Method of obtaining polymers or copolymers of ethylenic hydrocarbons

The present invention relates to a process for producing olefin polymers or copolymers.

The patent literature widely describes polymerization and copolymerization of olefins in which catalysts containing titanium halide supported on anhydrous magnesium halides in active form are used.

Since the use of magnesium halides in active form as carriers for Ziegler-Natta catalysts has been described for the first time in U.S. Patent Nos. 4,287,188 and 3,395,338, the patent literature in this area is becoming more and more extensive.

The most active forms of magnesium halides are characterized by an X-ray spectrum, in which the reflex of maximum intensity appearing in the spectrum of inactive halides no longer occurs, but is replaced by a halo with the maximum intensity shifted towards smaller angles relative to the reflex angles of maximum intensity in the inactive halide.

In less active forms of magnesium chloride, the reflex with maximum intensity that occurs at 2.56 A (2v = 35 °) is not present, but is replaced by a halo with a maximum intensity between the angles of 2 v 33.5 ° and 35 °, at what reflexes are always present at 2 v 14.95 °.

The introduction of magnesium chloride based catalysts in industrial practice has enabled significant simplification of polyolefin production processes. In particular, the possibility of obtaining catalysts in the form of spherical particles allowed the production of polymers which

165 028 copy the form of a catalyst, have satisfactory morphological characteristics (flowability, bulk density) and do not require granulation, which is known to be expensive in terms of energy consumption.

Examples of controlled particle size catalysts are described in U.S. Patent No. 3,953,4-4.

The polymer (polyethylene) that can be obtained using these catalysts has very good morphological characteristics, however the yield of these catalysts is not high (usually from 2000 to 15000 g / g catalyst). When the polymer yield increases to values ​​higher than 20,000 g / g of catalyst, the polymer particles formed are brittle and the apparent density is very low.

The catalyst components described in the above-mentioned US patent are made from the MgCb.óHaO adduct, which was transformed into spheres in a dry-cooling apparatus and then reacted with TiCU.

U.S. Patent No. 4,399,054 describes catalyst components for olefin polymerization, which are further suitable for producing a polymer (polypropylene) with good flowability and bulk density. The polymer yield when using such a catalyst is not very high (from 3000 to 9000 g / g catalyst, when polymerized in heptane at 70 ° C for 4 hours at a partial pressure of propylene of 0.68 MPa).

Catalyst components are prepared from MgCl2 adducts with alcohols, in the form of spherical particles usually containing 3 moles of alcohol.

Before the reaction with TiCl4, the alcohol content is reduced to 2.5 - 2 moles, resulting in the use of such catalysts to obtain non-fragile spherical forms of polymers. The alcohol content never drops below 2 moles, as it drastically reduces the catalyst activity.

In the case of magnesium chloride, at least in less active forms (those in the spectrum of which there are two halo with intensity peaks between angles of 2 v from 30.45 ° to 3i ° and 33.5 ° to 35 °, respectively), a reflex that in the spectrum of inactive magnesium chloride occurs at v 14.95 ° is still present.

The present invention relates to a process for the preparation of olefin polymers or copolymers of the formula CH2 = CHR in which R is a hydrogen atom, an alkyl or aryl radical of 1 - 8 carbon atoms, which are in the form of spherical particles with an average diameter in the range of 50 - 5000μτη and optimal characteristics morphological (flowability and bulk density).

The process according to the invention consists in the polymerization of monomers at a temperature in the range 20 - 50 ° C in the presence of a catalyst that comprises a reaction product between i) a catalyst component containing titanium halide alcoholate or titanium halide and optionally an electron donor compound supported on anhydrous magnesium chloride, which component has form of spherical particles with an average diameter of 10 to 350μτη, specific surface from 20 to 250cm²/ g, porosity greater than 0.2cm³/ gi is characterized by an X-ray spectrum (CuK a) in which (a) reflections occur at 2 v35 ° and 14.95 ° (characteristic for magnesium chloride) or (b) reflections at 2 v 35 ° are replaced by a halo of maximum intensity between 2 v 33.5 and 35 ° angles, and reflex at 2 v 14.95 ° does not occur and 2) an aluminum alkyl compound.

