FI57422B - CATALYST FOR POLYMERIZATION AV ETEN ELLER PROPEN TILL SFAERISKA POLYMERPARTIKLAR - Google Patents

Description

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Patent- och registeratyralaan 'Ainekin utitgd och uti. * Kriften pubitcend 30. CA. 80 (32) (33) (31) Requested front —Begird prlorltet 13.09.72 Italy-Italy (lT) 29126 A / 72 (71) Montecatini Edison SpA, 31, Foro Buonaparte, Milan, Italy-Italy (IT) (72) ) Paolo Galli, Ferrara, Giovanni Di Drusco, Milan, Saverio De Bartolo,

The present invention relates to highly active supported catalysts for the polymerization of ethylene or propylene to the polymerization of ethylene or propylene. The present invention relates to highly active support catalysts for the polymerization of ethylene or propylene to spherical polymer particles. , which can be used to make polymers as spherical particles that do not break or clump when compressed.

The particles prepared with these catalysts have such mechanical properties that the granulation step normally used in the preparation of crystalline polymers of olefins can be omitted.

Due to the particularly high activity of the catalysts, in many cases the step of purifying the polymers from the catalyst residues is avoided and thus the preparation of crystalline polymers of olefins is considerably simplified.

Ziegler-Natta type supported catalysts are known which are capable of polymerizing olefins into polymers having a converted form of the particulate form of the starting catalyst.

Examples of supported catalysts for obtaining polymers in which the spherical shape of the catalyst repeats are described in U.S. Pat. No. 3,599,330 and DE Application No. 1,957,705 · r 2,547,422.

Polymer granules obtained with known support catalysts, in which the phenomenon of recurrence occurs, are brittle or clump easily when compressed.

It is known that the olefinic granulation step used in conventional processes for the preparation of granular polymers is a laborious delivery which greatly affects the economics of the processes. To date, numerous attempts have been made to eliminate this phase.

Hitherto known processes for obtaining directly usable polymers without granulation have used Ziegler-Natta catalysts (without support) in which the Ti trichloride used as a catalytic component is prepared by a special technique from titanium tetrachloride by reduction with an organic compound A1.

The polymers obtained using such a catalyst are in the form of a powder in a narrow grain region where the particles do not occur in any regular geometric form and decompose when subjected to decomposition experiments. These non-granular powders can only be used in fiber production processes.

The invention relates to catalysts for the polymerization of ethylene or propylene into spherical, highly friability-resistant polymer particles obtained from (a) a reaction between an organometallic compound of aluminum and (b) a support consisting of an anhydrous magnesium halide or an anhydrous magnesium halide. of a titanium compound containing an elemental compound of groups I-IV of the Periodic Table of the Periodic Table and a halogen in an amount of 0.1 to 20% by weight, expressed as Ti metal, which is chemically attached to or dispersed in the support, if desired on or after contact with the titanium compound has been treated with an electron donating compound. The invention is characterized in that the support of component (b) is magnesium halide hydrate obtained by spray-drying into spherical particles with a diameter of 1 to 350 μm and substantially dehydrated after reaction with the boiling Ti compound, and that the catalysts obtained have resistance to crushing. expressed in Wh / 1 by supersonic vibrations, the average pore radius and surface area are as follows: 1) mechanical resistance to supersonic vibrations 1-26 Wh / l, average pore pore radius 3-7 nm and surface area 3 ~ ? 0 m / g, "or 2) a mechanical resistance to supersonic vibrations of 1-5 Wh / l, an average pore radius of 7-15 nm and a surface area of more than 70 m / g.

3 57422

By mechanical resistance to supersonic vibrations is meant the minimum energy (Wh / l) which, when applied to the particles of the catalyst component suspended in an inert liquid, causes them to decompose almost completely. By "almost complete disintegration" is meant that more than 80% of the particles have an average size that is smaller than the initial size.

The catalyst component according to the invention was measured by subjecting the supersonic vibrations to a suspension of the particles in anhydrous heptane, at a concentration of 2-3% by weight, in a glass test tube immersed in a water bath.

As a source of supersonic oscillation, a device was used which developed a specific force of 10-80 W / 1 at a frequency of 22, h-k5 kHz.

The specific force of the device was expressed as the ratio of the force of the transfer system to the volume of liquid (through which the supersonic energy propagates) contained in the metal vessel to which the transfer system itself is connected.

