FI71569B - FOERFARANDE FOER POLYMERISERING AV 1-OLEFINER OCH VID FOERFARANDET ANVAENDBAR KATALYSATOR - 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

1 71569

Process for the polymerization of 1-olefins and a catalyst useful in the process

The invention relates to a process for the poly-polymerization of 1-olefins using a polymerization catalyst system comprising an organic boron or aluminum compound and a halide-activated intermetallic compound of transition metal alkoxides as cocatalysts, and to a catalyst system used in the process.

10 Polyethylene produced by solution or slurry processes at lower pressures or in autoclaves or tubular reactors at higher pressures has been the subject of commercial production for many years.

Recent interest has been in straight-chain, high-pressure polyethylene resins characterized by linearity and short-chain branching by alkene comonomers, and they provide a narrow molecular weight distribution, improved strength properties, improved EC properties, higher melt viscosity, higher melt viscosity, higher softness. as well as improved low temperature brittleness. These and similar properties provide benefits to the user in applications such as blown film, wire and cable coating, cast film, co-extrusion, and injection molding and centrifugal forming.

These linear olefin polymers are typically prepared using catalysts of the general type disclosed by Ziegler, thus comprising a transition metal compound, usually a titanium halide, mixed with an organometallic compound such as alkylaluminum. The transition metal component can be activated by reaction with a halide promoter such as an alkyl aluminum halide. Improved catalysts of this type include those to which a magnesium component is combined, usually by the interaction of magnesium or a compound thereof with a transition metal component or an organometallic component, such as by grinding or chemical reaction or combination.

It is also of interest to prepare an intermediate of low pressure resins with modified properties using these types of coordination catalysts. In particular, resins with a wider molecular weight distribution and a higher melt index are sought.

The invention relates to an olefin polymerization catalyst system comprising a mixture of a first and a second cocatalyst, the first cocatalyst being an organoaluminum or organoboron compound and the second cocatalyst being a halide Akti-15 intermetallic compound which is a polymeric oxide having a higher oxidation potential than the transition metal, a reaction product wherein the transition metal is titanium or zirconium, the reducing metal is magnesium, calcium, zinc, aluminum or mixtures thereof, and wherein the polymeric transition metal oxide alkoxide is a controlled partial hydrolysis of titanium or zirconium alkoxide.

The invention also relates to a process for the polymerization of 1-olefins, alone or in combination with at least one copolymerizable monomer, under polymerization temperature and pressure conditions with an olefin polymerization catalyst system as defined above.

Transition metal-containing intermetallic compounds are prepared by the reaction of a polymeric transition metal alkoxy-30 dialkoxide with at least one reducing metal, i.e., a metal having a higher oxidation potential than the transition metal. Thus, for example, a polymeric titanium alkoxide or oxoalkoxide is reacted with a magnesium metal to give a reaction product which can be activated to form a 71569 3 olefin polymerization catalyst element.

The polymeric transition metal oxide alkoxide may be separately prepared by controlled hydrolysis of the alkoxide; or the polymeric oxoalkoxide can be obtained by an in situ reaction, e.g. by hydrolysis in a reaction medium containing a reducing metal. For example, titanium or zirconium tetrabutoxide can be reacted with a magnesium metal in a hydrocarbon solvent and in the presence of a controlled water source, preferably a hydrated metal salt such as magnesium halide hexahydrate.

Transition metal alkoxides, especially titanium alkoxides, are known for their compatible properties in organic solutions and their sensitivity to hydrolysis. It has been shown that the hydrolysis reaction starting from oligomeric, usually trimeric titanium alkoxides results in polymeric titanium oxide alkoxides, generally expressed by formula 20.

Ti (OR.) + NH-O -> TiO (OR). + 2n RÖH.

4 i n 4-2n

Condensation reactions can also take place at particularly elevated temperatures to structures comprising primary metal-oxygen-metal bridges such as:

OR OR

30 1 I

OR - Ti - O - Ti - OR

I i

OR OR

35 71569 which in turn can take part in the hydrolysis reaction or form precursors therefor.

These polymeric titanium alkoxides or oxoalkoxides (sometimes also called u-oxoalkoxy-5-dei) are represented by the series / Ψ ± 3 (x + i) ° 4χ (° R) 4 (x-3j7 'at X = 0, 1, 2, 3 ...., wherein the structure reflects the tendency of the metal to extend its coordination beyond its primary valence combined with the ability of the alkoxide to form a bridge to two or more metal atoms.

Despite the specific form that the alkoxide appears to have taken, it is in practice sufficient to know that the alkoxide oligomers, after controlled hydrolysis, form a series of polymeric oxide alkoxides extending from the dimer through cyclic forms to a linear chain polymer having a chain chain. On the other hand, more complete hydrolysis leads to the precipitation of insoluble products and complete hydrolysis to orthotitanic acid.

For ease of description, these materials are referred to herein as polymeric oxide alkoxides of the corresponding transition metals, which represent partial hydrolysis products. The hydrolysis reaction can be carried out separately and the products isolated and stored for further use, but this is inconvenient especially considering the possibility of further hydrolysis, therefore it is a preferred practice to develop these substances in the reaction medium. The evidence shows that the same hydrolysis reaction occurs in situ.

The hydrolysis reaction itself can be controlled directly by the amount of water fed to the transition metal alkoxide and the rate of addition of water. Water must be fed differentially or intermittently or sequentially; the simultaneous addition of the whole amount does not lead to the desired reaction, 5 71569 but causes excessive hydrolysis, precipitating insoluble substances. Dropwise addition is suitable as the reaction water is consumed, but it has been found more convenient to introduce water into the reaction as water of crystallization, which is called cationic, anionic, crystal lattice or zeolite water. Thus, conventional Hydra-fed metal salts are usually used in which the presence of the salts themselves is not detrimental to the system. It has been found that the bond provided by the coordinated water region in the hydrated salt is suitable for controlling the release and / or availability of water to the system as needed to induce, participate in and control the reaction.

As mentioned above, the total amount of water used has a direct effect on the oxy-dialkoxide form of the finished polymer and is thus selected in relation to the catalytic performance. (It is assumed that the stereoconfiguration of the partially hydrolyzed transition metal alkoxide determines or contributes to the nature or outcome of the catalytic activity of the partially activated catalyst component).

In general, it has been found sufficient to introduce as little as 0.5 moles of water per mole of transition metal. Amounts up to 1.5 moles are suitable and larger amounts up to 2.0 moles are useful whenever soaking of the hydrolysis products from the hydrocarbon solvent medium can be avoided. This is in principle achieved by reducing the rate of addition and stopping the addition as soon as signs of precipitation appear. Although the reaction is believed to be substantially equimolar, in some cases a suitable excess of water is used, which is conventional.

It is clear that the stereoisomeric form, chain length, etc. of the hydrolysis product change at the somewhat elevated temperature required for the reaction with the reducing metal 71569, and likewise the in situ processes affect the equilibria by mass action.

Likewise, the alkanol formed in the reaction affects equilibria, reaction rates, etc.

5 The hydrolysis reaction takes place under ambient pressure and temperature conditions and does not require special conditions. A hydrocarbon solvent may be used but is not required. Mere contact of the substances for a period of time, usually 10-30 minutes to 2 hours, is sufficient. The resulting 10 substance is stable under normal storage conditions and can be brought to a suitable concentration level, if desired, simply by dilution with a hydrocarbon solvent.

Polymeric transition metal oxide alkoxides are reacted with a reducing metal having a higher oxidation potential than the transition metal. Preferably, the polymeric titanium oxide alkoxide is used in combination with magnesium, calcium, aluminum or zinc or a mixture thereof as the reducing metal. Combinations of a transition metal alkoxide, a reducing metal, and a hydrated metal salt are preferably selected for their electropotentials such that side reactions are reduced, as is known in the art; and to ensure generally preferred levels of activity for the olefin polymerization, magnesium moieties are fed into the system by appropriate selection of a reducing metal / hydrated metal salt.

In a preferred embodiment (referred to below to illustrate the invention for convenience), titanium tetra-n-butoxide (TBT) is reacted with magnesium turnings and a hydrated metal salt, most preferably magnesium chloride hexahydrate, at a temperature of 50-150 ° C in a reaction vessel at self-evolving pressure. TBT forms the reaction medium or a hydrocarbon solvent may be used. Ti / Mg molar ratios can range from 1: 0.1 to 1: 1, although for the most homogeneous reaction system, a stoichiometric ratio of Ti to Mg of 1: 1 is preferred, with the amount of hydrated metal salt such that it donates the reaction. during n.

