DK147796B - PROCEDURE FOR THE PREPARATION OF A SOLID CATALYTIC COMPLEX FOR USE BY POLYMERIZATION OF ALFA OLEFINES - Google Patents

Description

147796

The present invention relates to a process for preparing a solid catalytic complex for use in the polymerization of <X-olefins at a pressure of atmospheric pressure to 100 kg / cm, the polymerization taking place in the presence of a catalytic system consisting of an organometallic compound and the solid catalytic complex.

It is known that catalytic systems containing a transition metal derivative and an organometallic compound can be used in low pressure polymerization of olefins.

It is also known from British Patent Specification No. 1 140 649 that one can use as a transition metal derivative in the above catalytic systems a solid obtained by reacting a halogenated transition metal derivative with an oxygen-containing compound of a divalent metal such as magnesium. The catalytic systems thus obtained are very active in comparison with those where the halogenated transition metal is used alone.

Belgian Patent No. 791,676 describes catalytic systems having a component obtained by reacting: (a) an oxygen-containing organic compound of a metal, such as a magnesium alcoholate or phenolate, (b) an oxygen-containing organic transition metal compound, and (c) an aluminum halide.

Using such catalytic systems, it is possible to produce, at high catalyst activities, high average molecular weight polyolefins and a very good impact strength.

However, the preparation of the catalytic systems according to the above-mentioned Belgian patent specification 791 676 has certain disadvantages due to the use of the oxygen-containing organic compounds (a) which are unstable and / or subject to immediate hydrolysis. These compounds are also exceptionally dangerous to handle. Thus, they must be stored and transported under inert conditions and treated with care. Furthermore, the catalytic compounds produced therefrom often have poor flow properties as they may have too fine granulometry.

It has now been found that catalytic systems with the same advantages as the above can be prepared without the use of an oxygen-containing organic compound (a) from readily available products.

The invention thus relates to a process for the preparation of a solid catalytic complex for polymerization of olefins at a pressure from atmospheric pressure to 100 kg / cm 2, the complex comprising 4- a catalytic system which further comprises an organometallic compound (component B) of a group I-III metal of the periodic table. The solid catalytic complex (component A) contains magnesium, aluminum and halogen as well as a transition metal from Group IVa, Va or Via in the periodic table.

The process of the invention is characterized by reacting: (1) metallic magnesium, (2) a hydroxyl group-containing organic compound containing at least one OH group attached to a C or Si atom (hereinafter referred to as "compound (2)"), (3) an oxygen-containing organic compound of the general formula [TrO ^, (OR ')] ^, where Tr is a group IVa, Va'or metal

Via in the Periodic Table, R 'is a hydrocarbon group having 1-18 C atoms, x'> 0 and y> 0, where 2x '+ y is the valence of the metal Tr and m represents an integer (hereinafter referred to as " compound (3) "), (4) an aluminum halide of the general formula AIR X wherein R is a hydrocarbon group having 1-20 C atoms, X is a halogen atom, and 0 <x <3 (hereinafter referred to as" compound ( 4) "), and optionally (5) a further compound selected from oxygen-containing organic compounds of a group of Hib or IVb metal in the periodic table.

The metallic magnesium (1) used to prepare the catalytic component A may be in any physical form suitable for chemical reactions, e.g. in the form of powder, granules, foils, ribbons or chips. The qualities usually used for conducting organic reactions can be used.

Compound (2) is preferably selected from compounds containing 1-12 carbon atoms per minute. hydroxyl group, and most preferably 1-6 carbon atoms per hydroxyl group. These compounds may be straight-chain or branched aliphatic compounds or alicyclic saturated or unsaturated compounds, aromatic and heterocyclic compounds and their substitution products. In particular, these may be alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkylaryl and arylalkyl compounds.

Particularly suitable compounds (2) are monovalent and polyhydric alcohols containing 1-12, preferably 1-6, carbon atoms in the molecule. They may be saturated or unsaturated, straight or branched chain aliphatic or alicyclic alcohols. They can also be aromatic and heterocyclic alcohols. Other suitable compounds are hydrocarbyl silanols, wherein the hydrocarbyl groups have a number of carbon atoms similar to that defined above.

Thus, among useful compounds (2) are mentioned: Saturated or unsaturated straight or branched chain mono- or polyhydric aliphatic alcohols, such as methanol, ethanol, butanol, isobutanol, isopentanol and octanol, allyl alcohol and ethylene glycol; substituted or unsubstituted saturated or unsaturated monovalent alicyclic alcohols, e.g. cyclopentanol and cyclohexanol as well as 3-cyclopentan-1-ol; substituted or unsubstituted mono- or polyhydric aromatic alcohols, e.g. phenol, benzyl alcohol, o-, n- and p-cresol, xylenes, resorcinol and hydroquinone, as well as ef- and (i-naphthols; heterocyclic alcohols, for example 3-hydroxy-piperidine, and alkyl and arylsilanols, f. eg trimethylsilanol and triphenylsilanol.

Among the metals (Tr) in compound (3), titanium, zirconium, vanadium and chromium are preferred. The best results are obtained with titanium. The hydrocarbon groups bonded to the metal Tr via oxygen may be of any nature. They contain 1-18 carbon atoms, preferably 1-10 carbon atoms. The best results are obtained with groups containing 1-6 carbon atoms. The hydrocarbon groups are preferably straight or branched chain alkyl, cycloalkyl, arylalkyl, aryl or alkylaryl groups.

147796 5

Compounds (3) are represented by the general formula [Tr 0χ, (OR ') ym / wherein Tr represents a metal of group IVa, Va or Via in the periodic table, R' represents a hydrocarbon group as defined above, x ' and y is any number such that x1> 0 and y> 0, and 2x '+ y is equal to the valence of the metal Tr, and m represents an integer. It is preferred to use compounds (3) wherein 0 <x '<1 and 1 <m <6.

Among the compounds (3) which can be used according to the invention are mentioned:

Alkoxides, e.g. Ti (OC2H5) 4, Ti (OnC3H7) 4, Ti (OnC4Hg) 4,

Ti (OiC3H7) 4, Ti (O-tert.-C4H9) 4, Ti (OiC4Hg) 4, V (OiC3H?) 4 and Zr (OiC3H7) 4? phenolates, e.g. Ten (0CgH, -) 4; oxyalkoxides, e.g. (VO (OiC3H7) 3; condensed alkoxides, for example Ti2O (OC3H7) g, and enolates, for example titanium acetylacetonate.

The use of compounds (3) containing several different hydrocarbon groups is also possible, as well as the use of several different oxygen-containing organic compounds of one and the same metal as well as several oxygen-containing organic compounds of different metals.

Compound (4) has the general formula AIR wherein R represents a hydrocarbon radical of 1-20 carbon atoms, preferably 1-6 carbon atoms, X represents halogen, and 0 <x <3. Preferably, R is a saturated aliphatic, saturated alicyclic or aromatic group. .

The best results are obtained when R represents alkyl, X represents chlorine, and 0 <x <2.

Examples of aluminum halides which can be used in accordance with the invention include A1C13, Al (CH3) 2Cl, A1 (C2H5) 2C1, Al (C2H5) Cl2, A1 (C3H7) 2P, Al (iC3H7) 2Cl and Al2 ( C2H5) 3Cl3 ·

It is not always necessary that the connection (4) be a single connection. In particular, in combination or successively, a compound of formula AlX3 and a compound of formula A1R3 can be used.