Each specimen is subjected to successive treatments with increasing intensity (mean time and force) until almost complete disintegration of the particles is achieved. After treatment and separation of most of the heptane, the samples are photographed under an optical microscope.

This makes it possible to estimate the lowest energy that causes almost complete decomposition by mere comparison of different photographs, due to the fact that the specimens or samples showed uniformity in granular dispersion after treatment.

Particularly interesting results with regard to the mechanical strength of the spherical particles of polymers have been obtained with catalysts in which component b) withstands supersonic vibrations of 10-30 Wh / l and in which the average pore radius is 3.5-6 nm.

Equally satisfactory results have been obtained with catalysts in which component b) had a surface area greater than 70 m, resistance to supersonic oscillations at 1-10 Wh / l and a mean pore radius of 7-10 nm.

The ability of the catalysts of this invention to produce crystalline polymers of ethylene and propylene in the form of spherical particles that do not decompose or agglomerate is even more unexpected given that catalysts that differ from the catalysts of the invention only in that their support catalyst components exhibit different values in mechanical in resistance to supersonic vibrations, surface area, and central pore radius, either do not cause reproductive phenomena or, if they do, the spherical particles they form are brittle or easily agglomerate.

Component b) of the catalysts of this invention can be prepared in various ways.

1 57422

The preferred method for preparing a component having the properties indicated in h 1) is to spray molten or, if desired, hydrated magnesium halide, more preferably molten MgCl 2, by known techniques and equipment. 6h 2 O so as to obtain particle sizes which are generally 1-300 μm, preferably 30-180 yarns, then subjecting said particles to a partial dewatering treatment until the water of crystallization falls below h mol / mol magnesium halide, while avoiding causing hydrolysis reactions of magnesium halide, then reacting the partially dehydrated particles in a liquid containing a halogenated titanium compound, preferably titanium tetrachloride, heating to a temperature generally greater than 100 ° C, and finally removing the unreacted titanium compound to give a product in the form of spherical particles.

In the case of MgCl 3.

The particles thus obtained, from which the finer and coarser particles are separated by sieving if necessary, are dehydrated under conditions in which no hydrolysis of hydrated magnesium chloride takes place until the amount of water of crystallization has decreased to 0.5 ~ 3.5 mol / l mol MgCl 2, but preferably to 1-3 mol / l mol MgCl 2.

The partially dehydrated particles are then introduced into titanium tetrachloride, heated to boiling point, then freed of excess TiCl 4, washed with heating in fresh titanium tetrachloride, and then washed with heptane to remove residual titanium tetrachloride that is not attached to the support.

In another method for preparing a component having the properties indicated in b.1), an anhydrous magnesium halide solution in an organic solvent such as an alcohol, ether, ketone or ester having a boiling point of 60-150 ° C is sprayed at a temperature and pressure using known techniques and equipment suitable for producing spherical particles, in which the spherical particles are formed, have a granularity of 1 to 300 and are substantially free of a solvent which is not chemically bound to the magnesium halide, and then the removal of the solvent bound to the support is completed by heating under reduced pressure at 150 ° C, at the end of treatment 200 -350 ° C.

The spherical particles thus obtained are contacted with a halogenated titanium compound to attach the desired amount of titanium to the support.

This can be achieved, for example, by suspending the carrier particles in an inert solvent in which the titanium compound is dissolved in an amount corresponding to the amount desired to be attached to the carrier, and then evaporating the solvent.

5 57422

One method, which is also preferred for obtaining a component having the properties indicated in h 2), comprises reacting SO 2 Cl 2 with spherical magnesium halide particles containing more than 1+ moles of water of crystallization until the water of crystallization decreases to 1-2 moles / 1 mole of magnesium halide, then the support thus obtained is treated with titanium tetrachloride at its boiling point by the method described in connection with the preparation of component b 1).

In the case where the catalysts of the present invention are used for the polymerization of propylene, it is preferable to treat component b) with an electron donating agent before or after the titanium compound is bound to the support. In this case, the organometallic compound used for the preparation of the catalyst is also treated with an electron donating agent, which is preferably less than 1 mol / l mol of the organometallic compound and especially 0.1 to 0.1 mol.

The electron donating compounds are preferably selected from esters of organic and inorganic oxygen acids and mono- and polyamine compounds having no primary amino groups.