1 mole of water per mole of Mg.

The hydrocarbon-soluble catalyst precursor mainly comprises Ti moieties together with Mg moieties as one or more stereoconfiguration complexes which are believed to form predominantly oxidized forms. Some evidence exists in the mixed oxidation-10 facilities of titanium parts; it refers to a mutual system of Ti ^ +, Ti ^ + and Ti ^ + forms, which is possibly almost in equilibrium at least under dynamic reaction conditions. The preferred precursor is assumed to contain (Ti-O-Mg) bridge structures.

The intermetallic compounds prepared according to the invention are of particular interest as catalyst precursors, in reinforced or unconfirmed systems, for the isomerization, dimerization, oligomerization or polymerization of alkenes, alkynes or substituted alkenes, reducing agents or activators II, e.g. in the presence or absence of organometallic compounds.

Preferably in the use of such precursors, they are reacted with a halide activator such as an alkylaluminum halide and combined with an organometallic compound to form a catalyst system particularly suitable for the polymerization of ethylene and comonomers to polyethylene resins.

The transition metal component is a titanium or zir-30 conium alkoxide containing mainly -OR substituents in which R may contain up to 10 carbon atoms, preferably 2 to 5 carbon atoms, and is most preferably n-alkyl such as n-butyl. The selected component is normally liquid at ambient conditions and reaction temperatures due to ease of handling and also soluble in hydrocarbons for ease of use.

8 71569

When carrying out the hydrolysis reaction in question, it is generally preferred to use transition metal compounds containing only alkoxide substituents, although other substituents may be used as long as they do not interfere with the reaction in the sense that they would cause a significant modification in use. Halide-free n-alkoxides are generally used.

The transition metal component is used at the highest degree of oxidation of the transition metal to provide the desired stereoconfiguration, among other things.

Suitable titanium compounds include titanium tetraethoxide and compounds of the type containing one or more alkoxy radicals such as n-propoxy, iso-propoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, tert-butoxide. pentoxy, tert-amyloxy, n-hexyloxy, n-heptyloxy, nonyloxy, etc.

Some indications suggest that the rate of hydrolysis of n-alkyl derivatives decreases with increasing chain length and decreases with the complexity of the molecule, i.e., in the tertiary, secondary, normal direction, so these factors must be considered when selecting a preferred derivative. In general, titanium tetrabutoxide has been found to be very suitable for the practice of this invention, and tetraalkoxides of the same type are also preferred. It will be appreciated that mixed alkoxides are perfectly suitable and may be used when suitably available. Complex titanium alkoxides, which sometimes contain other metal components, can also be used.

The reducing metal is fed at least in part in the zero oxidation state as an essential base of the reaction system. A suitable source is ordinary chips, tape or powder. Commercially available, these materials 35 may be in a passivated surface oxidized state and grinding or grinding to provide at least a somewhat fresh surface is desirable, at least to control the rate of the reaction. The reducing metal may be added to the reaction as appropriate, e.g. as a slurry in a transition metal component and / or a hydrocarbon diluent, or may be added directly to the reactor.

Either in the in situ preparation or for the separate preparation of the polymeric transition metal alkoxide, a water source is used which releases or diffuses amounts of water or enters the reaction in a slow, rate-controlled manner during the reaction. As mentioned above, the coordination range provided by the hydrated metal salt has been found to be suitable for this purpose; but other water sources in the same proportions are also useful. Thus, a calcined silica gel free of other active ingredients but containing controlled amounts of bound water can be used. In general, the preferred water source is an aquocomplex in which the water is coordinated with the base in a known manner.

Suitable substances include hydrated metal salts, especially inorganic salts such as 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, to which a reflux condenser is preferably connected for the components volatile at the elevated temperatures generated in the reaction vessel. Self-generating pressure is used when the reaction proceeds steadily under ambient conditions, heating to initiate and maintain the reaction. As in any such reaction, stirring is preferred simply to avoid agglomeration or coating of the vessel surfaces, to achieve thorough mixing of the components, and to ensure a homogeneous reaction system.

Typically, a hydrocarbon solvent such as hexane, heptane, octane, decalin, mineral spirit, etc. is used to facilitate mixing of the components, heat transfer, and maintenance of a homogeneous reaction system.

Saturated hydrocarbons with a boiling point between 60 and 190 ° C are preferred. The liquid transition metal component can also at least partially act as a reaction medium, especially when the added solvent is not used. The reaction comprises the step of adding additional volatile components to azeotropic mixtures with the solvent or, if the components are used undiluted, to form a refluxing component, but in either case it is preferable to return the volatiles to the reaction mixture at least at intermediate intervals. Thus, when the titanium-15 component is titanium tetra-n-butoxide, butanol is formed which forms an acetropic mixture with the hydrocarbon solvent. The choice of solvent and / or alkoxide relative to the possible lowering of the reaction temperature is thus an important consideration, as will be appreciated by those skilled in the art.

The reaction temperature may, under certain conditions, be selected over a wide range depending on the reaction rate which may be conveniently carried out. It has been found that the reaction system (consisting of a liquid transition metal component, a dissolved hydrated metal salt, reducing metal particles and a solvent, if desired) exhibits visible gas evolution at about 60 ° -70 ° C, indicating the initial reaction temperature or activation energy. to a level of about 50 ° C, which thus forms the necessary mini-30 m temperature for the reaction of the polymeric oxide alkoxide with the reducing metal. The reaction is somewhat exothermic during the consumption of the reducing metal and can therefore be easily carried out to the next step, which is the reflux temperature. Since the developed alkanol 35 is widely consumed during the continuous reaction (as an independent component), the current temperature of the system changes and the completion of the reaction is evidenced by the cessation of visible metal and / or the recovery of pure solvent in only 30 minutes. up to 4 hours or more. Such temperatures can rise to 140 ° -190 ° C, and higher temperatures could of course be used, but without a clear advantage. It is most suitable to operate between 50-150 ° C, preferably between 70-140 ° C. In the absence of solvent, the upper limit is simply set according to the reflux temperature of the alkanol evolved during the reaction.

In addition to exothermicity, the reaction of the components is most evident in the significant change in color associated with the onset of gas evolution. When the translucency or brightness of the solution allows monitoring, it is seen that the evolution of gas, ranging from bubbling to strong gas effervescence, is evident on the metal surface, and usually light solutions turn immediately grayish, then rapidly darker to blue, sometimes purple, usually blue-black, sometimes there is a greenish tinge. The gas analysis does not show HCl and the gas 20 'is mainly H2> After a rapid color change, some color deepening occurs as the temperature gradually increases as the gas continues to evolve. At this point, an amount of alkanol corresponding to the alkoxide component is sufficient to suppress the boiling of the solvent, and it appears to be gradually consumed in a rate proportional manner with the remaining reducing metal.

The reaction product is at least partially soluble in the hydrocarbon and is kept in the form of a slurry for continued use. When isolated, X-ray diffraction analysis of the product, which is viscous to semi-solid, shows a predominantly amorphous nature.

The molar ratios of the components can vary within certain limits without significantly affecting the performance of the catalyst-35 precursor in end use. Thus, to avoid competing reactions that make the reaction product awkwardly gelatinous or difficult to handle, the transition metal component is usually fed in at least a molar ratio to the reducing metal, but the transition metal / reduction metal ratio can range from about 0.5: 1.0 to 3.0. : 1.0. Insufficient amount of reducing metal results in inhibiting the rise of the reaction temperature so that the reflux temperature of the pure solvent is not reached; while the excess reducing metal is immediately apparent from its non-consumable portion, so that the desired amount of this component can be readily ascertained by one skilled in the art.

Within these limits, a varying portion of the reaction product forms a hydrocarbon insoluble component, which, however, can be slurried and usually slurried with the soluble component for use, e.g., in further reaction with a halide activator to form an olefin polymerization catalyst. The amount of such insoluble component can be adjusted in part by using a solvent with a suitable partition coefficient, but when the use of a common hydrocarbon solvent such as octane is preferred for practical reasons, e.g. equimolar ratios of Ti / Mg / H 2 O components have been found to be most suitable for homogeneous reaction product formation. .

