JPS604203B2 - Catalyst for polymerizing olefins into spherical polymers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for producing olefins with high activity characterized by providing polymers in the form of spherical particles that do not break or aggregate when subjected to compression. It relates to supported catalysts for polymerization.

Thanks to the special mechanical properties of the particles, the granulation step normally used in conventional processes for the production of crystalline polymers of olefins can be avoided in forming the catalyst according to the invention.

In view of their particular high activity, these catalysts also in many cases avoid going through the steps of purifying the polymer from the catalyst residue and are therefore of great value in the production of crystalline polymers of olefins. It can significantly simplify traditional methods.

It is known that supported catalysts of the Ziegler-Natta type can be polymerized from olefins to polymers having particle shapes that regenerate or "repeat" the particle shape of the starting catalyst.

Examples of supported catalysts that result in polymers that repeat the spherical or elliptical shape of the catalyst are described in US Pat. No. 3,594,33 and German Patent No. 1,957,705.

Polymer particles obtained with supported catalysts, which are known in the art and which cause cyclical phenomena, are brittle or easily solidify when subjected to compression.

It is known that the granulation phase used in conventional processes for the production of crystalline polymers of olefins is a cumbersome operation that significantly affects the economics of the process.

Many attempts have been made in the past to completely eliminate this phase. The only method known to date that allows directly obtaining useful polymers from granulation in a modified process for the products produced is the reduction of titanium trichloride used as catalyst component with aluminum organic compounds from TIC14. Unsupported Ziegler, possibly produced by special techniques.

It is characterized by the use of a Natta catalyst. The polymers obtained with such catalysts are in the form of powders with narrow particle sizes, the particles do not reproduce any regular geometry and do not disintegrate when subjected to an abrasion test.

Furthermore, this non-granulated powder has application only in fiber manufacturing processes.

In the present invention, we have surprisingly provided a supported catalyst for the polymerization of olefins which can give crystalline polymers as spherical or ellipsoidal particles which are endowed with rather high activity and at the same time exhibit remarkable resistance to disintegration and agglomeration. discovered that it can be manufactured.

The catalyst of the present invention consists of 'a} a metal-organic compound of aluminum and {b} (c} anhydrous magnesium halide, or in a compound of anhydrous magnesium halide and an element from groups 1 to W of the periodic table. Inert cocarrier 2 selected from
a support consisting of a mixture with a weight of 0 to 8; and 'd} a halogen-containing titanium compound chemically bonded to or uniformly dispersed on the support, said product having a weight of 10 to 80 In terms of average radius, surface area and resistance to ultrasonic vibration of the pores, when measured using a device that generates its specific power and has a frequency of 22.4 to 4 Hz: [1] Resistance to ultrasonic vibration is 5 to 40 watt hours/sleeve, and the average radius of the hole is 30 to 40 watt hours/sleeve.
70A and a surface area of 3 to 70 W/W.
2} Characterized by satisfying one of the following relationships: resistance to ultrasonic vibration is 1 to 20 watt hours/sleeve, average radius of pores is 70 to 150△, and surface area is 70 watts or more. These are spherical particles with a diameter of 1 to 350 microns obtained by reaction with

The average radius of the hole is the ratio 2V no S. 1 (Formula V represents the total porosity of the particle in cc' and S is the planar area in cc).

Mechanical resistance to ultrasonic vibrations refers to the minimum specific energy (in watt-hours) required to deliver particles of a catalyst component suspended in an inert liquid to cause its almost complete disintegration. .

Almost complete disintegration means that more than 80% of the particles exhibit an average size less than or equal to their starting size. In the case of the catalyst component in the present invention, the measurements are carried out by subjecting a suspension of particles in anhydrous hebutane at a concentration of 2 to 3% by weight, placed in a glass test tube immersed in a water bath, to the action of ultrasonic wave vibrations. I went by that.

The ultrasonic vibration source uses a device that generates a specific power of 10 to 80 watts and has a frequency of 22.4 to 4 Hz.