Each of the compounds (2), (3) and (4) can, when the operating conditions are suitable, be used in solid, liquid, in the form of a solution or in the form of a vapor or gas.

It is preferred to prepare the catalytic component A in a liquid medium, if desired in the presence of an inert diluent which is preferably a diluent in which at least one of the reactants is soluble. Virtually all commonly used solvents in preparative organic chemistry can be used. However, it is preferred to use alkanes and cycloalkanes having 4-20 carbon atoms, e.g. isobutane, n-pentane, n-hexane, cyclohexane, methylcyclohexane or dodecaneme. When a diluent is used, it is preferred that the total concentration of the dissolved reactants be greater than 5% by weight, preferably greater than 20% by weight, based on the diluent.

As regards the order of addition of the reactants, they are preferably added to magnesium in the numerical order, i.e. first compound (2), then compound (3) and finally compound (4) or compound (2) and (3) together and then compound (4) or compound (2) and then compound (3) and (4) together.

In a preferred embodiment, magnesium is mixed with compounds (2) and (3) and the mixture is heated and matured. The heating and maturation preferably takes place under reflux and / or elevated pressure, so that the reaction agent is liquid. When the reactants are solid, they are preferably suspended or dissolved in a diluent as defined above, or melted if this does not cause decomposition. If one of the reactants is liquid at the heating temperature, it can be used as the reaction medium. In any case, the mixture may be in the presence of a liquid diluent. The heating temperature depends on the compounds (2) and (3) and is preferably 30 - 150PC. The duration of heating and maturation is not critical and it is usually between JO minutes and 15 hours, preferably 1-6 hours.

In carrying out this method, the heating and maturation can be accelerated by the addition of several well known substances capable of reacting with metallic magnesium to form an addition product such as iodine, mercury (II) chloride, xylene, alkyl halides and polar compounds such as organic acidic esters and organic acids.

After completion of the heating and maturation reaction, low-boiling compounds, if still present, are removed preferably by distillation. As a rule, the matured mixture thus obtained is a homogeneous liquid substance. The thus obtained matured mixture is then contacted with compound (4), preferably in the presence of an inert diluent of the kind set forth above. The duration and temperature of this reaction is not critical and the temperature is generally below 200 ° C, preferably 0 - 60 ° C. The duration is usually 1-8 hours, preferably 2-4 hours. When successively a compound of formula AIX ^ (compound 4a) and a compound of formula AIR ^ (compound 4t>) are used in the reaction as explained above, the reaction conditions are analogous to the conditions when a single compound (4) is used. However, the first reaction with compound (4a) is usually carried out under reflux for from 30 minutes to 6 hours, preferably 1-3 hours.

It is advisable that the presence of oxygen and water be carefully eliminated in the preparation of the catalytic complex.

The rate of addition of the reactants is also not critical.

It is advisable that it is not so high as to obtain a sudden heating of the reaction medium due to an excessively rapid reaction. The reaction may be carried out continuously or non-continuously.

Furthermore, in practice, compound (3), when held in liquid form, is frequently capable of dissolving the reaction product between magnesium and compound (2). In that case, the use of an inert diluent can be avoided. However, when this is not the case, and since it is preferred that the matured product is contacted with liquid (4) in liquid form, it is also possible to use another oxygen-containing organic compound of a group of Hib or IYb metal, preferably silicon and . preferably aluminum which is liquid and capable of dissolving the first, i.e. the oxygen-containing organic compound of a metal (Tr) (compound (3)). As far as the structure of the other oxygen-containing organic compound is concerned, it can be defined in the same way as compound (3), except that the incoming metal is from group Hib or ivb, and as mentioned it is called compound (5). Specific examples of oxygen-containing organic compounds useful as compound (5) are AKOC H 2) and Si (OC 4 H 9) 4.

The preferred amounts of compounds (2), (3) and (4) can be stated as follows:

The total amounts of metallic magnesium (1) and compound (2) are such that the mg / compound (2) ratio is less than 1 gram atom per liter. mol, preferably below 0.5 g / mole. The best results are obtained when the ratio is close to 0.3 g / mole. The total. amount of compound (3) is such that the atomic ratio Mg / metal (Tr) is 20 - 0.05 g.at./g.at., preferably 5 - 0.2 g.at./ g.at. The best results are obtained when this atomic ratio is close to 0.5.

Compound (4) is used in such amounts that the atomic ratio of magnesium to aluminum in compound (4) is 10 - 0.01 g.at./g.at., Preferably 1 - 0.05 g.at./g. .to. For best results, close to 0.2. However, when the preparation of the catalytic component A is carried out by successive use of a compound IVa and a compound IVb, the atomic ratio of magnesium to aluminum in compound (4a) is preferably 4 - 0.02 g.at./g.at. and compound (4b) is used such that the atomic ratio of aluminum in compound (4b) to metal (Tr) in compound (3) is preferably higher than 0.30 g.at./g.at.

Finally, when using a compound (5) as defined above, the amounts of magnesium and compound (5) are preferably such that the ratio of magnesium to compound (5) is 0.01-100 g.at / mol, preferably 0. 1 - 10, and most preferably 0.5 - 1.5 g.at./mol, to achieve the best results. The catalytic complex prepared according to the invention is solid. It is insoluble in alkanes and cycloalkanes which can be used as diluents. It can be used in the polymerization of tx olefins in the form in which it is obtained without first separating it from the reaction medium.

When the reaction medium is liquid, it is possible, if desired, to separate the complex, e.g. by filtration, decanting or centrifugation.

After separation, the catalytic complex can be washed out, eliminating excess reactants that still adhere to the complex. For this leaching, an inert diluent, e.g. one of the above as constituents of the reaction agent such as alkanes and cycloalkanes. After the leaching, the catalytic complex can also be dried, e.g. by passing a dry stream of nitrogen over it or it can be dried in vacuum.

The formation mechanism of the catalytic complex prepared according to the invention is not fully understood. Elemental analysis of the catalytic complexes after separation and leaching shows that they are chemically combined complexes, ie. products of chemical reactions, and not results of a simple mixture or of adsorption phenomena.

After the outgassing, the catalytic complex can be stored in powder form. Two important advantages of these catalytic complexes are their extremely good storage stability and the limited loss of metal (Tr) during the possible leaching steps: When metal (Tr) is titanium, more than 80% by weight combined in the catalytic residue usually remains in the complex, which is why the purification treatment of the wash liquids is greatly reduced.

The catalytic complex, whose exact nature is not completely understood, contains magnesium, metal (Tr), aluminum and halogen in variable amounts. Most often it contains per. kg 10 - 150 g magnesium, 20 - 250 g metal (Tr), more than 10 g aluminum and 200 - 700 g halogen. It is characteristic of a high 2 specific surface area, most often above 50 m / g, and 2 can be as high as 300 - 400 m / g.

The catalytic system for use in the polymerization of <X-olefins also comprises an organometallic compound which acts as an activator, namely an organic compound of a group I - III metal of the periodic system, e.g. an organic compound of lithium, magnesium, zinc or aluminum. The best results are obtained with organic aluminum compounds.

It is possible to use fully alkylated compounds whose alkyl chain contains 1 to 20 carbon atoms and may be chained or branched, such as n-hutyllithium, diethylmagnesium, diethyl zinc, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, n-decyl aluminum, tetraethyl tin or tetrabutyl tin. However, it is preferred to use trialkylaluminum compounds having 1-10 carbon atoms in the alkyl chain which may be straight or branched.

