~ Ho \ m> _ ° \ H @ mm. @ m «.m mßm.mm ~ _m m_m fl m. ° \ H \ m oo ~. «m« _m oHm.ßm ~ _m @ .m ¶ «mo \ H \ ~ mm @ _mv«. @ mwm.mm ~ _m m_ ~ «mO \ ä \ A ~ oH.mv «_m Qßw. ~« ~ .m m_m> ~ .o \ H \ H ^ .aHu | H @ m \ m @ mv ~ su \ mx Awwnm flfi w Hww fi oev ^ «w = ~ HHw = »Nm ~ oe,» w »fi> fl» xswøum = o mw. Humz \ fl e HH> qqmm 45 461 100 As can be seen from a comparison of the Ti / MgCl1.6H O molar ratio, the peak melt index is observed at a ratio of 9: 1 (1.5: 1 Ti / H2O).

B. In the following further experiments, the effect of the Al / Ti ratio in the activated TMMg (molar ratio l / 0.65 / 0.11) catalysts in the polymerization of ethylene was investigated. The results are reported in the following table VIII: 461 100 .uwuø fifi š om 1 flfl umxßm fl ßh .ucwuoum fl oog od 1: mmm: m> o Eomww © muw> Huxm .uxsøoumwco fi uxmmu Ommw. ~ Humz1mv 21 m m x ^ mm. uoumm> fi mumx1Emw Hm om m.æN w.wm m.om mm mm m_H ~ «_mm ~. ° m ~ .w ~ Hm ~ H: wHzq = .wwmnm Eomwm 1 muw> omm mo fi w fi w æma w fl m mmv moa ma fifl ßmm mww mmw fi www Hí⁇ m m fl mm m.-> _m mm Q_> Qm ~> _ ~ m_mm>.> m. «« H.æ Hm m. .> ~ v_ @ ° om. «~ ~ .m H \ m ~ .H ~ Hum» m øm ~. @ m «_m mm>.« @ ~ .m fi \ ~ ~ Hm »m oH ~.> @ «.M om> .ow ~ .m H \ fl N fl o fi mpm Q» m. «« @ .M ° ~ wm <~ .m H \ @ ~ HuH <fl: m mm ~.> @ «_M oH«. @ @ ~ .m H \ m_ «N fl u fl m fl øm @ mm.H @« .mm @ ß.mß ~ .m fl \ m N fi u fl m fl sm °> @. m «« _m m @ ~. «m -m fl \ ~ ~ HuH < «Sm A Eu \ mwv ^ ~ oE. ^ a fl »1fi a @ \ m @ w. N = fl a \ m = fl a @ uw« m = fi = wHw «umn fl>« uxD fl oum wU: muw> fl ux <wUcmum> fi ux4 HHH> Q fl ümdß 47 461 100 C. I and further series of experiments using a TMMg ~ catalyst at a molar ratio l / 0.75 / 0.28, the effect of activating agents was analyzed with the results given in the following Table IX: 461 100 ß_ ~ m ~. «m ß.w ~ m .mN ~ _ «~> _m ~ ~.> ~ ww ~ ~. @ ~ m_m ~ m.« ~ o_ «~ ~. ~ m @ .ß ~ m.mm wmwwmmm www ß ~ Hm mmm o.mN H fi m OHN æm fi ß ~ am owe vaw mmm m.wm mo fl omm mß fl H24: ucwuoum fi eyes o fi | : mun .wwmcm Eomww | wum> w_æ æ.H @m_> mm_o ~ _m ~ @wm m ~.> «m_H m. @ H m ~ .ß« .oH «v. ~ o_m ~ ~ .m w.- m_m mm uwmmxm: mmwuw> A5mwuHmm .uoææ I uøumummëws n .HQNSGHE ow U fi umxßmnwm mmm. «~ Wm omm.Hm ~ _m W o> @. A> vm omw.m« H ~ .m vw mm «\ mm qm oA ~ _H @ ~ .m NH o «H.w fl«. @ oHo.- ~ .mw ° ßß.w ~ «.m m-- ~ ~ .m« o-_A ~ «.m _ ° w @.« ~ ~ _m ~ H o @ o.ow «. @ ° m @.« m ~ _m w omm. @ H ~ «_m omm.« ~ H ~ _m W ^ .e fl ~ 1 HB @ \ m @ mv. ~ su \ mMv fl a \ Hu »w »H> al» ¥: wo ~ @ m wøqm flfi wnunw fl oz .A44 Emm MWV Ed al c al ë flfl et al æuw fi ua 1 uoummm al mumxlåmm _cmø: nom fl I fl wvmäwmn al cuwamun Hmm al w c al uwnuouxmw al «~ u« a w f O fl m «~ U fl w Aum al mmwz f U fl mm0E ~ Hu f w ~ w: NHUMHN N f u f æ al sm awuwë | MMC« nm> ux <NH Aümmd fi 461 100 49 D. Larger scale polymerization experiments were performed at 71 ° C with TMMg l / 0.75 / 0.2828 catalyst (slurry, separated from supernatant and washed with hexane) and TEA co-catalyst with use of ethylene and butene-1 as a comonomer, using varying butane-1 inputs, activators and activator ratios. The results are reported in the following table X: l ušë fi ï? im im ... of? HJ 26 ïïä 2 .; h, u fi ëm fi? in Small 22 m6 i .i I H 0 004m vi? im mâá QS wá 2.0 C12 .AJ m s UQÉ 2 :? in Små Nám »á 2.0 3.3 SJ w un? 2.2? im 135 i? wá I .i i m uåm fi? inämé .íå a; E. I. i m UQE 2.3? in 25.0 mJN N; SJ 2.3 QLN o fuä fi z: fi? Sw E20 .23 OJ å ... 3.3 .EJ u 30223 2A? HS m2 ... 3 ai E10 2 :. .äJ m NÜÉB: fi? Sw æï fl c oc? ï fi 2.0 3 :. S ... 