Water or an aqueous substance is also preferably fed in equimolar proportions to the transition metal component, as well as homogeneity and ease of reaction. Thus, in the case of MgCl 2, the amount of 0.17 moles gives about 1 mole of water during the reaction, and this portion up to about 2 moles of water gives the lightest possible reactions with one or more moles of transition metal component. More generally, I 0 may be about 0.66 to 3 moles per mole of transition metal. The amount of water present in a particular reaction step is apparently considerably less, ranging from amounts catalytic to the remaining components, depending on the manner and rate at which the water participates in the reaction, which is still unknown at this time. However, it is contemplated by working hypothesis alone that water or a water-containing substance that inhibits the rate of reaction is activated, released, available, or diffused so that it is available in a regular, continuous, unchanging, or rapid-dependent variable manner. However, if the same 5 molar proportion of free water is fed to the reaction at the beginning of it, it is completely inefficient in initiating the reaction at this or higher temperature and results in undesired complete hydrolysis reactions.

The amount of water used is substantially equimolar to the reducing metal component, or there is an excess of water, and the amount is proportional to its wear in the reaction because of the molar amount of water. inadequacy inevitably results in an excess of reducing metal. In general, a reasonable excess of 10-40% water is suitable to ensure a complete reaction. Higher proportions are suitable without limitation, but should be kept in relative stoichiometric equilibrium to the transition metal component.

The choice of aquocomplex or hydrated metal salt is essential for the controlled availability of the water it provides to the system. Thus, sodium acetate trihydrate is suitable as well as magnesium acetate tetrahydrate, magnesium sulfate heptahydrate and magnesium silicon fluoride hexahydrate. A salt having a maximum degree of hydration is preferred for the release determined by the coordination bond ratio. Most preferably, a hydrogenated magnesium halide such as magnesium chloride hexahydrate or magnesium bromide hexahydrate is used. These salts, as well as other hygroscopic substances even when supplied in commercial anhydrous form, contain some sorbed water, e.g., 17 mg / kg (see GB Patent 1,401,708), although well below the molar amounts of this invention. timed in accordance with. Thus, salts classified as anhydrous, unless specifically modified for purpose 35, are not suitable herein.

The reaction system described in the above description, although not tolerable, does not require an electron donor or a Lewis acid or solvent to perform some of these functions. As shown in the examples, in a preferred embodiment, the reaction is carried out with the aid of water of crystallization and the alcohol component in the system. Thus, it is not known otherwise whether proton transfer or electron donation mechanisms are involved or competing in reaction systems.

No distinctions are necessary because at least a portion of the reaction product is soluble in saturated carbon-10 hydrogen when used as a solvent or to form a solvation medium, so that even when a precipitate is formed and even after storage, a functional reactive slurry can be easily formed.

According to a preferred embodiment of the invention, the reaction product (catalyst precursor) is further interacted with a halide activator, such as an alkylaluminum halide, a silicon halide, an alkyl silicon halide, a titanium halide or an alkyl borohalide. It has been found that the catalyst precursor can be easily activated simply by combining the product with a halide activator. The reaction is strongly exothermic and therefore the halide activator is typically added gradually to the reaction system. Normally, the reaction is also complete after the addition is complete and can be stopped. The solid reaction product or slurry can be used immediately or stored for future use. Usually, for the best control of the molecular weight properties, and especially for the preparation of the high pressure resin, only the hydrocarbon-washed solid reaction product is used as the catalyst.

The halide activator is usually used in a molar ratio of 3: 1 to 6: 1 (ratio of aluminum, silicon or boron to the transition metal), although ratios of 2: 1 or higher have been used successfully.

The resulting catalyst product can be used directly in the polymerization reaction, although it is usually diluted, extended, or reduced to provide a suitable feed with an amount of catalyst equivalent to 80-100 mg of transition metal, calculated for a nominal productivity greater than 200,000 g of polymer-5 / gram of transition metal in continuous polymerization, which this catalyst usually exceeds. Adjustments are made according to reactivity and efficiency, usually by dilution alone and by adjusting feed rates.

The transition metal-containing catalyst is combined with an organometallic cocatalyst such as triethylaluminum or triisobutylaluminum or a non-metallic compound such as triethylboron for use in polymerization. A typical polymerization feed thus contains 42 parts of isobutane solvent, 25 parts of ethylene, 15.0002 parts of catalyst (calculated as Tiina) and 0.009 parts of cocatalyst (triethylaluminum or TEA, calculated as Alina) to a reactor maintained at 4583 kPa and 71 ° C. When a cocatalyst is used, its amount is generally calculated to be between about 30 and 50 ppm of the amount of isobutane, calculated as Alina or B.

Examples of metal cocatalysts are trialkylaluminum such as triethylaluminum, triisobutylaluminum, trioctylaluminum, alkylaluminum halides, alkylaluminum alkoxides, dialkylzinc, beryllium and aluminum boride, and sodium borohydrides, Non-metal cocatalysts include boroalkyls such as triethylborane, triisobutylborane and trimethylborane, and hydrides of boron such as diborane, pentaborane, hexaborane and decaborane.

The polymerization reaction is preferably a loop reactor adapted to treat the slurry, thus using a solvent such as isobutane from which the polymer separates as a granular solid. The polymerization reaction is carried out at low pressure, e.g. between 1380-6895 kPa 71569 16 and at a temperature in the range of 38-93 ° C, leading to hydrogen to control the molecular weight distribution if desired. Other n-alkenes can be fed to the reactor in small amounts relative to ethylene to copolymerize them with ethylene. Typically, butene-1 or a mixture thereof with hexene-1 is used in amounts of 3 to 10 mol%, although other amounts of alpha-olefin comonomers can be readily used. By using such n-alkene monomers, resin densities between 0.91 and 0.96 can be ensured.

Other alpha-olefin comonomers may be used, such as 4-methylpentene-1, 3-methylbutene-1, iso-butylene, 1-heptene, 1-decene or 1-dodecene, from as little as 0.2% by weight -%, especially when monomer mixtures are used.

However, the polymerization can be carried out at higher pressures, e.g. between 13.8 x 10 -27.6 x 10 Pa in an autoclave or in tubular reactors, if desired.

As used herein, an intermetallic "compound" or "complex" refers to any reaction product, whether obtained by coordination or combination, or in a form containing or enclosing one or more compounds, in clusters, or in any other arrangement under useful conditions, wherein the color change and gas evolution 25 are generally indicative of the reaction, likely to indicate reduction-oxidation, rearrangement, and association between the non-consumable elements of the reaction system.

The following examples are intended to further illustrate the invention and the manner in which it will be practiced and used. All parts are by weight unless otherwise indicated. Melt indices have been measured under ASTM D-1238-57T conditions E&F, MI and HLMI values for powder or resin samples, respectively, according to specification. HLMI / MI or MIR is the melt index ratio, a measure of shear sensitivity that reflects the molecular weight distribution. The tests are as described or as is normally performed in similar cases.

17 71 5 6 9

Example I

A. 6.0 parts of Ti (OBu) 4 (TBT) and 4.2 parts of CrCl 2 O 2 were combined in a reaction vessel. The chromium salt partially dissolved and some heat was evolved upon stirring. Complete dissolution was performed by gentle heating to 60-70 ° C. The chromium salt was further dissolved in 3.3 parts with stirring over 20 minutes. A total of 0.3 parts of magnesium turnings were added portionwise to the green solution, which caused the development of abrupt growth. The cooled reaction product, free of excess magnesium (which had completely disappeared), was a viscous green liquid and soluble in hexane.

B. In a similar experiment with anhydrous chromium chloride was used as the reaction of titanium but no formulation was not 15 occurred when heated above 100 ° C for half an hour. Addition of zinc dust and further heating above 150 ° C still showed no reaction. Replacement with magnesium turnings also did not give a reaction. It was concluded that the hydrated salt was an essential component for the reaction system.

Example II

A. TBT (0.121 mol), CrCl 3 .6H 2 O (0.015 mol) and Mg (0.0075 mol) were combined with stirring in a reaction vessel equipped with an electric heating mantle. The chromium salt completely dissolved at about 60 ° C and the reaction with magnesium turnings showed evolution of gas at 85 ° C and was violent at 100 ° C and ceased at 116 ° C with some Mg remaining. After dissolving the remaining Mg, heating was continued for a total reaction time of 1 hour and 45 minutes. The reaction product was a dark green liquid at room temperature that readily dissolved in hexane.

B. In a similar manner, a reaction product was prepared in a ratio of 0.116 mol TBT, 0.029 mol CrCl 2 .H 2 O and 0.029 mol Mg. At 118 ° C, the off-green reaction product at 35 ° C obtained 35 distinct bluish colors while gas evolution continued. The reaction was stopped after the magnesium had disappeared within one hour and 15 minutes. The reaction product was soluble in hexane.