It is also possible to use alkyl metal hydrides in which the alkyl groups also contain 1-20 carbon atoms, e.g. diisobutylaluminum hydride or trimethyltin hydride, and alkyl metal halides in which the alkyl groups also contain 1-20 carbon atoms, e.g. ethyl aluminum sesquichloride, diethyl aluminum chloride or diisobutyl aluminum chloride.

Finally, it is also possible to use organoaluminum compounds obtained by reacting trialkylaluminum or dialkylaluminum hydrides, whose radicals contain 1-20 carbon atoms, with diolefins containing 4-20 carbon atoms, and especially compounds known as isoprenylaluminum compounds.

147796 11

The catalytic complex prepared according to the invention can be used for polymerizing olefins with terminal unsaturation, the molecule of which contains 2-20, preferably 2-8 carbon atoms, such as ethylene, propylene, butene-1, 4-methyl-pentene-1, hexene-1 or octene-1.

The complex prepared according to the invention is particularly suitable for the preparation of ethylene homopolymers and copolymers containing at least 90 mole percent, preferably 95 mole percent ethylene.

The polymerization can be carried out by any suitable method. In particular, it can be carried out in solution or in suspension, in a solvent or hydrocarbon diluent or in gas phase. If the process is carried out in solution or in suspension, solvents or diluents of the same kind used to prepare the catalytic complex can be used. These are preferably alkanes or cycloalkanes such as butane, pentane, hexane, heptane, cyclohexane, methylcyclohexane or mixtures thereof. It is also possible to carry out the polymerization in the monomer or one of the monomers, held in liquid form.

2

The polymerization pressure is between atmospheric pressure and 100 kg / cm 2, preferably 1.5 - 50 kg / cm. The temperature will generally be 20 - 200 ° C. When polymerizing an olefin with terminal unsaturation, as defined above, the temperature is especially 50 - 120 ° C when the polymerization is carried out in suspension and 120 - 150 ° C when performed. in solution. The polymerization can be performed batchwise or continuously.

The catalytic complex prepared according to the invention and the organometallic compound can be added to the polymerization medium separately.

However, if desired, the components can be contacted at a temperature of -40 - 80 ° C for up to 2 hours before being introduced into the polymerization reactor; It is also possible to contact them in several steps, or a portion of the organometallic compound may be added prior to introduction into the reactor, or several different organometallic compounds may be used.

The total amount of organometallic compounds is not critical. It can usually be 0.02 - 50 mmol / liter solvent, diluent or reactor volume, preferably 0.5 -5 mmol / liter.

The amount of catalytic complex used is usually determined taking into account the content of transition metal (Tr). The amount is usually such that the concentration is 0.001 - 2.5, preferably 0.005 - 1.5 mg.at. metal / liter of solvent, diluent or reactor volume.

The relationship between the quantities of the two components is also not critical. It is usually such that the ratio of organometallic compound to transition metal compound expressed in moles / g.at. is above 1, preferably above 10.

This average molecular weight indicated by the melt index of the polymers produced can be regulated by the addition of one or more molecular weight modifiers to the polymerization medium, e.g. hydrogen, diethyl zinc, diethyl cadmium, an alcohol or carbon dioxide.

The density of the homopolymers obtained by the polymerization can also be controlled by adding to the polymerization medium an alkoxide of a group IVa or group Va metal in the periodic table. Thus, it is possible to produce polyethylenes having a specific density between the density of polyethylenes produced by high-pressure polymerization and the density of the classical HD polyethylenes.

Among the alkoxides useful for controlling density, titanium and vanadium alkoxides having 1-20 carbon atoms in the alkoxy groups are particularly effective. These alkoxides are, for example, Ti (OCH3) 4, Ti (OC2H5) 4, Ti OCH2CH (CH2) 2 4, Ti (OCgH17) 4 and Ti (OClgH33) 4.

The catalytic complex prepared according to the invention makes it possible to produce polyolefins with productivity as high as in the catalytic systems described in the above-mentioned Belgian patent no. 791 676. In the homopolymerization of ethylene, the productivity is expressed in grams of polyethylene per liter. grams of catalytic complex usually over 10,000 and often over 20,000. The activity calculated on the amount of transition metal present in the catalytic component A is also high. By homopolymerization of the ethylene, the activity is expressed as grams of polyethylene per liter. grams of transition metal usually above 50,000 and in many cases over 100,000. In the most favorable cases, it is over 1 million.

For this reason, the content of catalyst residues in the polymers formed is extremely low. In particular, the residual content of transition metal can be extremely low. It is the transition metal derivatives that are particularly troublesome in the catalyst residues due to certain colored complexes which they form with the phenolic antioxidants usually included in polyolefin mixtures.

It is for this reason that the polymers prepared by the well known processes for polymerizing olefins by catalysts containing a transition metal compound must be purified from catalyst residues, e.g. when treated with alcohol. When using the complexes made according to the invention, the content of cumbersome residues is so low that it is possible to avoid the purification treatment, which is a costly operation considering the consumption of raw materials and energy and the considerable capital investment they entail.

Like the polyolefins prepared by the method of Belgian Patent No. 791,676, the polyolefins made by the complex made according to the invention are characterized by a remarkably high impact strength. Thus, polymers of ethylene may have a melt index of approx. 5, and an impact strength measured by the Izod test of approx. 10 kg cm / cm notch. Polyethylenes having the same melt index made using known reactive catalyst systems have a impact strength measured by the same sample not exceeding about 10%. 6 kg cm / cm notch.

The polyolefins obtained with the complex according to the invention can generally be used in any molding technique. Thus, they can be used for extrusion, injection molding, injection blowing or calendering. They can advantageously be used in areas where

U779S

14 Good impact strength is required, especially for the manufacture of boxes, barrels, pallets and bottles.

Finally, the catalytic complexes produced are excellent as catalyst components in the preparation of polymers suitable for blow molding. As a rule, polymers to be formed by blow molding are required to have a broad molecular weight distribution. The molecular weight distribution can be approximated by the ratio of melt index under heavy load (HLMI determined under condition E of standard ASTM D-1238) and melt index (MI determined under condition F of standard ASTM D-1238), namely the HLMI / MI value. When using the catalyst complexes prepared by the process of the invention, a polymer having an HLMI / MI value greater than 70 suitable for blow molding can also be prepared. Thus, it has been found that the catalyst complexes are suitable for the preparation not only of injection molding polymers but also blow molding polymers.

In short, with the catalyst complexes prepared according to the invention, polymers can be obtained in the same economical manner with the same basic advantages as polymers obtained according to Belgian Patent No. 791,676.

However, the significant technical advance of the invention is that the catalytic systems can be made in a much simpler manner and that a complicated magnesium compound which requires strict control or monitoring during manufacture, processing and quality standards is not used. Furthermore, the reaction of magnesium with compounds (2) and (3) is often exothermic. The heat of the reaction can thus be recovered, thereby saving energy costs in the other steps in the preparation of the complex. In contrast, the mixture of the magnesium compound and the transition metal compound is usually heated to high temperatures by the process of Belgian Patent No. 791,676.

15 147796

The invention is further illustrated by the following examples.