The specific power of the device is expressed by the ratio of the power of the transducer to the volume of liquid contained in the metal tank that supplies the transducer itself (through which the ultrasound energy spreads).
Each specimen is subjected to successive treatments (duration and force) of increasing strength until almost complete disintegration of the particles is obtained. After processing and pre-separation of the bulk of hebutane, the sample is photographed under an optical microscope. Due to the fact that after processing the specimens or samples exhibit non-uniformity in grain distribution, it is possible to perform the lowest energy generation that would cause almost complete disintegration on the basis of a simple comparison between the various photographs. can. Particularly interesting results regarding the mechanical resistance of spherical or elliptical particles of polymers were achieved with catalysts characterized by component'b's ultrasonic resistance of 10-30 watt-hours and an average pore radius of 35-60 A. be given

Quite satisfactory results are obtained with catalysts in which component (b) is characterized by a surface area of more than 70 meters/ta, a resistance to ultrasonic vibrations of 1 to 10 watt hours and an average radius of the pores of 70 to 100 A.

The ability of the catalysts of the present invention to produce crystalline polymers of olefins in the form of spherical or ellipsoidal particles that do not disintegrate or aggregate is due to the fact that the catalytic support component has a high mechanical resistance to ultrasonic vibrations, a large surface area, and a large pore size. Catalysts that differ from those of the invention only by the fact that they exhibit different values for the mean radius do not exhibit the phenomenon of "returning" or, if they do, the spherical or elliptical particles they form This is highly unexpected when one considers that the material is brittle or easily aggregates.

Component (b)' of the catalyst of the present invention can be prepared in a variety of ways.

A preferred method of producing components exhibiting the characteristics shown in {b} {1} above is by melting or preferably in water to obtain particles with a size generally between 1 and 300 microns, preferably between 30 and 180 microns. The molten hydrated Mg halide, and more particularly the molten MgC12 string 20, is exposed using known techniques and equipment to form a product of spherical particles, and then the particles are mixed with a crystalline water content of 1% of that of the Mg halide.
Halogen-containing Ti compounds, in particular, which have been subjected to a controlled partial dehydration treatment without any hydrolysis reaction of the Mg halide until 4 moles per mole, and then the partially dehydrated particles are heated to a temperature generally above 100°C. TIC14
The process consists of reacting in a liquid medium containing Ti and finally removing unreacted Ti compounds.

In the case of MgCl2 fine 20, the molten chloride is rolled into a stream of hot air or hot nitrogen by a nozzle with an orifice chosen such that the spherical particles formed have a particle size composition of 1 to 300 microns. be misted.

The particles thus obtained, preferably separated by fine and coarse particles, have a hydrolysis of hydrated Mg chloride ranging from 0.5 to 1 mole of water of hydration per mole of MgC12.
Dehydration occurs under conditions that do not occur until a reduction to a value of 3.5 mol, preferably 1 to 3 mol.

The partially dehydrated particles were then heated to the boiling point of T.
It is then washed hot with fresh TIC14 to eliminate excess TIC14 and then washed with hebutane to remove any traces of TIC14 that were not immobilized on the carrier.

A further method for producing components having the characteristics indicated is, for example, using alcohols, ethers, ketones or esters, using known techniques and equipment suitable for obtaining products in the form of spherical particles. Forming a solution of anhydrous Mg halide in an organic solvent having a boiling point of 60 to 150 oC, generally having a particle size of between 1 and 300 degrees Fahrenheit, the solvent is substantially free from chemical bonding with the Mg halide. Atomize at a temperature and pressure such that the temperature and temperature disappear, and then under reduced pressure at a temperature of 150°C or higher, and at the end of the process a temperature of 200°C
It consists of completing the removal of the solvent bound to the carrier by heating at a temperature of 5000 °C.

The thus obtained spherical particles are then coated with a desired amount of T on a carrier.
Contact with halogen-containing Ti to fix i.