71569 ° C. The above experiments were repeated with reactant amounts of 0.11 mol TBT, 0.058 mol CrCl 2 -O 2 O and 0.0145 mol Mg. The reaction was complete in 115 minutes to give a hexane soluble product.

5 D. The ratio of reactants was again changed in an additional experiment as follows: 0.115 mol TBT, 0.0287 mol CrCl 2 -HH 2 O and 0.0144 mol Mg. At 114 ° C, the off-green material turned blue on the Mg surface. The recovered reaction product was soluble in hexane.

E. In a similar experiment, 0.176 mol of TBT, 0.30 mol of CrCl 3 and 0.176 mol of Mg were reacted in octane. The bright yellow color of the reaction became dirty at 70 ° C with increasing gas evolution and darkened almost black at 90 ° C. The color returned to green at 119 ° C and the reaction was stopped at 121 ° C with complete disappearance of the magnesium. Reaction product (6.9 wt% Ti, 3.5 wt%

Mg and 1.3 wt% Cr) was a dark olive green liquid and a darker solid (ca. 50:50 / v / v) which settled apart.

20 F. In another experiment, octane-reactive substances were used in ratios of 0.150 mol TBT, 0.015 mol CrCl 2 O 2 O and 0.150 mol Mg. Again, the dirty green color turned almost black under a violent effervescence, forming at 109 ° C a dark blue-black reaction product.

25 (5.7 wt% Ti; 2.9% Mg, 2.1 wt% Cr).

Example III

A. The reaction product IIE was combined in a reaction vessel with isobutylaluminum dichloride, which was added dropwise in ratios to give an Al / Ti molar ratio of 30 3; The green-colored mixture initially changed from brown to purple at 38 ° C, which had changed to reddish-brown in appearance after the addition of the reactant at 39 ° C. After stirring for an additional 30 minutes, the reaction was quenched to give a dark red-brown liquid and a dark brown precipitate.

B. Reaction product IIF was reacted in a similar manner with isobutylaluminum dichloride (Al (Ti molar ratio 19 71 569 = 3.1). The peak temperature at the end of the addition was 48 ° C, but no brown color change was observed. 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 (88 ° C, 10 mole% ethylene, 0.0002 parts of catalyst, calculated as Ti, triethylaluminum about 45 ppm, calculated as Al, H 2 as shown) with results shown in Table I below:

Table I

Catalyst H2 Production Resin properties

__ kPa g Pe / g Ti h MI HLMI HLMI HLMI / MI

15 IIIA 515 35160 10.1 265 26.3 928 29220 18.9 618 32.6 IIIB 515 30380 6.6 264 27 928 26880 32.8 855 26.1 In the following example, the catalyst component of the invention was prepared from the reactant mixture without further -liuotinta.

Example V

A. 0.1212 mol Ti (OBu) 4 iTBTj, 0.121 mol magnesium-25 chips and 0.0012 mol MgCl2.6H2O (TBT / Mg / MgCl2.6H2O = 1: 1: 0.01, molar) were combined with stirring in a vessel, which was equipped with an electric heating mantle. The magnesium salt completely dissolved at room temperature to form a homogeneous reaction mixture. The mixture was heated stepwise and at 95 ° C gas evolution began on the surface of the magnesium turnings. At 140 ° C, where the mixture refluxed, bubbling had become violent. The color of the solution darkened and bubbling ceased at 170 ° C after which time the reaction was stopped. The reaction product contained an excess of magnesium - Only n.

8.5% of the feed had reacted - and was soluble in hexane.

71569 20 B. In the second experiment, the molar ratio of MgCl 2 .6H 2 O 2 was increased (TBT / Mg / MgCl 2 · βΗ ^ Ο = 1: 1: 0.1, molar). The golden yellow liquid turned gray with gas evolution at 104 ° C and darkened on further heating to 168 ° C. After a reaction time of 125 minutes, the reaction product contained some excess magnesium - about 63% had reacted.

C. The molar ratio used in the additional experiment was 1: 1: 0.17. The dark blue reaction product was very viscous and could not be easily diluted with hexane. All the magnesium was consumed.

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

Example VI

15 A. 50.2 parts (0.148 mol) of TBT were added with stirring to a vessel equipped with an electric heating mantle and containing 58.6 parts of octane. Magnesium turnings (0, C74mol) were added, stirring was started and then 0.0125 mol of MgCl2 was added with heating for 1 minute. At 75 ° C the magnesium salt was completely dissolved at 20 (20 minutes) and at 95 ° C (25 minutes) the evolution of gas began on the surface of the magnesium turnings, which intensified when the solution turned gray and then deep blue at reflux at 117 ° C (35 minutes). ). The magnesium metal had reacted completely in 25 hours (128-129 ° C) and the reaction was stopped. The dark reaction product dissolved in octane (a small amount of greenish precipitate remained) was calculated to contain 6.8% by weight of Ti and 2.0% by weight of Mg (Ti / Mg = 3.4: 1 by weight, 1.7: 1 molar). .

30 B. The above experiment was essentially repeated, except that the molar ratios of the reactants were modified with the following results: 21 71569

Ti / Mg / MgCi2 · Ti / Mg Notes

Molar ratio_ (molar) 1.0 / 0.65 / 0.11 1.32 Dark blue-black liquid and green precipitate. 6.6% by weight

Ti, 2.6% by weight Mg (calcined) ^ 1.0 / 0.75 / 0.128 1.14 Blue solution with a greenish tinge, 6.5% by weight Ti, 2.8% by weight Mg (calcined) ) 1,0 / 1,0 / 0,085 0,92 Blue-black liquid and light green precipitate (insoluble in acetone, alkane and methylene chloride) somewhat unreactive Mg 1/1 / 0,17 0,85 Inch blue-black liquid, 6 .6% by weight Ti, 3.9% by weight

Mj (calcined) 1/1 / 0.34 0.75 Tuna blue liquid, 6.7% by weight Ti, 4.6% by weight 15 Mg (calcined) 1/1 / 0.51 0.66 Turbid blue liquid, 3.7% by weight Ti, 2.9% by weight Mg (calcined) 1/2 / 0.17 0.46 lmmm blue liquid and viscous green gel, 2q somewhat unreacted Mg 1/2 / 0.34 0.43 Tiinmansblue liquid and vis constituent gel. Somewhat unreacted Mg.

2/1 / 0.17 1.70 Example IIA

2/1 / 0.34 1.50 Blue-black solution, 7.1% by weight 25 Ti, 2.3% by weight Mg (calcined) 3/1 / 0.51 1.99 Blue-black liquid with a light greenish tinge . 6.1% by weight of Ti, 1.6% by weight of Mg (calcined) 3 C C. The above preparation in a 1/1 / 0.34 ratio was repeated, except that 63.7 parts of TBT with 67.5 parts of hexane were used, which was as a solvent reaction medium. The result was a tan blue liquid containing 8.2% by weight of Ti and 1.6% by weight of Mg by calcination.

35 The following example shows the stepwise preparation of a catalyst component.

71569 22

Example VII

2.61 parts of MgCl 2 and 34.2 parts of TBT were combined with stirring. After 30 minutes, the mixture of yellow liquid and crystalline salt was replaced with a cloudy yellow, opaque, viscous liquid. As stirring continued, the turbidity disappeared to give a clear yellow liquid in 2 hours (in another experiment performed with octane for 30 minutes, the salt was completely dissolved to form a ketal liquid without any precipitate or turbidity).

The Ti / Mg / MgCl reaction product was prepared as in the previous examples using the bright yellow liquid prepared above and 1.83 parts of Mg components in a molar ratio of 1 / 0.75 / 0.128 octane. The reaction proceeded steadily, forming a dark blue-black liquid and a green precipitate in the same manner as in the other reactions shown.

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

20 The following example shows the importance of the amount of water bound.

Example VIII

A series of similar experiments were performed at a molar ratio of 1 / 0.75 / 0.128 (TBT / Mg / MgCl2.6H2O), except that the degree of hydration of the magnesium salt was modified.

When MgCl2.4H2O was used (H2O / Mg = 0.68 / 1 while the ratio was 1: 1 for MgCl2.6HCl> 20), only 89.1% of the magnesium metal reacted. The use of MgCl 2 .2H 2 O at the same total molar ratio (H 2 O / Mg = 0.34 / 1) gave only a 62.1% reaction to Mg.