EXAMPLES 1 - 3

Eremstilling_af_de_faste_katal2tiske_komj) lekser_ (KOIN £) onent_A)

Example 1a Into a 1000 cm 2 flask equipped with a stirrer was placed 21 g (0.45 mole) of anhydrous ethanol and 3.7 g (0.15 mole) of metallic magnesium powder and 102 g (0.3 mole) of titanium tetrabutylate were added [Ti (0-n- ° 4H9 ^ 4 ^ · The mixture was stirred at reflux at 130 ° 0 for 2 hours excluding water or steam, removing hydrogen formed by the reaction. Low-boiling distilled off at 90 ° C and removed from One remaining mixture (1) was cooled to 60 ° C.

Then 200 ml of n-hexane was added to the mixture and 95 g (0.75 mol) of ethyl aluminum dichloride [AliCgH 2 C 2] was added dropwise to the mixture over 4 hours at 45 ° C, then the reaction mixture was stirred at 60 ° C for 1 hour. Then, n-hexane was added to the reaction product which was washed out by decanting, i.e. The leaching was performed by repeating the following steps: Stirring the mixture, standing, removing the supernatant and adding fresh n-hexane to the residue until no chloride ions in the supernatant could be determined. The volume of the resulting suspension was adjusted to 500 ml by the addition of n-hexane.

Ted determination of the titanium content of the suspension thus formed with hydrogen by a colorimeter as described by G.O. Muller, Praktikum der Quantitationen Chemical Analysis (1957) Ρ · 243, found that 10 ml of the suspension contained 5.0 mmol of the titanium compound. The supernatant from the suspension was removed and n-hexane was removed by drying the residue in the presence of nitrogen to give 72 g of a reddish brown powder in which the titanium content was found to be approx. 15.9% by weight.

Example 2a

Proceed as in Example 1 except that after cooling to 60 ° C the remaining mixture (1) was diluted with 400 ml of 16-n-hexane. Then 100 g (0.75 mole) of aluminum chloride was gradually added to the flask contents so that the temperature remained below 50 ° 0. Then the temperature was raised and the reaction mixture (2) was stirred at reflux at 72 ° C for 2 hours. The product was then washed and dried as in Example 1a. 20 g of a white powder, whose titanium content was 4.50% by weight, were isolated.

Example 5a

Proceed as in Example 2, and after the reaction mixture (2) was stirred, quenched at 72 ° C for 2 hours, cooled to which was added dropwise 44 g (0.385 mol) of triethyl aluminum [Al (C at 45 ° C for 4 hours. After stirring the mixture for 1 hour at 60 ° C, the product was washed and dried as in Example 1a. 77 g of a light brown powder were obtained, the titanium content of which was 18.6% by weight.

Polymerization of Ethylene (Example 1b) 3

The internal atmosphere of a 1600 cm stainless steel autoclave equipped with electromagnetic stirrer was replaced with nitrogen, then 1 liter of n-hexane was placed in the autoclave and the internal temperature was adjusted to 90 ° 0. Then 0.98 g (5 mmol) of triisobutyl aluminum [ Al (1C 3 Hg) 2] and 20 mg of the dry powdered catalytic complex A obtained in Example 1a above.

The internal pressure in the autoclave was adjusted to 1 atmosphere and hydrogen was introduced under a partial pressure of 7 atmospheres and ethylene under a partial pressure of 12 atmospheres in the autoclave.

Then, the polymerization was carried out under ethylene conduction so that the total pressure in the autoclave was maintained at 20 atmospheres.

After 2 hours, the supply of ethylene was stopped and the unreacted gas was vented from the autoclave. The resulting polyethylene was taken out, separated from the solvent by filtration and dried. Thus, 330 g of a polyethylene (PE) having a melt index (MI) of 5.8 g / 10 min were obtained, an apparent density (AD) of 0.39 g / cm 2, a density (D) of 0.965 g / cm and a impact strength of the Izod test (IZ) of 13 kg cm / cm.

17 147796

Example 2b

Example 1b was repeated except using a 2.2 liter autoclave and adding 0.91 g (4.6 mmol) of Al (1C 2 Hg) 2 and 6.9 milligrams of the dry powdered catalytic component A obtained in Example 2a above. The hydrogen partial pressure was 6.7 atmospheres and a total pressure of 20 atmospheres was maintained for 2 hours. 161 g of PE with a MI of 2.5 g / 10 min were obtained. and an IZ of 25.2 kg cm / cm.

Yield PE / mg li: 540 grams.

HIMI / MI ratio for PE: 28.

Example 5b

Proceed as in Example 2b, however, using 0.90 g (4.5 mmol) of Al (C ^Hg) og and 24.9 mg of the dry powdered catalytic component A obtained in Example 3a. The following results were obtained: 258 g PE with MI 8.3 g / 10 min, AE: 0.35 g / cm 2, E: 0.964 g / cnr 5 and IZ: 5.9 kg cm / cm 2.

Yield PE / mg Ti: 56 g.

HLMI / MI ratio for PE: 29.

EXAMPLE 4 (Example 4a)

Example 1 was repeated, however, using 8.6 g (0.27 mol) of methanol; 1.95 g (0.08 mol) of magnesium powder; 109 g (0.32 mol) Ti (O-nC 2 Hg) 2; 0.21 g of iodine. The mixture was stirred at reflux at 120 ° for 3 hours, treated as in Example 1a except 220 ml of n-hexane and 71 g (0.40 mol) of Al whose titanium content was 16.7% by weight.

Example 4b (? Olymerization_of_ethylene)

Ethylene was polymerized as given in Example 1b using 22 mg of the dry catalytic component prepared in Example 4a. 350 g of PE were obtained with MI 1.5 g / 10 min, AB: 0.40 g / cm 2, E: 0.964 g / cm 5 and 1Z: 48 kg cm / cm 2.

EXAMPLE 5

The solid catalytic component A was prepared in the same manner as in Example 1a except that ethanol was used instead of 0.45 moles of n-butanol and 0.4 g of iodine was added to the mixture with stirring and stirring at 120 ° C. 3 hours. The distillation was carried out at 140 ° C.

81 g of a thin powder with a titanium content of 15.5% by weight were isolated.

The polymerization conditions were the same as in Example 1h. 310 g of PE were obtained with MI 6 g / 10 min, AD: 0.39 g / enr, D: 0.965 g / cm 2 and IZ: 10 kg cm / cm.

EXAMPLE 6

The activity changes after different periods were examined for the catalytic components A prepared according to Examples 1a and 5.

The catalytic components A were stored under the conditions set out in Section 1 for a predetermined period, and using the stored catalyst, a homopolymerization of ethylene was carried out under the same conditions as described in Example 1b.

The results are shown in Table I below, which shows that the catalytic systems in question have a very good activity which does not decrease during storage.