Examples of such compounds are esters of benzoic acid and its alkyl derivatives, Ν, Ν, Ν, Ν-tetraalkylethylenediamines and piperazine.

The magnesium halide can be used in a mixture of 20 to 80% by weight of a magnesium halide with an inert carrier selected from the compounds of Groups I to IV of the Periodic Table.

Examples of such compounds are: NagCO 2, Na 2 SO 4, BgO 2.

Halogenated titanium compounds useful in the catalysts of this invention include, for example, halides, haloalcoholates, halide amides, ammonium halotitanates and halogen titanates, titanium salts of organic halogen acids. Preferably, liquid titanium compounds are used, such as: TiCl 2, TiCl Solid compounds such as TiCl 4 are used in the form of solutions in inert solvents containing their complexes with electron donating substances. The amount of the titanium compound to be used, expressed as titanium metal, is generally 0.1 to 20% by weight based on the support-catalyst component.

The organometallic compounds of the metals of groups II and III of the Periodic Table are trialkyl-Al compounds, dialkyl-Al halides, Zn and Mg-alkyl compounds.

Examples of such compounds are: Al (C 8 H 5) 2, Al (C 2 H 5) 2, Al (C 3 H 5) 3, A 1 (C 2 H 5) 2 Cl, Zn (C 2 H 5) 2, Mg 2 H 2

As already mentioned, when catalysts with higher structural accuracy in the polymerization of propylene are desired, part of the organometallic compound is used in the form of complexes with electron donors.

The polymerization of ethylene and propylene with the catalysts of this invention is carried out by conventional methods.

The polymerization is carried out in the liquid phase either without or with an inert diluent or in the gas phase.

The polymerization temperature is generally i + 0-200 ° C, preferably 50-100 ° C.

The molecular weight of the polymers is adjusted using molecular weight regulators of the type known in the polymerization step, such as, for example, hydrogen, Zn dialkyls.

The resistance of the spherical polymer obtained with the catalysts of this invention to crumbling and caking is determined using granular clumps and not individual particles, according to the following methods.

Determination of resistance to crushing 20 g of polymer are placed together with two small porcelain spheres (diameter 25 mm) in a metal cylinder (inner diameter 38 mm - length 160 mm) fitted with a metal plug and fixed to a horizontal carriage capable of passing a distance of 50 mm and made to vibrate 2l + 0 times per minute for 20 minutes.

The granularity of the polymer (with screens, ASTM Series No. 1+, 7, 10, 18, 35 and 70) is then compared to the granularity of the original polymer. The polymers obtained with the catalysts of this invention show substantially the same granularity both before and after the experiment. On the other hand, a significant reduction in particle size was observed in the polymers obtained with catalysts not within the scope of the invention.

For the agglomeration resistance test, U tablets weighing 2 to about 10 g were prepared by compression at a pressure of 39 μg / cm in a cylindrical die (diameter 18 mm) for 6 minutes for the same treatment used to determine the resistance to crumbling.

In the event that the tablets remain substantially compact, the separated fine particles are weighed, while in the case of complete crumbling, the granularity of the crumbled material is determined with the same screens used to determine the particle size of the polymer.

The polymer tablets obtained with the catalysts of this invention disintegrate almost completely as a result of the treatment, thus producing reshaped particles which, however, have almost the same dimensions as the original small spheres.

τ 57422 In contrast, polymers obtained with catalysts whose properties did not correspond to those of the catalysts according to the invention do not degrade or degrade slightly during the shaking test.

As already shown, the polymer particles obtained with the catalysts according to the invention are resistant in both the crumbling test and the compression test.

Another important feature of the catalyst used in the polymerization is that the particles (usually 1-2 mm in diameter) are evenly distributed in the mass of the particles of the magnesium compound used as support, the residues generally containing less than 30 ppm Ti of residual titanium compound.

The invention is illustrated by the following examples. Unless otherwise indicated, percentages are by weight.

Example 1

Preparation of MgCl 2 -SHgOin in spherical form

Molten MgCl 2 / H 2 O was sprayed countercurrently with hot air into a jet-cooled type apparatus manufactured by Niro Atomizer. The diameter of the spray nozzle was 0.3 μm. The overpressure was provided by nitrogen.

The spherical particles were collected at the bottom of the dryer and then screened to obtain a fraction with a particle diameter of 53-105. The fraction thus obtained was then dried in an oven at 130 ° C under a stream of nitrogen.