In repeated experiments, the amount of hydrated salt fed was added to give a H 2 O / Mg ratio of 1/1. All magnesium metal reacts. It was also found that the amount of insoluble reaction product increased with increasing salt amounts.

The following example illustrates the use of other titanium compounds.

71569 23

Example IX

A. 45.35 parts (0.159 mol) of Ti (O-i-Pr) 4, 0.1595 mol of Mg and 50.85 parts of octane were placed in a stirred reaction flask equipped with an electric heating mantle and 0.027 mol of MgCl 2 was added. O. Samea yellow

^ ^ O

The mixture turned gray at reflux at about 88 ° C and turned blue at 90 ° C with gas effervescence. Based on the remaining magnesium, it was concluded that the reaction was partially quenched by the presence of 10 azeotropic octane / isopropanol mixture.

B. The reaction described in A was repeated at a molar ratio of 1 / 0.75 / 0.128 reactants using decalin as a diluent (b.p. 185-189 ° C). After 6 hours, the reflux temperature had reached 140 ° C and the reaction was stopped. A dark blue-black liquid with a small amount of dark precipitate was obtained. Only 8.8% of the magnesium had reacted.

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

D. In the same manner, titanium tetranonate was used with magnesium and MgCl 2 * 6H 2 O in a molar ratio of 1 / 0.75 / 0.128. A blue liquid formed, 45% of the magnesium had been consumed.

E. The reaction product of titanium tetrachloride and butanol (believed 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 previous examples. Approximately half of the magnesium was consumed in about 3 hours, after which a dark blue liquid and an olive green precipitate (50/50 v / v) were recovered.

35 The following example uses zirconium metal alkoxide.

71569 24

Example X

A. 12.83 parts of Zr (OBu) → BuOH (0.028 mol); 0.34 parts of Mg (0.14 mol) 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 signs of reaction. 0.97 parts of MgCl 2 O 2 O (0.005 mol) were added, after which a vigorous stirring was observed and the reaction mixture became cloudy in appearance.

B. In another experiment, 31.7 parts of this zirconium compound (0.069 mol) were combined with magnesium metal chips (0.069 mol) and 57.6 parts of mineral spirit (b.p. 170-195 ° C) and 4.79 parts of MgCl 2 - H 2 O (0.0235 mol). Heat was introduced into the reaction vessel through an electrical jacket 15. Within 5 minutes the reaction mixture had become opaque in appearance and gas evolution from the surface of the magnesium metal was evident when the temperature of 85 ° C was reached after an reaction time of 8 minutes. The evolution of gas continued to effervesce and the temperature rose to 108 ° C, 20 when a white solid appeared. By continuing to heat to 133 ° C (1 hour reaction time), all of the magnesium metal had disappeared and the reactor contained a milky white liquid and a white precipitate. The reaction mixture was cooled and 92 parts of a mixture containing 6.8% by weight of Zr and 2.4% of Mg (Zr / Mg = 2.8: 1, by weight; Zr (Mg molar ratio 0.75) and which was soluble in hydrocarbons.

The reaction product can be activated in a known manner, e.g. by reaction with an alkylaluminum halide, suitably in an Al / Zr molar ratio of about 3 / 1-6 / 1 to give, together with an organic or orthometallic reducing agent, an olefin polymerization catalyst system suitable for forming a polyethylene resin.

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

25 71569

Example XI

A. 0.074 mol TiiOBu): 0.07 mol Ca (commercially supplied thick chips, mechanically cut into smaller particles.) And 0.0125 mol MgCl 2 / H 2 O were combined in octane with stirring in a reaction vessel equipped with an electric heating mantle. When 105 ° C was reached, the solution darkened in color and at 108 ° C the solution changed to a dark gray appearance, developing a gas. At 110.5 ° C, rapid gas evolution was observed, followed by the formation of a dark blue liquid. After 90 minutes, the reaction was quenched and the reaction product consisting of a dark blue-black liquid with a greenish tinge was isolated.

The experiment was repeated at the same molar ratio. 50% of the calcium reacted to give a tan blue liquid and a gray precipitate containing 66.2% 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 Ai).

In another experiment, the same reactants were combined in a molar ratio of 0.75 / 0.128. Calcium reacts 63% to give a blue-black liquid and a green precipitate. The reaction product (molar ratio 1 / 0.47 / 0.128) contained 6.6% by weight

Ti, 2.6 wt% Ca and 0.4 wt% Mg (XI A2).

B. Reaction product XI AI was further reacted with ethylaluminum dichloride in an Al / Ti molar ratio of 3/1 and 6/1. The reaction products were diluted with hexane and the halide activator was added slowly to quench the highly exothermic reaction. In the 3/1 experiment, the initially formed grayish slurry disintegrated after completion of the reaction to a pink liquid and a white precipitate. With an Al / Ti ratio of 6/1, the slurry turned gray-30 and then lime green.

Reaction product XI A2 was similarly treated with EtAlCl 2 at an Al / Ti molar ratio of 3/1 and 6/1. The reactions were uniform, giving 3 / l of a deep brown slurry and 6 / l of a red-brown liquid with a brown precipitate.

35 C. The reaction products prepared in Part B were used in ethylene polymerization with the results shown in the following table.

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71569 27

The experiments showed a somewhat wider Mole weight distribution in the resin compared to the use of magnesium as a reducing metal.

Replacement with zinc as a reducing metal is shown in the following example.

Example XII

A. 0.204 mol of Ti (OBU) ^, 0.153 irol Zn granules, and 0.206 mol of MgCl 2 / O 2 O were combined in octane in a stirred closed system equipped with a reflux condenser and heated externally. In 13 minutes (85 ° C) there was a rapid discoloration to blue-black with gas evolution increasing with vigorous effervescence and foaming. The reaction product, a blue-black liquid (no precipitate) containing 7.7% Ti, 0.9% Zn 15 and 0.5% Mg by weight, fades to yellow when exposed to air.

B. The reaction product TiZnMg (molar ratio 1 / 0.86 / 0.128) was reacted with isobutylaluminum dichloride in a molar ratio of Al / Ti of 3/1, in hexane at 10-13 ° C. (XII Bl).

C. The preparation of the TiZnMg reaction product (XII A) was repeated using Zn dust, with similar results. In a further experiment, sponge-like zinc consumed only 7% of the zinc and a green layer was found to form on the surface of the zinc.

D. The activated reaction product XII B1 prepared above was washed thoroughly in hexane and used to prepare a high pressure polyethylene resin. The reactor was preloaded with sufficient butene-1 to ensure the target density and the reaction was carried out (by differential additions of butene-1 together with ethylene) at 77 ° C and 343 kPa in the presence of triethylaluminum as cocatalyst. The recovered resin had the following properties: density 0.9165, 35 MI 1.68, HLMI 52.1 and MIR 31.

28 71 5 69

The following example uses potassium as the reducing metal.

Example XIII

62.7 mmol of TBT, 47 mmol of fresh potassium metal-5 (scraped clean from its oxide / hydroxide coating immersed in octane) and 8.0 mmol of MgCl 2 -O 2 O were combined in octane in a closed system equipped with a reflux condenser and heated externally. . In 2 minutes at 35 ° C, the color changed to 10 blue-black and bubbles appeared. This was followed by violent gas evolution and turmoil. After the potassium metal disappeared, the reaction was stopped (within 5 hours). A dark blue-black liquid was recovered along with a small amount of a dark blue precipitate.

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

Example XIV

A. 112.31 parts of Ti (OBU) 4 (0.33 mol), 8.91 parts of Al (alpha-inorganic spherical aluminum powder, sieve number -45 mesh) and 11.4 parts of MgCl 2 -6H 2 O (0.056 mol). The molar ratio of 1: 1: 0.177 was stirred in a reaction vessel with stirring and heat application using an electric jacket.

After reaching 100 ° C in about 10 minutes, the yellow color deepened and at 118 ° C a strong turmoil began with the evolution of gas. At 122 ° C, the refluxing solution had a gray tinge and the temperature stabilized as the reaction mixture changed from deep gray to blue with a dark blue tinge and then a sinimus-30 taxi after heating the reaction for 27 minutes. The temperature was maintained by raising to 145 ° C in 1 hour and 20 minutes, after which gas evolution had essentially ceased and the reaction was stopped.

The reaction product was a viscous liquid at room temperature, indicating unreacted aluminum particles.

29 71569

The unreacted aluminum was separated, washed and weighed, revealing that 6.7 parts of Al had reacted. The reaction product contained 7.9 wt% Ti, 3.4 wt% Al and 0.7 wt% Mg (molar ratio 1: 0.75: 0.17).