19 147796 H W) θ '

Q) d M

H H '' HH o o o o

<D H O O O O

• r O O m Ln • -P * * * * H 01 CO C "C" ΙΛ 5 r v— v— g a> 6

CD 'H

X — s g --- o

g H H tiD

CD Hί H CD d

H m M h -H

• Η · Η (S HH O O O O

Η H 0 0 H O O O O

> s Η h o oo tn tn HH · η · · · 0 g O Η M [> - CO t- tn ί> Η Η Π g ^^

O Π3 CD g CD

t ^ a fh bfl · Η (Μ Ή ti ®H _ 'ti £ JC \ J ~ HØ W) g Η Η H ti

8>} {D EH

Blil-P +3 H O O O O

µ-ΡΉ Hri o o o o

øøøø h o m o O

H> 5 · Η

Q Η Η Π CQ CO CO CO CO CO

f> oij gø i- i- ·> - * - • H ft 0 0 H ti T- S4

X ttDO <H

^ -

!- IN ISLAND

I Λί W) arrow Fl ti

(H || EH

pq I -PH O O O O

<J I Η H O O O O

^ I ø H in O tn in +3 · · · · ø ra co c— co in ijD S f- v- v- i- H ø t-q H Vi S +3 rt ® O I 0 "øf! HH g Π

-Day -P Beer W) H

g O 5jD Η H cs3 ft ttOH Lake H tø) £ fto ØH ra o >> æ g g Ή g h -p hh g h g ® -p h up> ø increase raggø 0 h

Smh h ho ce ^ tgn ^ H h xg w> go g m o 0 0 g m h C h e c 0 0 m, n g g h 1, ¾ Η H ft O ΗΛΉΗ Η H ra

Scratch g rapsj o 1 h _ «g g g i hh w) h g ^ ngngg-H w) S ω μη o o ra rank ftg o o fi

p> 3 H 'H g ra η H ft g m' H

.g HH HH HCS> 3Hg H Hm C tftj 00 øm hh ghog ø (uh μη g Η!> H g 0 mg tn h> 0 P? hh tøw · ^ η ηh gg Hh hjsg gi bh HH »go sg« Η ^ eh ft The Girl MHngftra eh ft o ti 0

43 H

, ¾ ø. 0 ra η H ra g h g h iM ° g h 0 h ø g g g s> 3 g H 1- v- -r- m h o ra · 00 g ft g ω

H g I1H

g o h <h O

. Μ Ή Η K

EXAMPLE 7-29

Using the catalytic components obtained in Examples 1a - 3a and 5, ethylene was copolymerized at 80 ° C for 2 hours with propylene or butene-1 in the amounts set forth in Table 2 below and under the polymerization conditions set forth in Example 1¾. Le results obtained are shown in Table 2.

Le catalytic components A are further prepared as set forth in Examples 2a and 3a using compounds (2) other than ethanol. Specific conditions for preparation are shown in Table 3 below.

Analogously to Example 2b, ethylene has been polymerized for 2 hours with triethylaluminum and dry powdered catalytic components A obtained in Examples 12a - 29a, and the polymerization conditions and results used are shown in Table 4 below.

- 21 I co 147796 NS *> 11 H O tr \ 00 C— * 0 ^ ^ ± 4 ___ 'c — c CC \ φ- VO E ~ - 00 · Φ S φ φ Φ "V-

Ro σ »cn crt cn oa \ r« r> t «fv

taO O O O O O

C-c co o cn o S Φ- ia Φ-

R O ·> * · ·> I I

<aj ^ O O O

Tao

-—- <aj

"7 -P

£ £ • H 117

S σι co to. t- oa S

L | r »* n r. *» O

S O CM Ό CO 00 R

^ s \ o

W) £ M

__ ω ————— ^ _ d nrf +3 om

cd o O O O O · Η R

-p OOOOO -P -P

• H ^ 00 CO 00 O cd> 3

f> cm · · · · · m H

H W O CQ 00 C ~ - 00 · Η Cd

+3 CM V- t- T- T- P -P

Jxj <D ce

S M

· - 'ϊ> 3

p H taO

cd d £ o g i- -s- i- CD CD R ·

R O I I I Η H P

cm in CD ££££> »>» £ R

| o cd cd cd R R s RI -PS-P-P-POO R £

Hl P o d d £ P P .o

RI -ajORRR RR £ R

<J | I i - CD -P

S 1 £> -¾

CD · ^ CD CD

practice CO H 0)

(D O'- '*> & P

H d φ- CM T- C— O

ijOO CO v- t— v IA -P H5

fj £ P

æ O taO ce ω g a ____R · Η

M -P

3> 3 "P

| p M w d-P ^ -v cd

CD HCM C- CO C- 00 φ- P P

taO CQ S Λ Λ n · * «* R CD

0 R o φ- VO LO Φ CM £ -Ρ

p -ρ \ 3 R

ti Ρ tao „07 l ^ cdAJ £ -P-L .rer - s ω £ ° 3 1 CD £ £ • h m o 3

PH S

cd CD · o m tao m on • HdAirQRRRR, 2

p * H © T-r-v-r - * - R S

CD -P CD> i

g 0 · H

l ?, R tao Φ O

H ran H R

o d R 5P o ROR__g o <jj -p s ω cd. ra-pH m • H £ {rH / • —a ✓ — v -p cd r cd cd cd cd cd cd t-cm> 3 d -P r- T- t- t- T- ^ V_ ^ H om . cd RØ tao -p S 07 H cd o pr M pj R R__ • m P4 c- co σ \ o v- H t- T-

22 U779S

Λ1Ν Μ.

Η -Ρ Ο Ο m 00 Ο ν 00 Ον- Ο C— Μ ρ οο m tn m tn mm ιο to mm cn cm -φ c ~ - in m tJ Pi - - - - -------- - - - - Sp min -Φΐη «φιο 1φιο mm inr- -Φ ιο> φ tn vo cm • ΗίϊΟν-ν-ν-Τ- V“ V— V V- Τ Ι æ • H i> EH 'ai "1

CQ -P

p ΜΑ i> - v— cm cm oo i— Win m 0 .p 0 y · ->, r> r> n »i ti ti n» \ tv ρ ø> i <Ei tn tn tn in c ~ - ιο co ιο "Φ v- tn in · Φ oo σι tn cn O in ø Μ H o— 'nj c— cvj c— ene- -φφ- cu c- cm c— Φ tn tn cm tn o HIjDcSPi V- T- i- i- t- ° ^ S to æ ro o H 3 Ai Al S Α-Γ w in incMtnoo m -Φ · cn tn tn Μ I «1 | ·> | ·> I ·> I - | τ [λ | h | · 1 © cm co cn co c- co cn c1- tn oo

• a} CQ O CM CM CM Ln CMCM in Φ CM

I — 1 1—

-P cu H

s · 2 <{ø si --———-—--—— „si Ή o rQ tn oo cm cm

Si S4 I—) λ η ι \ λ r> η η κ ft tt ή naoo fc— co co cc- mm t- oooo -Φ 14- v- i- io io o <P h covo co id coio tntn co \ a ιοιο tn tn o O ιο ιο

Ai <ri i-ι— i— i— i— i— ø ___ 44 $ - | 03 Ό Μ 'φφ φφ ΦΦ 00 00 Φ φ ΦΦ 00 00 ΙΟ ιο Φ φ • Η S ° .1 «. · '' '. ·' ..... '.' Λ.2 »---- cn ι -ρ ro h œ œ œ œ œ œ œ œ œ œ I

fll Η 'Η (Hi ι ro ro φ pq I -Ρ ^ <aj ι ro ø ro Ei I Λ4 ϋ pq i-ι- cmcm -Φ φ ιοιο i- i- i-ι- mm cm cm tn tn y> si oo oo oo oo oo oo oo oommoo * Η SO 1—1— 1—1— 1—1— CMCM 1— 1— 1—1— CM CM i— i— i— i— ro ^^ tao. · & s > -----------...........