After drying, the product was found to be MgCl 2.

The equipment used consisted of a Pyrex glass reactor of about 3 liters with a sintered glass filter plate at the bottom. Heating was accomplished by means of an electric heater wrapped around the lower, tubular portion of the reactor. Furthermore, the reactor was equipped with a reflux condenser, a stirrer, a thermometer and a bellows system to obtain anhydrous nitrogen. The carrier MgCl 2 211 O 0 was fed in powder form through the orifice by means of a test tube which could be pressurized with nitrogen.

The reaction and washing liquids of the filtrate were collected in a glass flask connected to the bottom of the reactor, while another flask arranged next to and connected to the end of the reactor heats and feeds the washing liquids.

The support-binding reaction took place by introducing 2500 ml of TiCl 4 into the reactor and then raising the temperature of the TiCl 4 to a boiling point of 136.5 ° C. After boiling for a few minutes, 120 g of support were introduced into the reactor with vigorous stirring. In this case, the temperature dropped mainly due to the hydrochloric acid developed in the reaction, which dissolved in TiCl 4, causing this boiling point to decrease.

Gradually, the temperature rose to 138 ° C, which is the boiling point of TiCl 4 when it contains a certain amount of TiOCl 4 as a by-product of the reaction. This temperature β 57422 was maintained for one hour to complete the reaction. The reacted TiCl 4 containing by-products was then filtered hot. Two washes with TiCl 2 while hot, then 5 times with dehydrated heptane by distillation in the presence of sodium metal.

Chemical analysis of the support catalyst component dried in vacuo gave the following results: Ti = 2.95%; Cl = 69% \ Mg = 20.5 HgO = 2.85% · X-ray analysis showed that. MgCl 2 and MgCl 2 H 2 O were present. The surface area of the carrier component was 33.7 m 2 / g.

The minimum specific supersonic energy required for complete disintegration of the particles was 10.3 Wh / L.

The average radius of the pores was 5.9 nm.

A U.5 liter autoclave equipped with a paddle stirrer, a heating oil circuit, and a cooling water circuit was charged with 2000 mL of purified heptane containing U g of Al-triisobutyl. The temperature was raised to about 75 ° C, then the catalyst component dispersed in heptane was added under hydrogen pressure obtained from the bellows system. The amount added corresponded to 0.00U52 g Ti. 7.5 kg / cm of hydrogen and 5.5 kg / cm of ethylene were then introduced into the autoclave and the temperature was allowed to rise to 85 ° C.

The pressure was kept constant by continuously feeding ethylene. The polymerization was continued for k hours. After degassing and cooling, the mixture gave 7 + + 0 g of polyethylene. The polymer was in the form of spherical particles, 1-2 mm in diameter, which withstood the standard crushing and compression tests described previously.

Example 2 The support used was the same as in Example 1. The method for preparing the catalyst component and the amounts of reagents were also the same.

At this the catalyst was subjected to propylene polymerization experiments in and with liquid propylene without complexing agents.

Polymerization without complexing agents

To the U-liter autoclave already described, 3.1 g of Al-triisobutyl in about 10 ml of heptane were added under hydrogen pressure. The autoclave was charged with 1150 g of propylene from a small 2 liter flask. The temperature was raised to 30 ° C. In this case, 0.01 U1 g was injected from a 50 ml flask using hydrogen overpressure. catalyst, corresponding to 0.000 x 5 g Ti, and 0.9 g Al-triisobutyl in 20 ml heptane.

The temperature was then raised to 60 ° C and at this temperature the pressure was found to be 27 atmospheres (overpressure due to injected hydrogen). During the U hour polymerization, the pressure dropped to 21 atmospheres.

After cooling and removal of propylene, 750 g of polypropylene were obtained.

9 57422

Yields were found to be 1,670,000 g polymer / g Ti.

The residue after extraction with heptane was 18.8

After extraction of the amorphous substance, the polymer was in the form of spherical particles, about 1 mm in diameter, which withstood both compression and crushing tests.