This can be achieved, for example, by suspending the particles of the support in an inert solvent in which the Ti compound is dissolved in an amount corresponding to the amount desired to be deposited on the support, and then evaporating the solvent. One of the preferred methods for obtaining a component having the characteristics shown in {2) of {b} is to prepare 1 spherical Mg halide particles containing 4 moles or more of water of crystallization.
The particles are reacted with SOC12 until dehydrated to a water content of 1 to 2 moles per mole of Mg halide, and the support thus obtained is then used for the preparation of component '1' of 'b' above. It consists of treating with TIC14 at the boiling point according to the method described.

When using the catalyst according to the invention for the polymerization of alpha olefins, more particularly propylene, it is convenient to treat component 'b} with an electron donor before or after supporting the Ti compound. good.

In these cases, the metal-organic compound used for the preparation of the catalyst is treated with an electron donor, which is preferably used in an amount of up to 1 mol, more particularly in an amount of 0.1 to 0.4 mol per mol of metal-organic compound. It is. The electron donor compounds are preferably chosen from esters of organic and inorganic oxygen acids and especially from mono- and polyamine compounds free of primary amino groups.

Important examples of such compounds are esters of benzoic acid and its alkyl derivatives, N·N·N·N-tetraalkylethylenediamine, piperazine, and the like.

The Mg halide can be used in admixture with 20 to 8% by weight of a carrier selected from compounds of elements of Groups 1 to W of the periodic table and which is inert to the Mg halide. .

Examples of such compounds include Na2C03, Na2S04, B
It is 03.

The halogen-containing titanium compound that can be used in the catalyst of the present invention is
Examples are halides, halo alcoholates, halo amides, ammonium halo titanates and halo titanates, Ti salts of organic halogen acids.

For example, TIC14, TIC12 (OC4 day 9) 2, Ti
Preferably, a liquid titanium compound such as Br4 is used. A solid compound, such as TIC13, is used in the form of a solution of its complex with an electron donor in an inert solvent. In general, the amount of titanium compound that can be used, expressed as titanium metal, is between 0.1 and 20% based on the supported catalyst component.
Weight%. Metal-organic compounds of metals of groups 2 and 2 of the periodic table are trialkyl aluminum compounds and dialkyl aluminum halides.

Examples of such compounds are AI(C2day5)3, Yama(iC4day9)3, N(C3day7)3, AI(C2day5)2CI. As already mentioned, when it is of interest to have a highly stereospecific catalyst for the polymerization of alpha-olefins, some of the metal-organic compounds are used in the form of complexes with electron-donating compounds. . Ethylene, alpha
The polymerization of olefins, in particular propylene, butene-1, 4-methylbentene-1 and ethylene/alpha-olefin mixtures with the catalysts according to the invention, is carried out in a conventional manner. Polymerization is carried out in the liquid phase in the presence or absence of an inert diluent or in the gas phase.

Generally the polymerization temperature is 40~200oo, preferably 50~1
It is 00℃.

The molecular weight of the polymer is controlled by using known types of molecular weight regulators in the polymerization phase, such as hydrogen, Zn-dialkyl, and the like.

The resistance to disintegration and agglomeration of the spherical polymers obtained with the catalysts of the invention is determined by operating on large quantities of particles, but not on individual particles, in the following manner.

To measure the resistance to disintegration, a 20-meter polymer with two small balls (diameter 25 ribs) of porcelain was fixed with a similar metal plug with a horizontal movement of 5 meters. It was introduced into a cylinder (inner diameter: 16 mm long) and subjected to vibrations of 240 times per minute for 20 minutes. Next, the particle size (ASTM system No. 4, 7, 10, 1
&35 and 70) with the particle size of the polymer itself.

The polymers obtained with the catalyst of the invention exhibit substantially the same particle size before and after the test. In contrast, polymers obtained with catalysts outside the scope of the present invention show a significant reduction in particle size. For setting resistance, 4 tablets of approximately 10 mm were prepared by compressing in a cylindrical die (18 rib diameter) under a pressure of 394 k9 / 6 lbs. in the same process used for the measurement of disintegration resistance. Serve for a minute.