ASTM D-3854 standard is cited for the definition of magnesium chloride X-ray spectrum. Spectra are obtained using copper anti-cathode and K a radiation.

Spectra with the characteristics (a) is appropriate for catalytic components with a specific surface area less than 70 - 80 m / g and a porosity greater than 0.4 cm³/ G. The spectrum with the characteristic (b) is appropriate for components with a specific surface area greater than 60 m²/ g and porosity from 0.25 to 0.4 cm³/ G. _e

The pore volume distribution is such that more than 50% of the pores have a radius greater than 100 A. In components with an area of ​​less than 100 m2 / g, more than 70% of the pores have a radius greater than 100 A.

As already indicated, in the polymerization process of the invention using a catalyst based on the above-mentioned component, olefin (co) polymers are produced in the form of spherical particles with valuable morphological characteristics (high bulk density, capacity

165 028 flow and mechanical resistance). The average diameter of polymer particles is from 50 to 5000 pm.

For the production of high and low density ethylene polymers (HDPE and LLDPE), catalysts obtained from components with a specific surface area less than 100 m are particularly suitable²/ g and porosity greater than 0.4 cm³/ G. The catalysts have very high activity and the resulting spherical polymer has attractive morphological characteristics (very high bulk density, flowability and mechanical strength).

For the production of crystalline polymers and copolymers of propylene, so-called impact copolymers obtained from subsequent polymerizations of (1) propylene and (2) mixtures of ethylene and propylene, catalysts obtained from components with a specific surface area greater than 60-70 m2 / g and porosity less than 0 are preferred. 4 cm3 / g. They are also used for the production of ethylene propylene rubbers (EP rubbers) or ethylene propylene hydrated rubbers (EPDM rubbers) and propylene polymer compositions which contain such rubbers.

By the method according to the invention, using the catalysts described above unexpectedly, these types of rubbers with spherical particles, good flowability and bulk density can be obtained, while up to now it has not been possible to obtain elastomeric polymers of the types mentioned above, with granular liquid particles due to insurmountable problems of contamination reactors and / or particle agglomeration.

Especially in the case of polypropylene, when using stereospecific catalysts obtained from components with a specific surface area of ​​about 60 - 70 m2 / g, porosity less than 0.4 cm3 / g and X-ray spectrum type (b), it is possible to obtain crystalline polypropylene and propylene and ethylene copolymers, containing less ethylene, characterized by significantly increased porosity, which makes them very attractive for making master batches with pigments and / or additives.

It is also remarkable that the catalysts used in the process of the invention are very active, although the magnesium chloride contained therein has an x-ray spectrum specific for low activity magnesium chloride.

Finally, it is surprising and completely unexpected that magnesium chloride is present in the crystalline form, with the X-ray spectrum indicated in (b).

The catalyst component is produced in various ways. The preferred method is to start with magnesium chloride / alcohol adducts containing such an amount of alcohol moles that the adduct is solid at room temperature but melts at temperatures between 100 and 130 ° C. The number of moles of alcohol varies depending on the type of alcohol.

Alcohols of the formula ROH in which R is an alkyl, cycloalkyl or aryl radical with 1-12 carbon atoms are suitable. It is possible to use mixtures of these alcohols. Examples of alcohols are methanol, ethanol, propanol, butanol, 2-ethylhexanol and mixtures thereof.

For alcohols such as ethanol, propanol, butanol, the number of moles in the adduct is about three per mole of MgCl2. The alcohol and magnesium chloride are mixed in the inert liquid hydrocarbon immiscible with the adduct, bringing the melting point of the adduct. The mixture is stirred vigorously (using for example an Ultra Turrax T-45N apparatus rotating at 2000 - 5000 rpm (Jonke and Kunkel (KG IKG Werkel)). The resulting emulsion is cooled in a very short time. This solidifies the adduct in the form of spherical particles of the desired dimensions. The particles are dried and then subjected to partial de-alcoholization by heating to temperatures rising from 50 ° to 130 ° C.