Polymerization with Triphenylphosphine Complexing Agent In this example, the same autoclave and the same method were used as without complexing agents. Using a stream of hydrogen, U grams of Al-triisobutyl in about 15 ml of heptane and then 1150 g of propylene were fed. 0.009 g of catalyst (corresponding to 0.00029 g Ti) were weighed and fed into a small 50 ml flask containing 0.02 g of triphenylphosphine in 20 ml of heptane; these were left in contact with each other for about 15 minutes. The catalyst and phosphine were then injected into the autoclave under hydrogen pressure. The temperature was raised from 50 ° C to 60 ° and the pressure rose to 26 atmospheres. After 1 h, the reaction mixture was cooled, the propylene was removed to give 1 g of polymer. Yields corresponded to 500,000 g polymer / g Ti. The residue after extraction with heptane was 29.5%. · After extraction of the amorphous substance, the polymer was in the form of spherical particles which withstood standard crushing and compression tests.

Polymerization with an ethyl hhenoate complexing agent

3 g of Al-triethyl in 11 ml of heptane and 1.5 g of ethyl benzoate were introduced into the autoclave already described under hydrogen pressure.

The autoclave was then charged with 950 g of propylene and catalyst, 0.0171 g in 20 ml of heptane (corresponding to 0.00055 g Ti) was injected with a hydrogen pressurized flask. The temperature was then raised to 65 ° C and the pressure settled to 28 atmospheres.

After k hours of polymerization, the polymerization mass was cooled, degassed to give 1 * 3 g of polymer in the form of small flowing spheres which withstood crushing and compression experiments, yield 78,000 g / g Ti residue after extraction with heptane was 63.6%.

Examples 3-7

Examples 3 and k are comparative examples. The preparation of hydrogenated magnesium chloride in the form of spherical granules was carried out in a 6-liter jacketed autoclave fitted with a liquid-phase retractable siphon and a thermocouple for measuring temperature and a manometer for measuring pressure.

An externally shielded pipe with a spray nozzle (0.6¾ mm diameter) screwed to the siphon is attached to the siphon. Heating is performed with steam at a pressure h, 3 atmospheres by circulating this in the heating flange.

U kg of MgCl 2 .H 2 O was introduced into the autoclave. The temperature was raised to 128 ° C

.0 57422 by circulating steam in the jacket. The pressure was raised to 22 atmospheres by introducing nitrogen into the autoclave. After the outer part of the siphon leading to the spray nozzle was heated with steam, the valve was opened and the molten chloride was sprayed.

The sprayed chloride was collected in a sealed container containing an anhydrous heptane with a nitrogen bellows. At the end of the spraying, the spherical powders were separated from the solution and heated in an oven at a temperature slightly below 80 ° C under a stream of nitrogen to remove the solvent.

The carrier was found to consist of spheres less than 350 μm in diameter, about 30% less than 150 μm.

After the field material was screened and the fraction 105-11 + 9 jnn selected, this fraction was dried in an oven at different temperatures.

Data on the dehydration of spherical chloride, with a view to obtaining different degrees of hydration, are given in Table 1.

The preparation of the support catalyst components was carried out using water-separated supports and using the method described in Example 1.

The reaction conditions, amounts of reagents, and analytical values of the carrier components are shown in Table 2.

The polymerization with ethylene was carried out in the same apparatus by the same method as described in the previous examples.

The polymerization conditions, the results obtained and the properties of the polymers are shown in Table 3.

table 1

Dehydration conditions Example 3 Example H Example 5 Example 6 Example T

ratios Temperature, ° C 80 95 115 135 135

Time, h 1 * it It U Θ

Cl 36.1 * 5% UO, 95% U6.35% 53.75% 60.95% H 2 O 51, fc0% U3.05% 37.20% 26.80% 16.00% RX: crystalline form MgCl 3 .HHO MgClg.UHgO MgCl 2 HgO MgCl2.2H2O MgCl2.H2O

MgCl2.2H20

Cl, theoretical amount $ 3 **, 85 1 * 2.9 1 * 8.5 5 **, 1 62.7 H „0, theoretical amount 2 53.2 U2, U 3 * +, 9 27, U 15.9 ”57422

Table 2

Example 3 Example H Example 5 Example 6 Example 7

Amount of carrier 80 g 80 g 60 g 80 g 39 g

Amount of TiCl 2 2000 ml 2000 ml 2000 ml 2000 ml 2000 ml Temperature, ° C 137 137 137 138 137