• h S tao tt- tt- tc- mtn o- t- ct- m tn Φ-c- c-- H - - - - - - - - - - H tntn tntn tntn cc- tn tn tntn c— c— φ φ mm • H ........ 1 .........—. ·

-P <j-P

03 Ai © · θ 03-PH 02 0 -H S H Ai

Sh -ρ 0 · Η © 1 = 4 >> a -p rororororororororororororororororororororororororor Hor cq · cm tn cm tn cm tn cm tn cm tn cm tn cm tn cm tn cm tn

ro aa tao -p a © h ro o SN

MA4 9H-H

© «—i ai ba 0 Hv- ^

^ 0 VO VO VO CVJ OJ

tjO ^ ti fl ti «V« s SS vo tn m m cm c- cn cm io S-p cm cn o in m in ε- φ tn S r? v- v-

o CM

_Q-iw

H Μ Μ H M

1 O H HUJ HO O OM I td M O

s © SM Offi ΟΟ o i- I c- so S o O ι ni

ora roo SO S c- S ni hh tn ro o- ω i I S W

<whw ftt-rocnrov-roM> 5 om -ρ i- ρ,, Α, η Λ © ho © cm oM -p M -PM o o PM oo OM ohI — I o fr 71 Ho cm

• Ό— Stnro ^ oco © v-red-ooOHo s ^> jOM

!> S PiO ιθ O ΟΟ Μ O © Ai O oo os © M> sO

S1H II II II I I -Ρ Η I o I> s ro Μ -PHO

<5. © SSSSSSSSraroS'H'HO-p S2) © taOM

2 oi rorororororororororororororo ro ro ro ro

Ai mtn ^ m vo c- co σι O v- mtn -Φ m id c- co cn M v— i— i-ι- i-ι- i-ι- m m mm mm m m m m 25 U7796 / ->.

toe

g o oo σ σ \ o σ v - σ σ co o σ o oo σσι o tA c-

\ tA tA tA «Φ tA * φ tA tA tA-Φ CA * φ CA tA tA · φ tA tA

tjfl

w o O O O O O O O O O O O O O O O O O

o <1 β 0 -P ^ β · ω β β * d Ο · <—S ^ ρ, es ir \ o tA αι σοο αι τ-ο σοο οο στ-co t-οο αι d σ Ο ο All τ- σσΐΑ · φ-σ-φ · 'φΙ £> ν £> CM Α) σσ-φτί-τί-σσ Αί \ IW) ø - Μ cå ra Al Η • Η ν- g +3> 5 · ________ Η CQ- - β, Μ +3 0 β «5 row

ο Λ α) X

• Η ti * Φ I +3 ω β +3 I <8 ti α> ø η) ι ra β -ρ ωι · η tioj · η omO'-oi-oøoiAOr-οΦθΑΐΜη cq ι ρ ø |> |> oo vo co γ-'Φοο ['"ΦσΜΟ« Φστ-c- ^ co co φ-

<j! IØ Lake · Η CMCMCMCMCMCMCMCM

Β I β Η -Ρ -Ρ · Η Λ! Η β-Ρ <! Ο S ^ Ρ (<Η® β ti ti __———- ro β _ +> • Η · Η β „g1 **“ ΐ »-» & Ρ! & «A C \ J · Η ^ · +3 'β -y 00 LAt- στ- ο LAU) Al Al CA 00 σ LA v- O β I CQ! jm - ft dt: ϊ o co σο-οο o i-cm oo oo οίτ-ooco oi> ^ oo φ {SS τ- 1- 1- Alt-T- t- Al 1-rT-KMA β CM β ft g rtH β ε I, so r? m ** 3 rX Pi P \

^ hD

0

• P

[A +3 * —n σ "Φ CO CO CO CO 1ΑΙΛΦ0 0 0 ΙΛ0 ΙΛ0 0 0 0 & jxj ^ σσσσσσσσσσσσσσσσσσσσ ti CM t} 0 | Z>

o w o O O O O O O O O O O O O O O O O O

3 'x

Ai AitAtHnøf-comO'-AitAM-inø> æø

(3q τ- t- 1- i- τ- τ- τ- v- T- Al Al Al Al Al Al Al Al Al CM

EXAMPLES 30 - 32 24 147796

The preparation of each of the catalytic components of Examples 1a - 3a was repeated, however, using titanium isohutylate instead of titanium n-hutylate. Clay was obtained respectively:

Example 30a: 63 g of a reddish-brown powder with a titanium content of 16.3% by weight (prepared analogously to Example 1a).

Example 31a: 21 g of catalytic complex with a titanium content of 4.0% by weight (prepared analogously to Example 2a except 66 g (0.49 mol) of aici3 was added).

Example 32a: 72 g of catalytic complex with a titanium content of 17.9% by weight (prepared analogously to Example 3a except 66 g (0.49 mol) was used)

AlClj and 29 g of AliC ^ Hj.) ^).

Clay polymerization experiments with ethylene were carried out under the general conditions set out in Example 1b with the catalytic components mentioned, and the results obtained are given in Table 5 below.

__—-, 25 9 147796 o

N

n g to Η O v- | | W) '- / - \ to tn g vo flocr »l l \« W) o v_ / tcT OD- σ \ p S ^ tO to <j ϋ · * * ** \ o o o w> S — v ΰ

• H

H S <M tO tO

g ». ·> ·> O lo in -Φ

V

\

tLO

H

o) eh ^ g + = to 3 in i -p m ^ -g I> 3 S fl

fl I O O!> 'H

I «) I tiH O in g pq I flft to cm 3

<j | H

EH | 6j0 d

v— /! —I

> 3 - + 3 to ^ fl

/ —S C \ J O

^ ra M

pq ω · η ø • Hv- ^ 't— · CM Η "· Η Η m σ \ cn Fh ft h -p a <J o o o o F-l, * 4

_ O

- «Η, M

M ra

ra -PH

• H © -P

43 lo in 'd> 3

0> 3 0 δΟ ·> * EH

d Η Η g m = - co ί> -P ø tuD ø ft ^ t- t- v 0 0 + 3

Hf Hø

S 0 O X -Η M

g, 14, M O

+3 to M

--- S ^ ø in ctv +3 ix | 1-

, 14 0 · H CM "N

ra H 0 O (3 • Η H, 14 CM w pq

+ 3M-HøØØ 0 ~ H

> 3 0 + 3 O T- CM CM <J tlO

Ra H ra · to to two

0 ft S M

+3 a 0 H ^ 0 O F4 «Η 1- CM to ΜΛΉ-Η ^^ CQ fl, Q * -x +3

, 14 O v- T- CM

(x) tO tOw tO

EXAMPLES 35-34 26 147796

The procedure was as in Example 1a, except that: 0.37 g of solute dissolved in 2 ml of ethanol was added to the reactants. 80 g of a brown catalytic complex containing 15.1 µm titanium (Example 33a) were obtained.

The remaining mixture (1) in Example 1a was cooled to 45 ° C and 181 g (1.5 mole) of A1 (C2H2) 2C1 was added. 76 g of a black-brown catalytic complex containing 18.2 wt% titanium (Example 34a) were obtained.

Polymerization experiments with ethylene carried out under the conditions given in Example 1b with the above catalytic complexes under the conditions given in Table 6 gave the results set out in the Table.

27 147796 la o> LO »n a H o in c- C \ l W)

X

w ta -ti "c-

and CO CD

R o σ> σ> s — s «V tt M o o to, a oo RO 'd- to, <j · ^ * ^ tlO o o ti • h co cn h a Ξ CM C- o' m

R

CO I Ph

R I -P

R I <D ^ -% o O

ffl I H ω CM CM

dj I d) w to, ta

Bi I H

o ra

H

ta β oo ia R'-v σ> and • h ao * · * ww o o

H

<1

M

CO

-p M

ω> 5 ω ^ ~ Ν ti Η Η Μ Μ 03 ft a c * - o

β -P gw! - CM

8 (βO

SRR

+3 ^ 4 0.

cq h ra • H H rM ce ce -p Μ -Η ω ta "M- j> 5 ø -p ta ta η H ra · teftSM -p a ran

ce O β <H

R ra R p R ta R ta ta 28 147798 EXAMPLE · 35 - 40

Mian proceeded as in Example 4 with compounds (2) other than methanol and under the conditions given in Table 7 below, where also the titanium content and amount of catalytic complexes isolated are listed.