4 H2 \ H2Qm H2 Aumšocoë Åhouxmwu .w uwE .Hc nu uoumš fl uxm umß fl us Amwcm flfi wn .fi muou ucmuonm: ocoë ucmoonm xww nu »w fi mšå 33 Lß fi om; What do you think ... t fi â ma? »Än 41.: Ana cmuw \ m Li .Tšwvsm xumšc fi cwum 1 / O N A fl mm fi n. The resin batches collected as above were stabilized with 100 ppm calcium stearate and 1000 ppm Irganox 1076, characterized by conventional tests and converted to blown film in a 38.1 mm Hard extruder (60 rpm screw; 76.2 mm nozzle with nozzle gap 2.08 mm; cooling air, 2.7-4.4 ° C) and further tested as reported in the following tables XI and XII: .mc fl cusumwmcmuum mHHxnw> »nu uwm fi wmc fl uwn> m mc fl uw fifl umo> m> o : mn umm fl> us äom uuounu fl wëm Hmu cm wcouwn fl äuw H mä H Nm om om om om om om om om oo = n = _ »wnu» wn | wuosm 2. oo »oo- oo; oo; oo; oo- ool oo- ool oo | ua .msn .o ooo mod o flfi NHH NHH od fi m fifl o fifl mao mod uo. »ßo fl> o_oo ~ o.oo ~ o.ooo o. ~ om ß_ooo o.ooH H_ooH m_o> ~ oo ~ H. ~ oH ~ eu \ aumx.ownummw fifl wnom fl mowun mo.o A fl_ o o «_ ~ oo_ ~ oßow o> _ ~ m« _o oo. ~ mo.o oo.o oo fi x ~ s0 \ @x .fl swosmmun o fi o oo fi ooo oo »ooo ooo oo fi ooo om fl oo fi n fl E \ eu o.oo o fl> o _o = fl = fi ma oo fi o_ «o ~ oo fi oo fi oo fl oo fl o- mod o- 1- = fi e \ eo o.om U fl> mEo \ mx .mcmumxumnuw ond o fifl ~ o ~ oow om fl m.oHH om fi ond oo fl wow »ø = fl s \ su o.om vH> ~ su \ mx .uwnumow fifl osomuo mod oo fl 1- - | 11 om fl Nm fi 11 oo fi oo fl ooo fi u »mw«> mc «cHHw> mmxo> um: ø2 mH ~ v mæ. ~ Hh2om.m HmEoo.w m2mm.m mm.m wm.m m2mm.v ßw.m wm. H mao fl x oooa cum w H m O mm QU m 4 uwmmxmcmmwwuum: .uwmuumnmuwu fl mcwwww fi æuw fi c fl q HX Ad fl má fi 461 100 461 100 53. WHHÛ% ^ mo.ovwN_v moo ~ o ^ mo.ovæv.N ^ mmo.ovvm ~ m Nwoo_o ^ mNo_ov ov_H w «~ N ^ mo \ o. Hm ^ Nmo.OV mv ^ mmo. °. Nm ^ m ~ o_ov m.oH ^ mm ° _ov NF ß fi mq wwßw wmwm ow fi w mmmw nafn vææm ß- «H ~ @« wwøm wm_o ~ wo vm.o ßm.o ßm.o @ m ~ ° «> _ °« m .0 ~ H_ ~> o ~ H www www ßß fi www ß fi mm - HN w m fl Qmm Qww owß omm omm omß ooß oßw oßw øwm omß mw fi qw fi vw fl mw fl QQN mm fi æm fi ww fl mß fl mw fi www o ~ H ow mm ~ «Mmm cow mww H_> mm m.« «.« ~ .M m_æH ~ _ ~ m «_w ~ 0.0» m_m «m ° _o m ~ cQ mQ.om ~ oo m ° _o ß um E flfl w vwm fl n Hmm uwmmxwcwwm. uwwuumzmuwu fl mcmøwma mnmmc fi q EE mc fl cwmuøuo AEEV mxlëu mc fl cuw fl un masa xw fl ëmcmn ^ es. m .fifi m munm fifl mm mc fl nvx fl uum> u mc flfl ux fi uc fi xmmë ~ Eo \ mx ~ H: w0EmmHQ mc «cux fi uum> u mc fl ayx fi nc fi xwme se m ~ oQ \ mx. fl u | wuo @: wE ~ mm: «Cux al uum> u mc al Cux f uc al xwmë w _mc al: fi m B: HcuxHnum> u mn al Cux al nc al xmmä ~ E o \ x ~ mcwuwxomuum cHcux al UHM> u toilet al Cux al uc fi xmmë neu \ mx .vwzuwmw fi amnmmun w .Qom _wcøHw W .no fi mouw al Uwo f q es .xw fi xuo fi ua flfl m HHX Qdmmdà 54 461 100. WHTHOM cow »ßf fl m mmmm wßmm æmæm wßmm @w« ~ mmw fl m fl om wvwm m> ~ m æ «~ m ° æ.o ° w_o« «.H mm.o HH mm.o @wQ m @ _o m ~ .H mo_H @ m. ° ~ o_ ~ mom mmm mmm ß »~ mwq ßßw mm øw Nm Om wm om o fi w oßw o ~ m oww omm omm m fifi m ~ H Nv fl mm fl>« H mm fl wm fi wq fi Hw fi mm fl æm fi mm fl «mN HMN Nmm Nßm mwm www mom Avm HQV ßwq How c. @ Ow Hw wm @_m wm o. ° ~ m. «~ M_ @ H«. «~ @ .-«. «~ M ~ oo m ° _c m ~ Qo wo ~ om ~ ° _ ° mo. ° n. = u Ea fi w umwan www Hmmmxwcumm .uwmuumnmumu fl mcmwmwa mnw fi n flfl mm m_m mm mm mm van Anm Hßw oem ovm bom Næa mw fl mm fi ßwa m U m Ea fi u umwan now uwmmxmcmmm .uwmuumnwuwu Q m z m z m ~ q. o ~ n: ew <»w;» m «« H ~ «=>« m se m ~ ° _ ° \ m. @ w; »m ~ wH ~ w;>« »m» ow = wsHm Q .mc fi u fi æa ~ Eo \ mx .mcmumzonuvm ~ eu \ mx .umsummw fifi mnmmnn W .cow .mnm fi ø w _no fl møww «@ m = nu se .go fl xuo fi ue flfl m uo ..maw @ uun fi @ w = mH> z ~ Eu \ mx ~ xo> uuU fl U0 _u: umummEmuuamEm ~ .mun0mv Hux nnmmma 461 100 «.« Mßw Nw fl mo ^ mo_Qv ~ @ .m ^ mO.ovmw wv mßm Nma ^ wQ.0, ~ @ _w ^ mNmo ~ ovmæ w_ ~ @ _ ~ m_m mm www mmm »Hm» Hm ~ o ~ »om ßow> o ~ 1- 1; m> oo_o nn ^ m ~ Q_oV ^ mßmo_ ° v ^ m ~ o.0V ^ m> mQ.Q, «H. ~ om.m HH.m Qm.m ^ m ~ @ _ovwm ^ m ~ mo.ovmoH ^ m ~ ooæm ^ m ~ mo.oVmoH h.