If the tablet remains substantially dense, weigh the separated fine particles; in case of complete disintegration, measure the particle size of the disintegrated material as used for the particles of the polymer itself. Measured by knots.

The polymeric tablets obtained with the catalysts of the invention become almost completely separated under treatment, giving deformed particles having almost the same dimensions as the original small, spherical particles. On the contrary, polymers obtained with catalysts which do not correspond to the features of the invention do not separate under the action of the vibration test, or only to a very small extent.

As already mentioned, the polymer particles obtained with the catalyst of the invention survive both the disintegration test as well as the densification test.

Another characteristic that may be attributed to the catalyst used in the polymerization is that the particles (generally having a diameter of 1 to 2 sides) are uniformly distributed within the mass of particles of the Mg compound used as a carrier. It is to show that.

Generally, the residual Ti compounds present in the particles are
The amount is as follows. Next, the present invention will be specifically explained with reference to Examples.

However, the present invention is not limited only to the examples. Percentages are by weight unless otherwise stated. Example 1 Production of spherical MgC12.2LO Melted MgC12.2LO was heated with hot air (60 mm) in a "rumor mist-cooling" type device of a sprayer (A's mizer) manufactured by Niro Shokai (Denmark). Discuss it in a flowing manner.

The diameter of the spray nozzle is 0.34 feet. Overpressure is obtained with nitrogen. The spherical particles are collected at the bottom of the dryer and then
Ring to obtain 3-105 micron sections.

The parts thus separated were then heated to 13,000 ml in a nitrogen stream.
Dry in the oven. The product after drying is MgC12.
It was proved that it consists of LO.

Preparation of Supported Catalyst ComponentsThe apparatus used consisted of a Pyrex glass reactor of approximately 3 holding volumes with a sintered glass furnace plate at its bottom.

Heating is obtained by an electrical resistor wrapped around the lower tubular section of the reactor. Additionally, the reactor is equipped with a reflux condenser, a rotor, a thermometer, and an anhydrous N2 pressure storage system. The feeding of the carrier as a powder takes place through a passage in a test tube which can be pressurized with N2. A glass flask connected to the bottom of the reactor collects the reactor liquid and wash liquid, while another flask placed laterally and connected to the top of the reactor heats and supplies the wash liquid. Helpful.

The retention reaction occurs by introducing 2500 cc of TIC14 into the reactor and then bringing the temperature of the TIC14 to a boiling point of 136.500.

After a few minutes of boiling, 120 g of carrier is introduced into the reactor with vigorous heating. The temperature decreases mainly due to the influence of HCI generated during the reaction and dissolved by TIC 14' which causes a drop in the boiling point. The temperature is determined by the reaction by-product TiOC
1380, which is the boiling point of TIC14 containing a certain amount of 12
It gradually rose to 0.

This temperature is maintained for 1 hour to complete the reaction. The reacted TIC14 containing by-products is then hot filtered. It is then washed twice hot with TIC 14 and refined five times with hebutane, which has been dehydrated by distillation over sodium metal. Chemical analysis of the retained catalyst components dried under vacuum gave the following results.

Ti=2.95%; CI=69%; M goods 0.5%; ratio○
=2.85% X-ray analysis showed the presence of MgC12 plaques 20.

The surface area of the retained catalyst components is 33.7〆/unit.
The minimum specific ultrasonic energy required to achieve complete particle destruction is 10.3 watt hours/sleeve.

The average radius of the holes is equal to 59A. 4. Equipped with a polymerized blade type lampshade, heating oil circuit, and cooling water circuit.
5 2000 cc of purified hebutane containing 42 AI tri-isobutyl are introduced into the autoclave of its holding volume.