The partially de-alcoholised adduct is in the form of spherical particles with an average diameter of 50 to 350 μm, specific surface of 10 to 50 m²/ g and a porosity of 0.6 to 2 cm²/ g (measured with a mercury porosity meter). The higher the degree of alcohol removal, the higher the porosity. The pore volume distribution is such that more than 50% of the pores have a radius greater than 10,000 A. De-alcoholization is carried out up to an alcohol content of not more than 2 moles per mole of MgCl2, preferably from 0.15 to 1.5 moles, particularly preferably from 0 , 3 to 1.5 moles. When de-alcoholization is carried out to values ​​lower than 0.2 mole of alcohol per mole of MgCk, the catalytic activity is significantly reduced.

Then the partially dealcoholized adduct is suspended in cold TiCL at a concentration of 40-50 g / l and brought to a temperature of 80 - 135 ° C and kept at this temperature for 0.5 to 2

165 028 hours. The excess TiCU is separated hot by filtration or sedimentation. The TiCU treatment is repeated one or more times if the desired alcohol content is to be very low (usually less than 0.5% by weight).

During the preparation of the catalytic component containing the electron-donor compound, it is added to TiCl 4 in an amount equal to the molar ratio relative to MgCl 2 of 1: 6 to 1:16.

After treatment with TiCU, the solid is washed with a hydrocarbon, for example hexane or heptane, and then dried.

According to another method, the molten adduct in the inert hydrocarbon emulsion is passed through a tube of suitable length by turbulent motion and then collected in the inert hydrocarbon kept at a low temperature. This method is described in U.S. Patent No. 4,399,054. In this case, the adduct particles are also partially dealcoholated and reacted with TiCl 2.

In a variant of the method described above, the titanium compound, especially when it is solid at room temperature, such as, for example, TiCU, dissolves in the molten adduct, which is then deaccolated as indicated above and reacted with a halogenating agent capable of reacting and separating hydroxyl groups, such as SiCU, for example.

In the initial molten adduct, co-agents such as AlCU, AlBr3, ZnCl may also be present in addition to the titanium compound and possibly other transition metals₂.

Titanium compounds suitable for the preparation of catalyst components in addition to TiCl2 and TiCl2 and similar halides, may also include titanium halide alcoholates, such as trichlorophenoxy titanium and trichlorobutoxytitanium.

Finally, the titanium compound can be used in mixtures with other transition metal compounds such as V, Zr and Hf halides and halogen alcoholates.

As already indicated, the catalyst component may also contain an electron-donor compound (inside the donor). This is necessary when the catalyst component must be used in the stereoregular polymerization of olefins such as propylene, 1-butene and 4-methyl-1-pentene.

Electron donor compounds can be selected from ethers, esters, amines, ketones.

Preferred compounds are the alkyl, cycloalkyl and aryl esters of polycarboxylic acids such as phthalic and maleic acid and the ethers of the formula shown in the drawing wherein R 'and R are the same or different and are alkyl, cycloalkyl or aryl radicals with 1-18 atoms coal, and R¹¹¹ and R^IV are the same or different and are alkyl radicals with 1 to 4 carbon atoms. Ethers of this type are described in U.S. Patent Application No. 3,592, 234, filed May 31, 1989.

Examples representing these compounds are n-butyl phthalate, diisobutyl phthalate, di-n-octyl phthalate, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane,

2,2-dii ^ butyl ^ -1, ^^ <^^^^ t ^ ok ^; y ^^ mastered, 2-isopropyl --- isopentyl-1,3-dimethoxypropane.

The internal donor is usually present in a molar ratio relative to Mg of 1: 8 -1: 14. The titanium compound, expressed as Ti, is present in an amount of 0.5 to 10% by weight.

Alkyl aluminum compounds selected in particular from among trialkyl aluminum such as triethylaluminum, triisobutylaluminum and tri-n-butylaluminum are used as catalysts.

The Al / Ti ratio is greater than 1 and is usually between 20-800.