B. B. 10.10 parts of the reaction product prepared above (0.719 parts of Ti or 0.015 mol of Ti) were added in hexane (13.0 parts) to a reaction vessel in a cooling bath. 0.045 mol of ethylaluminum dichloride was gradually added, keeping the temperature between 15-20 ° C. After stirring for 10 minutes, the mixture gave a dark reddish-brown slurry and a difficult-to-handle precipitate (B1).

A second experiment (0.175 mol / 0.0525 mol Al) was performed without cooling to a peak temperature of 38 ° C and again a reddish brown slurry with a difficult to handle solid precipitate (B2) was formed.

Example XV

The reaction products of Example XIV were used as catalysts in the polymerization of ethylene under standard conditions (88 ° C, 515 kPa H 2) using triethylaluminum as cocatalyst to give the following results.

MI HLMI MIR

Bl 0.14 6.45 46.1 B2 0.38 17.4 45.7

Example XVI

In the same manner as above, 0.133 mol of TBT, 0.100 mol of Al 1 and 0.017 mol of AlCl 3 * 6H 2 O in octane were combined and reacted for 7 hours and 15 minutes to give a dark blue-black liquid and a small amount of gray precipitate. About 40% of the aluminum reacted to give a reaction product containing 6.6% by weight of Ti and 1.6% by weight of Al. (XVI AI).

Similarly, the reactants were combined in a molar ratio of 1/1 / 0.17. Approximately 58% of Al was reacted to give a reaction product containing 6.5% by weight of Ti and 2.7% by weight of 35 Al (XVI A2).

30 71 569 B. The reaction products (XVI A1) and (AVI A2) were activated with ethylaluminum chloride in an Al / Ti ratio of 3/1.

C. A solid portion of the activated reaction product (XVI A2) was isolated from the supernatant and used with 5 TEA as a cocatalyst in ethylene polymerization at 77 ° C, 205 kPa H 2 to give a resin characterized by Mi 0.02, HLMI 1.01, MIR 50.5 and in the second experiment MI 0.02, HLMI 0.45 and MIR 22.5.

The following examples show catalyst-10 components prepared using other aquocomplexes.

Example XVII

A. 0.0335 moles of TBT and 0.0335 moles of Mg were mixed in octane and heated in a reaction vessel to which 0.0057 moles of MgBr 2 * 6H 2 O was added. (Reaction molar ratio 1/1 / 0.17). The salt dissolved in six minutes when heated to 65 ° C. As the gas bubbled, a gray color developed and the solution turned blue, then blue-black with a greenish tinge. The reaction was quenched at 123 ° C (ca. 10% unreacted Mg) after a reaction period of 4 hours and 10 minutes. (XVII A).

In a similar manner, a reaction product was prepared at a molar ratio (Ti / Mg / MgBr2.6H2O = 1 / 0.65 / 0.11) of 011 blue-black liquid and a dark green precipitate (6.5 wt% 25 Ti, 2.5 wt%). % Mg (calcination).

B. The decanted reaction product (XVII A) was combined with isobutylaluminum dichloride at Al / Ti levels of 3/1 and 6/1 with the gradual addition of alkylaluminum halide. In the first experiment (Al / Ti = 3/1), a peak temperature of 42 ° C was reached at an addition rate of one drop / 2-3 s, after which the green liquid turned brown. The reaction product was a red-brown liquid and a brown precipitate.

(IV B-1). The 6/1 product (IV B-2) was prepared in the same manner with the same results.

In a separate experiment, the reaction product (XVII A) was combined with SiCl 3 in the same manner. The reaction product from the 30 minute reaction with a Si / Ti ratio of 3/1 was a pale yellow liquid and a brown precipitate. A similar experiment gave a reaction product with a Si / Ti ratio of 6/1.

5 C. Activated reaction products XVII B1 and XVII B-2 (1% by weight Ti) were used in the polymerization of ethylene (10 mol% in isobutane) at 88 ° C, as a hydrogen modifier and as triethylaluminum cocatalyst (45 ppm Al) and were compared. for a similar experiment using magnesium chloride hydrate with the results shown in Table III below: 71569 32

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Example XVIII

A. 42.23 parts of TBT (0.124 mol) were combined with 3.02 parts of Mg (0.124 mol) in octane (42.8 parts) in the presence of 5.7 parts of FeCl 2 * 6H 2 O (0.02 mol) (TMgFe = 5 1/1 / 0.17, mol) in a sealed stirred reaction vessel equipped with a reflux condenser and an electric heating mantle. Heating was started and gas evolution began in 6 minutes at 65 ° C. The dirty yellow color turned dark brown at 80 ° C (7 minutes) and gas evolution increased. After about 30 minutes, gas evolution had slowed and ceased with the consumption of Mg and the reaction was stopped. There was no residue in the very dark solution. (XVIII AI).

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

B. Reaction Product XVIII Al was activated by reaction with a 50% by weight solution of ethylaluminum dichloride in hexane at an Al / Ti ratio of 3/1. A brown liquid and precipitate containing 16.5 mg Ti / g was collected.

(XVIII Bl).

In a similar manner, the reaction product (XVIII A2) was activated.

25 The dark brown liquid turned into a purple slurry and then into a dark gray slurry. The resulting clear liquid and gray precipitate contained 16 mg Ti / g.

C. Activated reaction product XVIII B1 was used in the polymerization of ethylene at 880 ° C, 414 kPa H 2 O. 114.320 g PE / g Ti / h were recovered and had the following properties: Mi 5.1, HLMI 155.3, MIR 30.3.

Example XIX

A. 1. 0.16 mol of Ti (OBu) 2, 0.160 mol of magnesium turnings and 0.027 mol of CoCl 2 * 6H 2 O were combined in a stirred reaction vessel with 51.2 parts of octane. Purple cobalt salt crystals give a dark blue solution 34 7 1 5 6 9 after dissolution. The mixture is heated using an electric jacket, and gas evolution on magnesium surfaces occurs at 58 ° C, increasing to strong effervescence at 107 ° C in 12 minutes. The bright blue color tu-5 turns grayish on further heating and turns almost black at 123-125 ° C when all the magnesium has faded and the reaction is stopped, after 90 minutes.

The cloudy blue reaction product was soluble in the hydrocarbon and decomposed into a dark blue liquid and dark precipitate after standing.

The experiment was repeated with essentially similar results.

B. The reaction product of the above preparation was shaken and 0.0111 mol (Ti) was combined with isobutylaluminum dichloride (0.0333 mol Al) which was added dropwise to the reaction vessel. The temperature peaked at 40 ° C, forming a greyish precipitate which turned brown upon further addition of BuAlCl 2. After stirring for an additional 30 minutes, the reaction was quenched to give 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 mol% ethylene, 0.0002 parts of catalyst calculated as Ti, triethylaluminum about 45 ppm calculated as Al, and as shown) , with the results shown in Table IV below:

Table IV

Catalyst H2 Productivity Resin ^^ det

kpa g Pe / g Ti / h MI_ HLMI HLMI / MI

30 XIX B 515 105 180 6.2 206 33.6 928 75 290 33.9 950 28.1 35! 71569

Example XX

A. 0.169 molTi (OBu) ^ / TBT7, 0.169 mol magnesium turnings and 0.029 mol AlCl 3 · 6H 2 O in octane used as diluent were 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 and effervescently violently on the surface of the magnesium due to the evolution of gas. The solution turned blue, and a uniform blue-black liquid with some residual magnesium was formed on heating to 122 ° C with uniform cooling to Palau-10. At 125 ° C, all magnesium metal disappeared and the solution had a slight green tinge. The reaction was stopped and the dark blue-black liquid and green precipitate were collected in a volume ratio of about 95/5.

B. The reaction product described above was combined with isobutylaluminum dichloride in a molar ratio of 3: 1 and 6: 1 Al / Ti by the dropwise addition of chloride to a reaction vessel containing titanium material. In the first reaction (3: 1), alkylaluminum dichloride was added at a rate of 1 drop / 2-3 seconds until a peak temperature of 42 ° C was reached, whereupon the color changed from blue-green to brown. After stirring for an additional 30 minutes, the reaction product, red-brown liquid and brown precipitate were isolated.

25 (XX B).