Time, h 11111

Wash with TiCl 2 22221

Wash with heptane 55555

Analysis,%

Ti 3.50% 1 +, 15% 3.00% 3.20% 1, 55%

Cl 69.00% 70.25% 68.95% 69.15% 68.15%

Mg 20.95% 20.95% 21.55% ~ 22.25%

Specific surface area, m2 / g 98.2 109.9 61 +, 9 21, 3 11, 1 +

Resistance to supersonic vibrations,

Wh / 1 3-3.17 2-3.2 10.3 25.6 25.6

Mean radius of the pores, nm 1 +, 1 3.6 l +, δ 3.8 6.3 12 57422

Table 3

Example 3 Example, Example 5 Example 6 Example 7

Amount of catalyst compound, g 0.0165 0.0153 0.021 + 5 0.029 0.031 + 3

Amount of Ti, g 0.00056 0.00061 * 0.00073 0.00093 0.00058

Amount of Al (iC ^ Hp) 3, g ^ k 1+ H 1 * Temperature, ° C 85 85 85 85 85

Time, h 55555

Ethylene pressure, 8.5 8.5 8.5 8.5 8.5 8.5

Hg pressure, ata 5 »5 5.5 5.5 and 5.5 5.5

Amount of polymer, g 508 81 + 0 310 195 23I +

Yield, g pol./g Ti 900,000 1,300,000 1 * 25,000 210,000 1 * 00,000 g pol./g catalyst 31,000 55,000 12,600 6,700 6,850 Apparent density g / cmn 0.268 0.300 0.1+ 00 0.1 + 35 0.1 + 00

Polymer

Resistance to crushing no no yes yes yes to compression no no yes yes I yes

Examples 8-10

Examples 8 and 9 are comparative examples. The catalyst components used in these examples were obtained using a grain fraction of 62-105 μm obtained from the magnesium chloride hexahydrate, tetrahydrate and dihydrate of Examples 3, 1+ and 6, respectively.

The catalyst components were prepared by the same method as in Examples 3, 1+ and 6.

13 57422

Polymerization experiments have also been performed under the same conditions as in the above examples.

Table 1+ shows the properties of the support catalyst components, the results of the polymerization experiments and the properties of the polymers obtained.

Table 1+

Example 8 Example 9 Example 10

Analysis of the carrier's component:

Ti% 3.69 3.25 2.55

Cl% 66.7 68.35 67.85

Mg% 18.9 19.85 21, Ho 2

Specific surface area m / g 156.1 82.9 12

Resistance to crumbling, Wh / 1 3.8-6, U 6.1+ 25.6

Mean radius, nm 3.8 3.1+ l +, 0

Polymerization

Yield, g pol./g Ti 760,000 1,066,000. 1 + 35,000

Resistance of the polymer to crumbling no no yes to compression no no yes

Example 11

Molten MgCl 2 / CH 2 Cl 2 was sprayed by the method described in Example 1. The product thus obtained was screened to separate a fraction with a grain size between 105-11 + 9 μm.

This fraction was then dried in an oven at 80 ° C for 1+ hours under a stream of nitrogen.

X-ray analysis of the product showed the product to be MgCl 2 .6HgO.

80 g of this product were then reacted with 2000 ml of TiCl 4 in the apparatus described in Example 1.

After a reaction time of 1 hour, the excess TiCl 4 was removed, and an additional 2000 mL of fresh TiCl 4 heated to 120 ° C was added to the reaction mixture and the temperature was maintained at 137 ° C for an additional hour. The TiCl 4 was then removed and the product was washed three times with hot Tielai and 6 times with heptane.

Analysis of the dry product gave the following values:

Ti = 8.55% Cl = 61.1 + 5% Mg = 17.25%.

2

The specific surface area of the product was 27.1+ m / g and the resistance of the particles to 11. 57422 crumbling was 12.8 Wh / l.

0.0151 g of this product was used for the polymerization of ethylene under the conditions of Example 1.

There was thus obtained 150 g of a polymer consisting essentially of spherical granules, but also containing granules of irregular geometric shape. When subjected to standard crumbling and compression tests, the polymer did not crumble or clump.

Example 12 In the form of spherical particles, size 53-105, obtained by spraying in the apparatus described in Example 1, was reacted with 2500 ml of SO 2 in a 3-liter flask equipped with a stirrer and a reflux condenser. The reaction started at 55 ° C with gas evolution. During the reaction, the temperature slowly rose to 70 ° C.

The reaction was continued until a product of MgCl 2 1.5H 2 O was formed.