Analogously to Example 1b, ethylene was polymerized for 2 hours with triisobutyl aluminum (Al (10Hg)) as component B and those of Examples 35a - 40a, cf. Table 7, obtained dry powdered catalytic components A. The specific polymerization conditions used and the results obtained are shown in Table 8 below.

~ 29 147796 Ό · ri 43 43 0 £ j O LA tc \ G \ r- cj ø JLj r »* s λ» s * s *> * d rf ^ o ^ Η- σ o CJO +3 T- T- V T- 1—

Ή ft tiO

1 s æ • H o t> EH Ai __ ^ __ x * CQ +3 -P 0 -Η d

Cd> d -P CD ^ CO CO "Φ MD T- C ~ - ta tiOsfj W) c- o vp o σ c ^ H ri H O W T- 1- Ή i (S Pi eh 0 + 3 s cd o

Ai Al____ LT \ LT \ I r-s H CM Ln -Φ f- int—

-φ I · Η Π O LT \ C- LT \ cn C— CO

-P <D H d * H S

Cti -d ·> 5 · Η ir ^ oooooo 02 ίώ £ 2 ί S'H o HSft-PitiH / -> vo lt \ cr \ co in i> • ri ίΒ OOH 0 il ¢ 50 M2 <J2 CO 02 "Φ eh gtM ^ oi io ^ __ 21_ f 0) §

Sd Μ HOOOOOO

02 ijQ <D g o o o in o o

H d .ri '-s CO * φ ”Φ CM CM CM

• h æ i eh a ri___ 'H d

Cd CD · O I i) J0P

HflOpO OOOOOO

• H O Al O w CM CM CM CM CM CM

-P Η -P CH 1— 1— T - \ - "f— T—

tQ +3 i> Π CD {S {S CD CD

c-1 rhhoi i> i ---

Hi co co cn

pc) I H ✓-% CM CM CM * Φ · Φ CM

PQ j O tUO »» ·. ff.

- = aj I H ^ O-t-OOOO

EH I M —--- CH <D -Φ ^ CO CO C— cd m ^ -νΗΟΟτ-όοιο H CnOCMtncMCntni- cDQ} M g HH "Φ ^ ΟΟΟΟΟΟ

¢ 50 ri Q

ri h ri -

iB O

s PH tiD O CM tn tn CM v- · Η 60 c— O c- cm o in -P l ·! EH --- f ~ -r- Π ---- d cd t n co t n in co p h o in o co in c-

^ H o · .— ^ - ·? - v * ^ - O

Γ) rj El r. Ff \ ff. n ffs ff> 3 3 δο ^ οοοοοο g ---- t- in cm in in cm r- ~. in vo vo -Φ vo oo ¢ 50 w cm tn cm -Φ tn 1- p ^ r-— vo K. H t- cn cm ό in cn o o tn c- tn in -Φ cm

Cj_ | 0 El ·. ·. ·. · »·· *.

tnwoooooo CD H ---

to CD CM

fyQH ~ d d ^ o in co co cm co £ B * H ftO 'Φ CM CO · Φ -Φ i— SP ^ _T-_

CD M

ta ίΠ M ixj M O

• PH K O O O O cm

'dd o <- C- L 1 K

flti ^ o cm cn o φ ri cm w w [_] Γ,] i

i> · Η W Hl o CO 1-1 CM

co i- T- ^ m

• 3 H O O O O

o I I I o s-ι · η d d ω • tQ cd cd cd cd o3 cd

Al in co i> co cn o ρί) tn tn tn tn tn -Φ 30 147796

S

0 \ 00 N g

ΟΟΜΟίηΦνΟΟΜΟ CM CM T- CM

M

, ¾ '—1

to, tn Φ in cow in lt \ s VO VO VD VD v £> \ D

pocncricncncricricn t «t \ 1 \ (« r> tlO O O O O o o 54 0 3 tn c- co c- O in [> - H natntntn ^ -> hto,

Qj Q r> λ λ · »» 1 λ g ^, 000000

ο taD

X V-X

© m d • η ο ΡΦ ti> 5 · Η η ι η g tn φ ο oo tn

Qj I »Λ Ι> Λ Κ ρ cg OCMOotnoavDtn S © in ίο tn \ • η ao οο ι -ρ © · ^ 1 © Ό 01 Ρ] I 0 Λ! ---— 111 I · Η tiø m ι μ ø Η <JI 0 g1H -PP4 E1 I g 0>. -p-p ti © in a o o o o

Hfnø øti ίιΟ in T- vo cm in vo o sΗ h ao cm tn cm φ tn ί— P4 4H o ςί 'ti Ή 01 æ ti -Ρ H g 01 p g --—— --- 0 0

4! 4 ^ I I

a ao> s o I ØHft '«' ce g, π + = o in co oo co Φ in

in 0 © ^ 4 «aj CM CM V- CM CM CM

t n τ) M

ao you -p • ti ti ra g 01 æ S · Η 0 M SP-Pfl 111 ___ tn ^ h in in mo v- oaCOv-oaco} rj e1 {\ »» 1 \ 1 \ iv Φ g in Φ Φ in Φ Φ ow • r4 '- <·

H - 'I

<1! ø 'ti ao cm co in T- oo co ΟΊ CTi O CTi CT, æ ao «·» 1 »· 1

g ^ i-OO ^ -OO

01 & p fil in co o oo cn o p £ j tn tn tn tn tn φ 31 147796

Comparative Example 1

Proceed as in Example 34a, except that the remaining mixture (1) is cooled to 60 ° C and diluted with 200 ml of n-hexane.

85.5 g (0.75 mole) of Al (C 2 H 3) 3 were added dropwise at 45 ° C for 4 hours. A homogeneous liquid of a black-brown color was obtained which was used in polymerization experiments as described in Example 1b.

When Al (C2H5) 3 was used as component B, no polymer was formed, and when Al (C2H5) Cl2 was used as component B, the polymerization occurred, but the yield was as low as 3700 parts by weight of polymer per liter. part by weight of titanium atom in the catalytic mixture. This shows that when using halogen-free reactants (4) there is virtually no catalytic activity, although component B may contain chlorine.

EKSEMPEL_42

Ca. 1 g of pure magnesium in the form of chips was heated together with 30 g of titanium tetrabutylate, 24.3 g of triphenylsilanol and 4.5 g of butyl chloride. Some iodine crystals were added and the mixture was maintained at a temperature of ca. 150 ° C for 270 minutes. The atomic ratio Mg / Ti in the mixture was approx. 0.5.

To the cooled mixture was added 70 ml of a 50% by weight solution in hexane of ethyl aluminum dichloride (Mg / Al atomic ratio: about 0.2). An exothermic reaction occurred and the mixture was kept at ambient temperature for half an hour. The obtained solid catalyst component was separated, washed with hexane and dried. Elemental analysis showed that it contained: 166 g / kg titanium, 343 g / kg chlorine, 47 g / kg magnesium, 32 g / kg aluminum, and 37 g / kg silicon.