For stereoregular polymerization of alpha-olefins such as propylene and 1-butene, in addition to the aluminum aluminum compound, an electron-donor compound (external donor) is usually also used. This compound may be the same or different from the electron-donor compound present as the internal donor.

When the internal donor is a polycarboxylic acid ester, especially phthalate, the external donor is preferably selected from silicon compounds of formula R1R2Si (OR)₂in which R1 and R₂ are alkyl, cycloalkyl or aryl radicals with 1 to 18 carbon atoms and R is an alkyl radical with 1 to 4 carbon atoms. Examples of these silanes are methylcyclohexyldimethoxysilane, diphenyldimethoxysilane, methyl-t-butyldimethoxysilane.

Conveniently, 1,3-diethers with the formula shown can also be used.

If the internal donor is one of these diethers, there is no need for an external donor because the stereospecificity of the catalyst is high enough.

165 028

Catalysts containing an internal donor are used to produce LLDPE with limited molecular weight distribution. As already indicated, the catalysts are used for the polymerization of olefins of the formula CH2 = CHR, in which R is a hydrogen atom, an alkyl or aryl radical with 1-8 carbon atoms and mixtures of these olefins with or without diene.

The polymerization is carried out according to known methods in the liquid phase, in the presence or absence of an inert hydrocarbon diluent, or in the gas phase.

It is also possible to use mixed gas-liquid processes in which one or more polymerization stages are carried out in the liquid phase and one or more subsequent stages are carried out in the gas phase.

Polymerization temperatures are usually in the range of 20 to 150 ° C, preferably 60 to 90 ° C. The operation takes place at atmospheric pressure or higher.

The data shown in the examples and description refers to the following properties, determined according to the methods indicated below:

MIL flow indicator according to ASTM-D 1238, MIE flow indicator according to ASTMD 1238, MIF flow indicator according to ASTM-D 1238;

xylene soluble fraction (see assay before examples);

isotacticity index (II) - weight percentage of polymer insoluble in xylene at 25 ° C. Basically, it agrees with the weight percentage of polymer insoluble in boiling n-heptane;

BET surface (Sorptomatic 1800 - C. Erba apparatus was used);

porosity - unless otherwise stated, porosity is determined by the BET method. Calculates from the integral pore distribution curve as a function of the pores themselves;

porosity (mercury) - determined by immersing a known amount of sample in a known amount of mercury inside a dilatometer and a gradual hydraulic increase in mercury pressure. The pressure for introducing mercury into the pores is a function of the pore diameter. The measurement is carried out using a porosimeter 2000 Series (C. Erba). The total porosity is calculated from the reduction of the mercury volume and the pressure used;

flowability - flow time of 100 g of polymer through a funnel whose outlet opening has a diameter of 1.25 cm and the walls are inclined at an angle of 20 ° C in relation to the vertical;

morphology according to ASTM-D 1921-63; bulk density according to DIN-53194.

Determination of percentage soluble in xylene.

g of the polymer is formed in 250 mil xylene at 135 ° C. with stirring. After 20 minutes, the solution is allowed to cool while stirring until the temperature reaches 25 ° C. After 30 minutes, the precipitated material is filtered through a filter, the solution is evaporated under a stream of nitrogen and the residue is dried in vacuo at 80 ° C until a constant weight is obtained. In this way, the percentage of xylene soluble polymer at room temperature is calculated.

Examples

Method for producing MgCU / alcohol adducts.

MgCU / alkOhol adducts in the form of spherical particles are prepared as described in Example 2 of US Patent No. 4,399,054 using 3000 rpm instead of 1000 rpm. The adduct was partially dealcoholized by heating at a temperature rising from 30 ° C to 180 ° C using a nitrogen flow.

Method for producing the solid catalyst component.

Into a liter flask equipped with a condenser and a mechanical stirrer, 625 ml of TiCU was added under a flow of nitrogen. At 0 ° C, 25 g of the partially alcohol alcohol adduct was added with stirring. The mixture was then heated to 100 ° C for an hour and when the temperature reached 40 ° C, diisobutyl phthalate was added in a molar ratio Mg / DIBF = 8. The temperature was kept at 100 ° C for 2 hours, then the mixture was allowed to decant and the hot liquid was poured off. 550 ml of TiCU were added and the mixture heated to 120 ° C for an hour. Finally, it was allowed to stand and the hot liquid was poured off. The residual solid was washed 6 times with 200 ml portions of anhydrous hexane at 60 ° C and 3 times at room temperature. Then the solid was dried in vacuo.