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

D. Reaction products XX B and XX C were used with a triethylaluminum cocatalyst (45 ppm Al) in the polymerization of ethylene (10 mol%) with an isobutane diluent at 88 ° C using hydrogen as shown. The experiments were terminated after 60 minutes with the results shown in Table V below:

Table V 715 6 9

Catalyst H_ PE Productivity Resin properties

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

XX B 515 406 84 580 17.2 517 30.1 5 928 542 75 280 54.9 1413 25.7 XX C 515 245 54 440 4.11 129 31.4 928 183 34 860 26.2 801 30.5

Example XXI

10 A. 0.53 mol Ti (OBU) 4 / TBTj7, 0.153 mol Mg chips and 0.026 mol NiCl 2 * 6H 2 O were combined with 61.75 parts of octane in a stirred vessel equipped with an electric heating mantle. Upon heating to 44 ° C, the yellow solution deepened in color and gas evolution on the magnesium metal surface became observed at about 57 ° C.

As heating continued, gas evolution increased until the reaction system at 102 ° C (15 minute reaction) turned pale brown in color. The vigorous stirring continued as the brown color darkened until at 126 ° C (75 minutes) all of the magnesium had disappeared and the reaction was stopped. The reaction product (XXIX-1) was a hydrocarbon-soluble dark brown liquid and a small amount of a fine precipitate.

In another experiment, 0.149 mol of TBT, 0.149 mol of Mg 25 and 0.051 mol of NiCl 2 * 6H 2 O were combined in octane in the same manner. The Mg metal disappeared at 115 ° C, 120 minutes, and the reaction gave a dark brown-black hydrocarbon-soluble liquid which decomposed on standing to a very fine dark precipitate and a yellow liquid, about 50/50 by volume (XXIA-2).

B. The reaction product IA-1 was shaken and a portion of it (0.0137 mol Ti) was placed in a reaction vessel with a hexane diluent to which i-BuAlCl 2 35 71569 (0.0411 mol Al) was added dropwise at a rate of 1 drop / 2 -3 s up to 28 ° C and 1 drop / s up to a maximum temperature of 39 ° C. When the addition was complete, the contents of the vessel were stirred for 30 minutes and the reaction product, a dark red-brown liquid and 5 dark gray precipitates, was isolated. (XXIB-I).

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

In essentially the same manner, the reaction product XXIA-2 (Ti / Mg / Ni molar ratio 1/1 / 0.34) was combined with i-BuAlCl 2 in an Al / Ti ratio of 3: 1, with the same results, except that the supernatant was a pale liquid. reddish brown in color. (XXIB-3).

In another experiment, the reaction product XXIA-2 was reacted in a similar manner in an Al: Ti molar ratio of i-BuAlCl 2 of 6: 1 to form a dark liquid and a dark precipitate in the same manner. (XXIB-4).

The same reaction product XXIA-2 was combined with ethylaluminum-20 dichloride in the same manner to give a dark red-brown liquid and a dark gray precipitate. (XXIB-5).

Example XXII

A. Example XXIA was repeated by feeding the reactants in a Ti: Mg: Ni molar ratio of 1: 0.65: 0.11. The change in color 25 occurred from dark brown to dark brown while gas evolved, and then through gray brown to dark blue-black when magnesium was consumed, in a reaction lasting 6 hours. (XXIIA).

B. Reaction product XXIIA was combined with ethylaluminum dichloride · as described in Example XXIB

In an Al / Ti molar ratio of 3: 1. A red-brown liquid and a red-brown precipitate were recovered. (XXIIB).

Example XXIII

Example XXIIA was repeated by feeding 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 dichloride in an Al / Ti molar ratio of 3/1.

Example XXIV

A series of TiMgNi catalysts prepared as described in Examples XXIB and XXIIB were used as catalyst components in the polymerization of ethylene (88 ° C, 10 mole% ethylene, triethylaluminum at about 45 ppm calculated as Al, ^ as shown). are shown in Table VI below:

Table VI

Catalyst H_ Productivity Resin properties

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

15 XXIB-3,515 90,750 9.55 270 28,928 104,980 24.6,683 27.8,515 111,940 0.29 10.7 36.8,928 112,260 3.1,119 38.9 20 XXIB-4,515 59 790 0.25 10.9 43.6 928 62 720 1.0 43.6 43.6 XXIIB 515 57 890 1.66 54.9 33.1 928 64 740 6.13 183 29.8 25 XXIB-2,515 238,670 0.65 19.5 30.2,928,271,560 6.7,188 28.1 XXIB-5,3081 175,000 small 30 ^ The experiments at higher amounts of hydrogen were extremely rapid, resulting in a polymer structure that required the experiments to be stopped.

39 71 569

Example XXV

A. TBT, Mg and MgSiFg.6H2O were combined in octane and heated in a reaction vessel equipped with a reflux condenser as described in the previous examples to give reaction products in molar ratios of 1/1 / 0.34 and 1 / 0.75 / 0.128, respectively.

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

10 C. The resulting brown precipitate was separated from the off-reddish-brown liquid and used with TEA to give about 45 ppm Al under standard conditions for polyethylene polymerization (88 ° C, 515 kPa H 2) to give a resin of 107.500 g PE / gTi / h, which the resin is characterized by MI 2.85, HLMI 84.5 and MIR 29.6.

D. The 1/1 / 0.34 reaction product prepared above was similarly activated with isobutylaluminum dichloride in 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 preloaded with butene-1 to give a target density resin at 77 ° C, 207 kpa H 2, ethylene / butene-1-succeed. The resulting resin had a density of 0.9193, MI 1.91, HLMI 60.8 and MIR 31.8.

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

Example XXVI

A. In the following experiments, the Ti / Mg / MgCl 2 reaction products were reacted with a halide component which was gradually added thereto, usually dropwise exotherm to quench its reaction. The reaction was allowed to proceed under ambient conditions for a period of time sufficient to complete the addition, while stirring the reactant 10-30 minutes after the peak temperature had reached (when possible, stirring was carried out).

The solid and liquid components of Ti / Mg / MgCl 2 were slurried together and used in this form). The reactants and their proportions are shown as follows:

Catalyst component, Halide- Molar ratio molar ratio activator

Ti / Mg / MgCl2-6H2O (H2O) 1 / 0.65 / 0.11 (0.66) i-BuAlCl2 2/1 Al / Ti 1 / 0.65 / 0.11 (0.66) i-BuAlCl2 3/1 5 1 / 0.65 / 0.11 (0.66) 1-BuA1Cl2 4/1 1 / 0.65 / 0.11 (0.66) 1-BuA1Cl2 6/1 1 / 0.65 / 0.11 (0.66) EtAlCl2 3/1 1 / 0.65 / 0.11 (0.66) EtBCl2 1.25 / 1 (B / Ti) 1 / 0.65 / 0.11 (0.66) ) EtBCl2 3/1 (B / Ti) 10 1 / 0.65 / 0.11 (0.66) SiCl4 3/1 (Si / Ti) 1 / 0.65 / 0.11 (0.66) SiCl4 6 / 1 (Si / Ti) 1 / 0.75 / 0.128 (0.768) EtAlCl2 3/1 1 / 0.75 / 0.128 (0.768) Et3Al2Cl3 3/1 1 / 0.75 / 0.128 (0.768) i-BuAlCl2 3 / 1 15 1 / 0.75 / 0.128 (0.768) i-BuAlCl 2 6/1 1 / 0.75 / 0.128 (0.768) EtBCl 2 3/1 (B / Ti) 1 / 0.75 / 0.128 (0.768) (CH 3) 2SiCl 2 6/1 (Si / Ti) 1 / 0.75 / 0.128 (0.768) (CH 2 SiCl 6/1 (Si / Ti) 1 / 0.75 / 0.128 (0.768) (CH 3) 2SiHCl 6/1 (Si / Ti) 20 1 / 0.75 / 0.128 (0.768) SiCl 4 3.1 (Si / Ti) 1 / 0.75 / 0.128 (0.768) SiCl 4 6.1 (Si / Ti) 1 / 0.75 / 0.128 ( 0.768) TiCl4 1.5 / 1 (Ti / Ti) 1 / 0.75 / 0.128 (0.768) TiCl4 3/1 (Ti / Ti) 1/1 / .17 (1.02) i-BuAlCl2 3/1 25 1/1 / .17 (1.02) EtAlCl2 3/1 1/1 / .34 (2.04) i-BuAlCl2 3/1 1/1 / .34 (2.04 i-BuAlCl2 6/1 71569 41

Catalyst component, Halide- Molar ratio molar ratio activator

Ti / Mg / MgCl 2 - 6H 2 O (H 2 O) δ 1/1 / 0.51 (3.06) i-BuAlCl 2 3/1 1/1 / 0.51 (3.06) i-BuAlCl 2 6/1 2/1 / 0.17 (1.02) i-BuAlCl2 3/1 2/1 / 0.17 (1.02) i-BuAlCl2 6/1 10 2/1 / 0.34 (2.04) i-BuAlCl2 3 / 1 2/1 / 0.34 (2.04) i-BuAlCl2 6/1 3/1 / 0.51 (3.06) i-BuAlCl2 3/1 3/1 / 0.51 (3.06) i-BuAlCl2 6/1 15

Example XXVII

A. Catalyst samples activated with i-BuAlCl 2 (3: 1 Al / Ti) were used in a series of polymerization experiments, with the results shown in the following Table VII: 71569 42

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As can be seen in the comparison of the molar ratio of Ti / MgCl 2 * 6H 2 O, a peak melt index of 9: 2 (Ti / H 2 O = 1.5: 1) is observed.