It was conducted a polymerization experiment with this component under the following conditions:

Autoclave: 1.5 liters

Hexane: 0.5 liters 32 Amount of solid catalyst: 6 mg

Type and amount of component B: trii's obutyl aluminum: 200 mg

temperature: 85 ° C

Duration: 1 hour 2

Ethylene partial pressure: 10 kg / cm

ISLAND

Hydrogen partial pressure: 4 kg / cm.

Approx. 108 g PE with MI of 0.38. This corresponds to a catalytic productivity of 1,800 g PE / g catalyst x h x atm. CgH 2 and a specific activity of 10,800 g PE / g Ti x h x atm. 02Η4 * HLMI was 9 »85, HIMI / MI ratio was 26; AD and D were 0.30 and 0.960 g / cm 2, respectively.

EXAMPLE 43

About 4.86 g of pure magnesium in powder form were heated together with 47 ml of anhydrous ethanol and 152 g of zirconium n-butylate. This mixture was held at ca. 90 ° C for 2 hours, then heated to 150 ° C until excess alcohol was removed. The mixture was then diluted with 250 ml of n-hexane. The atomic ratio Mg / Zr in the mixture was approx. 0.5.

300 ml of a 50% by weight solution of AlCCgH 2 Clg in hexane was added to the cooled mixture. The atomic ratio Mg / Al was thus approx. 0.2.

An exothermic reaction took place and the mixture was held at ca.

50 ° C for 1 hour. The solid catalytic component which was isolated was separated, washed with hexane and dried. Elemental analysis showed that it contained 125 g of zirconium, 387 g of chlorine, 91 g of magnesium and 48 g of aluminum per liter. kg.

A polymerization experiment with the same component was carried out under the same conditions as in Example 42 except that 33 mg of solid catalyst was used with 100 mg of triethyl aluminum.

There were approx. 75 g PE, with MI 1.53 · This corresponds to a catalytic productivity of 230 g PE / g catalyst x h x atm.

53 147796 and a specific activity of 1840 g PE / g Zr x h x atm. C ^.

AD of the polymer was 0.17 g / cm 5 and HLMI could not be measured.

D for the polymer was 0.962 g / yr

EXAMPLE 44 9.7 g of magnesium powder, 94 ml of anhydrous ethanol and 58 g of vanadyl n-butylate [VO (OnCl 2 Hg) 2 were mixed and heated in the same manner as in Example 43 (atomic ratio Mg / V: about 2). 75 g of the powder obtained by crushing the cooled solid product was diluted with 600 ml of a 25% by weight solution of A1 (C2H5) C12 (Mg / Al atomic ratio: about 0.4). Elemental analysis of the solid obtained in the same manner as in Example 43 showed that it contained 104 g of vanadium, 113 g of magnesium and 60 g of aluminum per liter. kg.

A polymerization test performed with 16 mg of this solid under the conditions set forth in Example 42 resulted in 10 g of solid PE with melt index of approx. 40. Productivity per Thus, the specific activity is 600 g PE / g catalyst x h and 6000 g PE / g V x h respectively.

EXAMPLE 45

The solid catalytic complex was prepared as set forth in Example 1a, except that Al (O-isoC 2 H 2) ^ as compound (5) was reacted with Mg, l1 (OO ^ Hg) ^, n-C ^ HgOH and iodine. Thus, a mixture was stirred

45.4 g of n-O 2 HgOH

2.43 g of magnesium powder 9.57 g of Ii (0-nC4Hg) 4 24.0 g of Al (O-isoC ^ Hy) ^ and 0.5 g of iodine under reflux at 100 ° C for 2 hours. Low-boiling compounds were distilled from the reaction mixture. Then, it was cooled at 60 ° C and 300 ml of n-hexane and 76.2 g of Al (C 2 H 2) C 12 were added over 2 hours at 45 ° C.

34 147796

23.7 g of a reddish-brown powdery catalytic complex was isolated after leaching and drying. The titanium content was 5.1% by weight.

The polymerization experiment was carried out under the following conditions:

Autoclave: 1.6 liters

Hexane: 1 liter Amount of solid catalyst: 36 mg

Type and amount of component B: triisobutyl aluminum: 200 mg

Duration: 2 hours

ISLAND

Ethylene partial pressure: 11.4 kg / cm p

Hydrogen partial pressure: 7.6 kg / cm

Temperature: 60 ° C,

Ca. 382 g of PE were obtained. AD, MI and HliMI / MI were 0.30 g / cm 5, 170 and 56.2, respectively.

EXAMPLE 46

The preparation of the catalytic complex of Example 45 was repeated, however, using as compound (5) Si (OC2Hpj) 4, and adding CgH2 OH instead of n-C2HgOH. Thus, a mixture was reacted with

13.7 g C2H50H

2.43 g of magnesium powder 10.2 g of Ti (0-nC4Hg) 4 24.2 g of Si (0-C2H5) 4 and 0.25 g of iodine analogous to Example 45, using, however, 76.2 g of AlC2HgCl2 ·

24.2 g of a reddish brown powdery catalyst complex were obtained, the titanium content of which was 4.9% by weight.

The polymerization experiment was carried out under the same conditions as in Example 45, except that 100 mg of catalytic complex was used. There were approx. 216 g PE. AD, MI and HLMI / MI were 0.40 g / cm 2, 0.15 and 51.9, respectively.

EXAMPLES 47 - 49

Catalysts were prepared in the same manner as in Example 42, except that in Examples 47 »48 and 49 instead of (CgH 2) ^ SiOH, (CH 2) ^ SiOH, (CgH The polymerization was carried out under the same conditions as in Example 42. The details of the preparation of catalytic component A and the polymerization results are shown in Table 9.

TABLE 9

EXAMPLE

47 48 _49_ Quantity Mg (g) 0.97 0.98 0.97

Compound (2) (CH ^ SiOH (CgH ^ SiOH (t-C ^Hg) (CH CH SiOH)

Amount of Compound (2) (g) 10.8 11.4 11.5 Amount Al (02H5) 012 (g) 27.2 27.5 27.0 Amount A1 (C2H5) 2C1 (g) 29.5 51, 0 50.4

Ti content in catalyst ($) 17.1 15.1 14.0

Catalyst Activity (g PE / g Ti) 128,000 152,000 112,000

Polyethylene Melt Index 1.5 2.1 0.9 EXAMPLES 50-51

Catalysts were prepared in the same manner as in Example 45, except that ZriO-nC 2 Hg) ^ was replaced by VOCOCgH 2) ^ in Example 50, and with condensed titanium butylate having the following average structural formula of Example 51: 36Ξ7796? 4Ξ9? 4Η9? 4Η9 0 0 0 04Η90— Ti - 0 - Ti— 0 - Ti-0C4H9 boo C4H9 C4H9 σ4Η9

The polymerization was carried out under the same conditions as in Example 43. The details of the preparation of catalytic component A and the polymerization results are given in Table 10.

TABLE 10 EXAMPLE 50 51 Amount of Mg (g) 4> 86 4.86

Compound (3) V0 (0CgH.jy) j see requirement for Amount of compound (3) (g) 91 51 Amount A1 (02H5) 012 (g) 127 127

Transition metal (Tr) / Mg atomic ratio 1 1

Al / Mg atomic ratio 5 5

Catalytic transition metal content ($) 9.2 12.8

Catalyst Activity (g PE / g Tr) 33,000 203-000

Melt index of polyethylene 0.05 0.70