IO A flfl w ßwman »now nmmmxmcwmw .uwwuum al Wuwu al wcmwmm al muwmc fl n H fl uøummëwunu al a mwcm al AEX ~ E o \ mx xu> ABU:>: m _u al umummEmuu al Wew EE .mc al cmmnwuo uo U0 AEEV mxaäo mc al cum al un et al dx xw al ëmcæn Ass * m .H f m wwnm flfl in ^ .w» uouv HHX qammma 461 100 56 E In further large scale polymerizations carried out in a similar manner using TMMg catalyst (collection separated from supernatant and hexane washed) in molar ratio l / 0.75 / 0.128 (3 / l Al / Ti, EADC) the hexene was fed to the reactor as a comonomer with ethylene and then butene-1 was used instead, followed by exhaust gas analysis, ethylene / butene-1 / hexene-1 copolymers and terpolymers in the course of the work. The results are reported in the following Table XIII: 461 100 57 Nm of mm mm mm .mm HZv HZÅm m.m ~ vm ~ o m ~ Hm_Q ~ .m ~ °> _ ° æ «Hm_ ° ~ .m ~ o> .o. @ «Hm_o« .Hm «m_Q ßmHm_ ° m_m ~ m>. ° mm ~ m_o mw ~ m @ .Q mm. ° Hzmm Immx mmmmmmmm cmuøm COUSm \ CUXGI cmxwm HÜEOCOEEM W mHHx adopt 461 100 EXAMPLE XXVATImation iMMg with the examples and activated with isobutylaluminum chloride (3 / l Al / Ti) was also used for the preparation of other copolymers in varying comonomer fill, isobutane diluent, 77 ° C reactor temperature, 3.1-18.8 kp / cm 2 H 2 and TEA for providing 60 ppm Al with the following results: Ethylene / 3-methylbutene-1 MI MIR Density 1.25 27.4 0.9488 1.25 28.9 0.9483 1.35 27.9 0.950? 1.55 27.7 0.949? 1.56 27.5 0.9495 1.87 29.9 0.9496 1.63 28.5 0.9455 2.25 28.8 0.9437 1.46 30.0 0.9428 5.01 30, 3 0.9411 1.59 31.9 0.94OO Isobuten '0.37 32.4 0.9518 1.35 29.6 0.9564 1.79 31.1 0.9542 1.17 31.7 0.956? 4.20 30.1 0.9582 3.30 32.9 0.955? Polymerization or copolymerization of other alpha-olefin monomers, such as propylene, 4-methylpentene-1, the alkyl acrylates and the methacrylates and alkyl esters can be carried out in a similar manner.