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£ I — I * · U) rH * H

3i 3 o x -H 3 3 3 '-' 3 -P CU 3

- ^ 3: θ E

= tj> X E CU 3 rH

Qjr— C X X G E: 3 -H

OS O) I H: 3: 3 en PECECU-r-Hd. > 1

Q ^ -HUrHC tn Φ -PO

3 E -H CD -H X> -P cn 33J «i3 E 3 Τ3

After 31Π.Χ-Η 3 rH £ 3

3 * · 3 · Η -H g rH 3 3: 3 rH

Q °> 1 3 0> i 3 3 Dj: 3 -H

= ~ ωλ; ch-p tn os Op 54 71 569 E. In another large-scale polymerization carried out in the same manner using a Ti / Mg / MgCl 2 catalyst (slurry separated from the supernatant and washed with hexane) in a molar ratio of 1 / 0.75 / 0.128 5 ( 3/1 Al / Ti, ethylaluminum dichloride), hexane-1 was fed to the reactor as a comonomer with ethylene and then butene-1 was substituted to give, as monitored by exhaust gas analysis, ethylene / butene-1 / hexene-1 copolymers and terpolymers during the process. The results are shown in the following Table XIII: 71569 55

M

S

m (N ro ro vd vo (N

2 ro ro ro ro ro ro

E

H σι σι (N <n σ S ......

i_q ro i — f ld tn σ K rs rs ro rs es rs

M

B

M

X

O ro ro -o · o O "S · χ oo t ~~ σ r- r ~ σ X Hl - p SI oooooo

r-H

3 (0

Eh tn σ ro r- oo oo in> σ σ m tt · <3 · ro

Q) ro rs i — I i — I '—I H

, G σ σ σ σ σ σ • Η “* * * * *“ Η ο ο ο ο ο ο ο * Η

G

φ φ -Ρ • h d Μ Λ Q) \ Q) -rt · Η e c c η ο φ φ c G Φ Φ Φ o to = m ω = = e χ λ: -ρ ο Φ Φ 3

X 33 33 CQ

56 7 1 5 6 9

Example XXVIII

The TMMg catalyst prepared according to the examples and activated with isobutylaluminum chloride (3/1 Al / Ti) was also used to prepare other copolymers with different comonomer preloads, as isobutane diluent, at a reactor temperature of 77 ° C, 308 At -377 kPa and with TEA to give 60 ppm Al, with the following results:

Ethylene / 3-methylbutene-1 MI MIR Density 10 1.25 .27, 40, 9488 1/25 28.9 0.9483 1.36 27.9 0.9507 1.55 27.7 0.9497 1.56 27.5 0.9495 1, 87 29.9 0.9496 1.63 28.5 0.9455 15 2.25 28.8 0.9437 1, 46 30.0 0.9428 5.01 30.3 0.9411 1 .59 31.9 0.9400

Isobutylene 0.37 32.4 0.9518 1, 35 29, 6 0.9564 1, 79 31, 1 0.9542 1, 17 31.7 0.9567 4, 20 30, 10 0, 9582 3, 30 32 .9 0, 9557

The polymerization or copolymerization of other alpha-olefin monomers such as propylene, 4-methylpentene-1, alkyl acrylates and 25-methacrylates and alkyl esters can be carried out in the same manner.

The following comparative experiments were also performed: 71569 57

Comparative Examples A. In the same reaction vessel used in other preparations, TBT, Mg and anhydrous MgCl 2 in octane were combined in a molar ratio of 2/1 / 0.34 and heated to reflux for 15 minutes without indication of reaction. Anhydrous MgCl2 remained insoluble. See. see also Example IB above.

B. To the same system was added free water in an amount corresponding to a Mg / MgCl 2 .6H 2 O ratio of 1 / 0.34 10 in one addition, but no change occurred.

C. TBT and Mg were combined in a molar ratio of 2/1 in octane and heated to reflux. While the yellow color became somewhat more intense, no reaction occurred.

D. An amount of free water corresponding to a Mg / MgCl 2 .6H 2 O ratio of 1 / 0.34 was added to the previous system C. A small amount of a pale yellow precipitate formed, indicating hydrolysis of the titanium compound, but 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 was completely dissolved, the solution became cloudy and somewhat viscous when heating at reflux was continued for 3 hours, but it clarified and settled to a cloudy yellow liquid and a harder precipitate overnight. An additional experiment at a molar ratio of 1 / 0.128 produced a clear golden yellow liquid when heated to reflux for only 16 minutes. At a molar ratio of 1 / 1.17, foaming and the formation of a thick creamy colored gel terminated the reaction after 45 minutes. See. to Example VII above.

Claims (10)

71569 A process for the polymerization of 1-olefins alone or in combination with at least one copolymerizable monomer 5, under polymerization temperature and pressure conditions with an olefin polymerization catalyst system, characterized in that the catalyst system comprises a mixture of a first and a second cocatalyst, the first cocatalyst the boron or organoaluminum compound and the second cocatalyst are a halide-activated intermetallic compound obtained as a reaction product when 1) a polymeric transition metal oxide alkoxide in which the transition metal is titanium or zirconium and is prepared by partial hydrolysis of the transition metal alkoxide wherein the water is reacted in the form of a hydrated salt such as an hydrate of an aluminum, cobalt, iron, magnesium or nickel salt or in the form of a hydrated oxide, preferably a silica gel, and 2) a reducing metal having a higher an oxidation potential other than said transition metal and which is magnesium, calcium, zinc, aluminum or a mixture thereof has been reacted with each other. Process according to Claim 1, characterized in that the molar ratio of transition metal to water is about 1: 0.5 to 1: 1.5. Process according to Claim 1 or 2, characterized in that the transition metal and the reducing metal are present in a molar ratio of about 0.5: 1 to 3: 1. Process according to one of Claims 1 to 3, characterized in that the first cocatalyst, calculated as metal, and the second cocatalyst, calculated as metal, are present in a molar ratio of approximately 3: 1 to 25: 1. Process according to one of Claims 1 to 4, characterized in that at least one of the following is used as halide activator: alkylaluminum halide silicon halide, alkyl silicon halide, titanium halide or alkyl borohalide. Process according to one of Claims 1 to 5, characterized in that the cocatalyst is an organoaluminum or organoboron compound, preferably triethylaluminum or triethylborane. 7. Polymerization catalyst system for the polymerization of 1-olefins alone or in combination with at least one copolymerizable monomer, characterized in that it comprises a mixture of the first and second cocatalysts, the first cocatalyst being an organic aluminum or organoboron compound and the second cocatalyst being halide activated an intermetallic compound which is a reaction product of a polymeric transition metal oxide alkoxide and a reducing metal having a higher oxidation potential than the transition metal, wherein the transition metal is titanium or zirconium, the reducing metal is magnesium, calcium, zinc, aluminum or mixtures thereof, and wherein the polymeric the transition metal oxide alkoxide is the product of the controlled partial hydrolysis of titanium or zirconium alkoxide. Catalyst system according to Claim 7, characterized in that at least one of the following is used as the halide activator: alkylaluminum halide, silicon halide, alkyl silicon halide, titanium halide or alkyl borohalide. Catalyst system according to Claim 7 or 8, characterized in that the transition metal 30 and the reducing metal are present in a molar ratio of about 0.5: 1 to 3: 1. Catalyst system according to one of Claims 7 to 9, characterized in that the first cocatalyst, calculated as metal, and the second cocatalyst, calculated as metal, are present in a molar ratio of 3: 1 to 25: 1. 71569