30 g of this product was then reacted with TiCl 3 under similar conditions as in Example 1.

Analysis of the product, dried under vacuum at 70 ° C, gave the following results:

Ti = 2.80% Cl = 67.80%.

2

The specific surface area was 77.2 m / g.

The resistance of the particles to crumbling was 3.9 Wh / l, while the average radius of the pores was 9 »2 nm.

0.0372 g of this product was used for the polymerization of ethylene under the same conditions as in Example 1. There was thus obtained 290 g of a polymer in the form of spherical particles which, when subjected to standard fracture and compression tests, did not crumble or clump.

Example 13 50 g of a spherical product of MgCl 3 .1.5H 2 O obtained under the conditions of Example 12 was reacted with 50 ml of ethyl benzoate. After 16 hours, the liquid was completely absorbed.

The solid product was diluted with heptane, the suspension was evaporated to dryness under high vacuum at about 70 ° C.

The dried product was screened with a 200 sieve to remove the coarse particle fraction.

30 g of the product thus obtained were reacted with 2000 ml of TiCl 4 under the conditions of Example 1. The product, dried in vacuo, gave the following analytical results: 57422

Ti = 2.5% i Cl = 6U% \ Mg = 21.2%.

2

The specific surface area was 118.9 m / g; the resistance to particle crumbling was 1.7 Wh / l. The average radius of the pores was 9.2 nm.

0.01 * 1 g of product was used to polymerize ethylene under the conditions of Example 1. The polymer thus obtained was in the form of spherical granules, 1-2 mm in diameter. They were subjected to standard tests to determine resistance to crumbling and agglomeration, neither crumbling nor agglomeration.

Example 11 *

MgCl 2 · 0.1 ^ 2 () was prepared in the form of spherical particles by removing water in a stream of HCl gas at 110 ° C, 53-105 μm in size, from the MgCl 2 O 2 particles obtained by the spraying method described in Example 1.

1 * 5 g of product was then reacted with TiCl 4 under the same conditions as in Example 1.

After drying, the support catalyst component thus obtained gave the following analytical results:

Ti = 0.3%, Cl = 69.80%, Mg = 25.60%.

2

The specific surface area was 3.7 m / g, the resistance to embrittlement was 6. U Wh / l.

0.1902 g of this product was used for the polymerization of ethylene under the same conditions as in Example 1.

There were thus obtained 70 g of polymer in the form of spherical particles, 1-2 mm in diameter. They were subjected to standard tests to determine resistance to crumbling and agglomeration; they did not crumble or clump.

Claims (3)

16 57422 Catalysts for the polymerization of ethylene or propylene into spherical, highly friability-resistant polymer particles obtained by the reaction of (s) an organometallic compound with aluminum and (b) a support consisting of anhydrous magnesium halide or anhydrous magnesium halide. by weight of a titanium compound containing 0.1 to 20% by weight, expressed as a Ti metal, of a elemental compound of Groups I to IV of a Periodic Table inert to a magnesium halide and chemically attached to or dispersed in a support which if desired before or after contact with the titanium compound, has been treated with an electron donating compound, characterized in that the support of component (b) is magnesium halide hydrate obtained by spray-drying into spherical particles having a diameter of 1 to 350 microns and the reaction residue substantially dehydrated with boiling Ti and that the catalysts obtained have a resistance to fracture due to supersonic vibrations expressed in Wh / l, the average radius of the pores and the surface area are as follows: 1. mechanical resistance to supersonic vibrations 1-26 Wh / l, an average pore radius of 3 to 7 nm and a surface area of 3 to 70 m / g, or 2. a mechanical resistance to supersonic vibrations of 1 to 5 Wh / l, an average pore radius of 7 to 15 nm and a surface area of area over 70 m / g. Catalysts according to Claim 1, characterized in that the organometallic compound is Al-trialkyl which is partially complexed with an electron-donating compound. Process for preparing a catalyst according to claim 1 by reacting an Mg halide with a halogenated Ti compound followed by an organometallic aluminum compound, characterized in that the hydrated magnesium halide is sprayed to form spherical particles having high mechanical strength, particles having a diameter of 1 to 3 un, separated, and the dihalide particles are dehydrated to give water values of 0.5-3.5 moles, the partially dehydrated particles are reacted in a liquid medium containing Ti compound at a temperature above 100 ° C, and finally the Ti compound not attached to the support is removed .