The following comparative experiments were also performed: COMPARATIVE EXAMPLE A. In the same reaction vessel used in other preparations, TBT, Mg ° and anhydrous MgCl 2 were combined in octane in a molar ratio of 2/1 / 0.34 and heated to reflux for 15 minutes without sign on reaction. The anhydrous MgCl 2 remained undissolved. See also example IB above. 461 100 59 B. To the same system was added a quantity of free water equivalent to a Mgo / MgCl 2 .6H 2 O ratio of l / 0.34 in lump, but no change was found.

C. TBT and Mgo were combined in a molar ratio of 2 / l in octane and heated to reflux. While the yellow color became slightly more intense, there was no sign of reaction.

D. To system C above was added an amount of free water equivalent to a Mg / MgCl 2 .6H 2 O ratio of 1 / 0.34. A small amount of a light yellow precipitate formed which showed hydrolysis of the titanium compound but the magnesium remained unreacted.

E. TBT and MgCl 2 .6H 2 O were combined in octane in a molar ratio of 1 / 0.34 and heated to reflux. After the salt had completely dissolved, the solution became cloudy and somewhat viscous with continued refluxing for three hours but clarified and settled to a cloudy yellow liquid and whitish precipitate overnight. A further experiment in a molar ratio l / 0.128 developed a clear golden-yellow liquid with heating to reflux for only 16 minutes. At a molar ratio of 1 / 1.17 foaming and formation of a thick alley-colored gel, the reaction terminated after 45 minutes.

Compare Example VII above.

Claims (2)

A process for the preparation of an intermetallic compound for use as a catalytic component in the polymerization of alpha-olefins alone or together with at least one copolymerizable monomer, characterized by the reaction of: (1) a polymer transition metal oxide alkoxide wherein the transition metal is titanium or zirconium, which polymeric transition metal oxide alkoxide is produced by partial hydrolysis of a transition metal alkoxide, which hydrolysis is carried out with an aquo-complex as a water source, the water being provided in the form of an aluminum, hydrated iron, magnesium or nickel or in the form of a hydrated oxide, preferably silica gel; and (2) a reducing metal having a higher oxidation potential than the transition metal, which reducing metal is magnesium, calcium, zinc, aluminum or mixtures thereof, the molar ratio of the transition metal to the reducing metal being from about 0.5: 1 to about 3: 1, the reaction being initiated by heating to an elevated temperature, wherein an exothermic reaction is initiated, the heating being continued until the stoichiometric amount of reducing metal is consumed, and optionally further reacting the product with a halide activator. A method according to claim 1, characterized in that the molar ratio of transition metal to water is from about 1: 0.5 to about 1: 1.5.