Polymerization of propylene.

165 028

Into a 41 stainless steel autoclave, equipped with a stirrer and thermostat, which was degassed with nitrogen at 70 ° C for one hour and then with propylene, was introduced at 30 ° C without stirring but with a slight flow of propylene, a catalytic system which suspended the above solid catalyst component in 80 ml hexane, 0.76 g triethylaluminum and 8.1 mg diphenyldimethoxysilane (DPMS). The suspension was prepared immediately before the trial. The autoclave was then closed and 1 NI H2 was introduced. While stirring placed

1.2 kg of liquid propylene and the temperature was brought to 70 ° C over 5 minutes, keeping it constant for 2 hours. At the end of the test, mixing was stopped and unreacted propylene was removed. The autoclave was cooled to room temperature, the polymer was removed and dried at 70 ° C in a drier under nitrogen flow for 3 hours and then analyzed.

Copolymerization of ethylene with butene-1 (LLDPE).

The autoclave described above was degassed with propane instead of propylene. A 25 cm catalytic system was introduced into the autoclave³ of hexane, 1.05 g of triisobutylguyne and the above catalyst component, at room temperature, with a slight flow of propane. The pressure increased by 0.54 MPa under the influence of H2, and then by 0.19 MPa under the influence of ethylene. Prepolymerization was carried out at 45 ° C using 15 g of ethylene.

Propane and hydrogen were degassed and after washing with hydrogen the gas phase was formed from 37.0 g of ethylene and 31.9 g of butene-1 and hydrogen at a pressure of 0.17 MPa (total pressure 1.5 MPa). Then a mixture of ethylene and butene-1 was fed in a 9: 1 weight ratio at 70 ° C for 2 hours. Finally the autoclave was degassed and cooled quickly to room temperature. The resulting copolymer was dried at 70 ° C under nitrogen for 4 hours in an oven.

Polymerization of ethylene.

A 2.51 stainless steel autoclave equipped with a stirrer and thermostat was blown as described above for the propylene test using ethylene instead of propylene. At 45 ° C, a stream of hydrogen, 900 ml of a solution containing 0.5 g / l of triisobutylaluminum in anhydrous hexane was introduced, and immediately afterwards the catalyst component suspended in 100 ml of the solution described above. The temperature was quickly brought to 70 ° C and hydrogen was fed until the pressure reached 0.29 MPa, followed by ethylene until the pressure reached 1 MPa. These conditions were maintained for 3 hours, replenishing ethylene continuously. At the end of the polymerization reaction, the autoclave was evacuated quickly and cooled to room temperature.

The polymeric suspension was filtered and the solid residue was dried under a stream of nitrogen at 60 ° C for 8 hours.

Example 1. A spherical MgCl2'3EtOH adduct (obtained as described in the general method) was dealcoholated until an EtOH / MgCl2 = 1.7 molar ratio was obtained.

A product with the following characteristics was obtained: porosity (mercury) = 0.904 cm³/ g, specific surface = 9.2 m2 / g, bulk density = 0.607 g / cm³.

From this adduct, by treatment with TiCl 2 as described in the general method, a catalyst component was obtained in the spherical form with the following characteristics:

Ti = 2.5% by weight,

DIBF = 8.2% by weight, porosity = 0.405 cm3 / g, specific surface = 249 m2 / g, bulk density = 0.554 g / cm³.

The X-ray spectrum of the component had no reflection at 2 v 14.95, while the halo was present with maximum intensity at 2 v 34.72 °.

The catalyst component was used for the polymerization of propylene carried out as described in the general method. Using 0.01 catalyst component, 430 g of polymer was obtained with the following characteristics:

xylene soluble fraction at 25 ° C = 2.4%,

MIL = 2.5g / 10 ',

165 028 Bulk density = 0.48 g / cm³, morphology: 100% spherical particles with a diameter of 100 - 5000 pm, flowability: 10 seconds.