The temperature is raised to about 75 oo and then the catalyst components dispersed in the hebutane are introduced under the pressure of day 2 supplied by the intake system. The amount introduced was 0.004, which corresponds to 0.00452 of Ti.
It was the 52nd evening. Then 7.5k 9' day 2 and 5.5k
9/20% ethylene is introduced and at the same time the temperature is raised to 8500. The pressure is kept constant by continuously feeding ethylene.

Polymerization is carried out for 4 hours. After degassing and cooling, 740
The polyethylene of the evening is taken out. The polymer is in the form of spherical particles of 1-2 rib diameter, which withstand the standard disintegration and setting tests described above. Example 2 The carrier used is the same as that in Example 1.

The method for producing the catalyst component is also the same, and the amount of reaction is also the same. With this same catalyst, propylene polymerization runs were conducted in liquid propylene with and without a composite agent.

Polymerization without Complexing Agents 3.1 days of N-tri-isobutyl in about 10 cc of hebutane in an atmosphere of 4 days and 2 days is introduced into the autoclave already described.

1150 for an autoclape with a small 2 bottles
Evening pool. Supply pyrene. The temperature is 30oo. Then, the Ti was removed using a 50cc bottle with overpressure twice a day.
．． It is introduced by charging 0.0141 parts of the same catalyst corresponding to 0.0045 parts and 0.9 parts of AI-triisobutyl in 20 cc of hebutane. Then the temperature is 60
00 and prove that at this temperature the pressure is equal to 27 atmospheres (overpressure depends on day 2 of injection). During the 4 hour polymerization the pressure drops to 21 atmospheres.

After cooling and releasing the propylene, 750 g of polypropylene is obtained.

The yield is 1,670,000 nights of polymer per night of Ti. The amount of residual bamboo from hebutane extraction is 18.8%.

The polymer is spherical in shape after extraction of the amorphous material with a diameter of about 1 sided and withstands both setting and disintegration tests. Polymerization of Triphenyl Phosphine with a Coupling Agent This example used the same autoclave and the same method as described for the operation without a compounding agent.

Four hours of Yamaichi tri-isobutyl in about 15 cc of hebutane are fed in two streams per day, followed by 1150 hours of propylene. Measure the catalyst at 0.009 (0.00 for Ti)
0.029 of triphenylphosphine in 20 cc of hebutane and are then placed in contact with each other for about 15 minutes).

The catalyst and phosphine are then charged into the autoclave at pressure twice a day. Then the temperature increases from 5000 to 60q0 and the pressure increases to 26 atmospheres. After 4 hours, the reaction mixture is cooled and the propylene is removed, yielding 143 g of polymer.

The yield is 500,000 nights of polymer per night of Ti.
The residue of hebutane extraction is 29.5%. The polymer is a spherical particle that withstands standard disintegration and setting tests after extraction of amorphous material. Polymerization with the Ethyl-Benzoate Complex The previously described autoclave was charged with 2 days under pressure of 3 times a day of triethyl and 1.5 times a day of ethyl benzoate in 11 cc of hebutane.

Then put 950 ml of propylene and 20 c in an autoclave.
The same catalyst (0.000
On day 2, a pressurized bottle of Ti (equivalent to 55 yen Ti) was introduced into the store. Then the temperature was set to 65 oo and the pressure was set to 28
Make it atmospheric pressure. After 4 hours of polymerization, the polymer is cooled and degassed, yielding a 43-day polymer in the form of flowing small spheres that withstands disintegration and setting tests, with a yield of 1 night's Ti. 78,000 per hour, and the extraction residue with heptane is equal to 63.6%.

Examples 3 to 7 Examples 3 and 4 are comparative examples.

The production of spherical hydrated MQ adsorbents takes place in a jacketed autoclave equipped with a thermocouple to measure the temperature and a siphon pump in the liquid phase in addition to having a pressure gauge. . The siphon pump is equipped with an outer sleeve tube into which a misting nozzle (0.64 mm diameter) is threaded.

Heating is provided by 4.5 atmospheres of water vapor circulating through the heating jacket. 4kg M or 12 for autoclape
・Introduce Fine 20.

The temperature is 128qo due to the steam circulating in the jacket.
rise to The pressure is brought to 22 atmospheres by introducing nitrogen into the autoclave. After heating the outside of the siphon leading to the Akebono nozzle with steam, open the valve,
Fog with molten chloride. The exposed chloride is collected in a closed nitrogen sump containing anhydrous hebutane.

Once the atomization is complete, the spherical powder is removed from the solvent and dried in an oven at <8000 in a stream of nitrogen to remove the solvent. The carrier has been shown to consist of spheres having a diameter of less than 350 microns; approximately 30% are less than 150 microns. After sectioning the support and selecting sections in the range 105-149 microns, the latter was dried in an oven at various temperatures.

Data regarding the dehydration of spherical chlorides to obtain various degrees of hydration are given in Table 1.

The supported catalyst component was prepared using a dehydrated support and operating according to the method described in Example 1.

Reaction conditions, amounts of reactants and analytical data for retained components are shown in Table 2. Polymerizations for ethylene were carried out on the same equipment and in the same manner as previously described. Data on the polymerization conditions, the results obtained and the properties of the polymers are given in Table 3.

Table 1 Table 3 Table 2 Examples 8-10 Examples 8 and 9 are comparative examples.

The catalyst components used in these examples were those of Example 3, respectively.
, 4 and 6 of magnesium hexahydrate, tetrahydrate and dihydrate with a particle size of 62 to 105 microns.

The catalyst components were prepared in the same manner according to Examples 3, 4 and 6.

Further, the polymerization operation was carried out under the same conditions as in the above-mentioned examples.

Table 4 shows data on the properties of the catalyst components retained, the results of the polymerization run and the properties of the polymers obtained. Table 4 Example 11 Melted MgC12.Navy 20 is atomized by the method described in Example 1.

The product thus obtained is fractionated to separate the fraction having a particle size in the range 105-149 microns. The part is then dried in an oven under a stream of nitrogen at 80° C. for 4 hours.

In X-ray examination the product is found to consist of MgC12.2.20.

80 minutes of this product is then reacted with 2000 cc of TIC14 in the apparatus described above in Example 1.

After 1 hour reaction, excess TIC14 was removed and 2000cc of fresh TIC heated to 120oo
14 is added and the temperature is maintained at 135 qC for an additional hour.

The TIC14 is then discharged and the product is washed three times with hot TIC14 and washed six times with heptane. The analysis of the dried product shows the following results.

Ti=8.55%, CI=61.45%: Mg=17.
The specific surface area of the 25% product is 27.4 Watt hours/hour and the resistance to particle disintegration is equal to 12.8 Watt hours/hour.
The average radius of the holes is 42A. 0.051 of this product
The polymer was used for the polymerization of ethylene under the conditions of Example 1.

Thereby, 150 particles of polymer were obtained, consisting essentially of spherical particles, but in which particles of irregular geometric shape were also present.

Polymers subjected to standard disintegration and densification tests did not disintegrate or aggregate. Example 12 60 minutes of MgC12 fine 20 in the form of spherical particles with a size of 53 to 105 microns obtained by atomization using the apparatus described in Example 1 was heated using a flywheel machine and a reflux condenser. React with 2500 cc of SOC12 placed in the flask provided.

The reaction starts at 5000 ml with gas evolution. During the reaction the temperature gradually rises to 70°C. The reaction continues until a product is formed, the composition of which is MgC12.1.
It was group 20.

Thirty minutes of this product is then reacted with TIC14 under the same conditions as in Example 1.

Analysis of the product vacuum dried at 7000 g gives the following results.

Tj=2.80%; CI=67.80% The specific surface area is 77.2 force/unit.

The resistance to particle decay is 3.9 watt-hours/sleeve;
The average radius of the holes is 92Δ.

0.0372 of this product is used to polymerize ethylene under the same conditions as in Example 1.

This yielded a polymer of spherical particles that did not fracture or aggregate when subjected to standard collapse and densification resistance tests. Example 13 Composition MgC12.1. obtained under the conditions of Example 12.
Fifty portions of the spherical product of Example 20 are reacted with 50 cc of ethyl benzene.

After one song time, the liquid is completely absorbed.

The solid product was diluted with hebutane to give a suspension of approx.
Dry under high vacuum at 0.

The dried product was heated to 200 ml to remove coarse particles.
Distinguish on the micron node.

Thirty minutes of the product thus obtained are reacted under the conditions of Example 1 with 2000 cc of TIC14.

The product dried under vacuum gives the following analytical results. T
i = 2.5%: CI = 64%; Mg = 21.2% The specific surface area is 118.9 〆' and the resistance to particle disintegration is 1.7 watt hours/sleeve. The average radius of the holes is 92Δ. 0.041 hours of the product was used in the polymerization of ethylene under the conditions of Example 1.

The polymer thus obtained was spherical particles with a diameter of 1 to 2 willows. It was subjected to standard tests to measure resistance to disintegration and densification and did not disintegrate or aggregate. Example 14 MgC12 fine 20 particles with a size of 53 to 105 microns obtained by the spraying method described in Example 1 were sprayed with a stream of gaseous HCI at 110 qo. Manufactured by dehydration in

45 minutes of the product was then treated with T under the same conditions as in Example 1.
React with IC14. The thus obtained retained catalyst component after drying gives the following analytical results.

Ti=0.3%; CI=69.80%, Mg=25.6
The 0% specific surface area is 3.7/sleeve and the resistance to collapse is 6.4 watt hours/sleeve.

The average radius of the holes is 45Δ. 0.190 of this product
The second batch was used for the polymerization of ethylene under the same conditions as in Example 1.

Thereby, 70 particles of spherical polymer having a diameter of 1 to 2 mm are obtained which do not disintegrate or aggregate when subjected to standard tests measuring resistance to disintegration and densification.

The embodiments of the present invention are summarized as follows.

(1-) In addition to the Mg halide, the carrier can also contain a co-carrier selected from compounds of elements of groups 1 to W of the periodic table and which is inert to the Mg halide.

[2} The carrier can be improved by reacting with an electron donating compound.

{3' Hydrated magnesium in the molten state or dissolved in water when reacting a magnesium halide with a halogen-containing titanium compound and then reacting it with a metal-organic compound of a metal of groups L and M of the periodic table. - Obtain spherical particles by blowing up the jihalides, with diameters of 1 to 350.
The micron particles are separated, the dihalide particles are dehydrated to a value of 0.5 to 3.5 moles of water of crystallization per mole of magnesium dihalide, and the partially dehydrated particles are placed in a liquid medium containing a halogen-containing titanium compound. Finally, the titanium compound not fixed to the magnesium dihalide is removed, and the final product is reacted with a metal organic compound.

Claims (1)

[Claims] 1. (a) a metal organic compound of aluminum selected from trialkyl aluminum compounds and dialkyl aluminum halides, (b) (c) a support consisting of anhydrous magnesium halide, and (d) chemical reaction on the support. A product consisting of a halogen-containing titanium compound bound to or homogeneously dispersed on a support, said product comprising 1
Generates a specific power of 0-80 watts/l, 22.4-45
In the average radius, surface area and resistance to ultrasonic vibrations of the pores, when measured using a device with a frequency of KHz: (1) the resistance to ultrasonic vibrations is between 5 and 40 watt hours/l, The radius is 30-70 Å and the surface is 3-70 m^2/g.(2) The resistance to ultrasonic vibration is 1-20 watt hours/l, the average radius of the pores is 70-150 Å, and Surface area is 70m^2/
A polymer having a diameter of 1 to 350 g, suitable for polymerizing an olefin into a spherical polymer having strong resistance to disintegration, and having a strong resistance to disintegration. A catalyst for the polymerization of olefins, which is micron spherical particles.