Example 1 I. By partial de-alcoholization (according to example 1) of the spherical MgCbEtOH adduct also obtained according to the method indicated in Example 1, an adduct with an EtOH / MgCk 1.5 molar ratio and the following characteristics was obtained:

porosity (mercury) = 0.946 cm³/ g, specific surface = 9.1 m2 / g, bulk density = 0.654 g / cm³.

From the adduct by treatment with TiCL as stated above, a spherical catalyst component was prepared with the following characteristics:

Ti = 2.5% by weight,

DIBF = 8.0% by weight, porosity = 0.389 cm^and/ g, specific surface area = 221 m2 / g, bulk density = 0.555 g / cm³.

The X-ray spectrum of the component shows no reflection at 2 v 14.95 °, only halo with maximum intensity at 2 and 2.5780 ° is present.

The catalyst component was used for propylene polymerization carried out as described in Example 1.

Using 0.015 g of the catalyst component, 378 g of polypropylene were obtained with the following characteristics:

xylene soluble fraction at 25 ° C = 2.6%,

MIL = 2.8g / 10 ', bulk density = 0.395 g / cm³, morphology = 100% of spherical particles with a diameter of 1000 - 5000 pm, flowability - 12 seconds.

Example I II. By partial de-alcoholization (according to example 1) of the spherical MgCL6EtOH adduct obtained according to the method described in the previous examples, an adduct with an EtOH / MgCL ratio = 1 and the following characteristics was obtained:

porosity (mercury) = 1.208 cm³/ g, specific surface = 11.5 m2 / g, bulk density = 0.535 g / cm ?.

From this adduct, by reaction with TiCL described in the previous examples, a spherical catalytic component was obtained with the following characteristics:

Ti = 2.2% by weight,

DIBF = 6.8% by weight, porosity = 0.261 cm³/ g, specific surface = 66.5 m2 / g, bulk density = 0.440 g / cm3.

The x-ray spectrum of the catalytic component showed reflex at 2vI4.95 ° as well as at 2v 35 °.

Using 0.023 g of the catalyst component for propylene polymerization under the conditions given in Example 1, 1.412 g of polypropylene with the following characteristics were obtained:

xylene soluble fraction at room temperature 3.0%,

MIL = 3.2g / 10 ', bulk density = 0.35 g'cm3, morphology - 100% of spherical particles with a diameter of 500 - 5000 i / m, flowability - 12sec.

By following the procedure described in the general procedure, ethylene-butene was copolymerized using 0.0238 g of the catalyst component. 240 g of copolymer were obtained with the following characteristics:

bound butene = 8.3% by weight, xylene soluble at room temperature = 12.2%,

165 028

MIE = 12 g / 10 ';

MIF = 12g / 10 ',

MIF / MIE = 30, morphology = 100% spherical particles with a diameter of 500 - 5000 / m.

Example IV By partial de-alcoholization (according to Example 1) of the spherical MgCl2 * 3EtOH adduct obtained as described in the previous examples, an adduct with an EtOH / Mg = 0.4 molar ratio was obtained, which had the following characteristics:

porosity (mercury) = 1.604 cm³/ g, specific surface area = 36.3 m²/ g, apparent specific gravity = 0.310 g / cm³.

By treating this TiCU support at 135 ° C., 50 g / L, three times an hour, a spherical catalyst component was obtained, which, after removing excess TiCU, washing and drying, had the following characteristics:

Ti = 2.6% by weight, porosity = 0.427 cm3 / g, specific surface area = 66.5 m²/ G.

The X-ray spectrum of this component showed reflex at 2 v 19.95 ° as well as at 2v35 °.

Using 0.012 g of the catalyst component in ethylene polymerization according to the general method described above, 400 g of polyethylene with the following characteristics were obtained:

MIE = 0.144 g / 10 ',

MIF = 8.87g / 10 ',

MIF / MIE = 61.6, morphology = 100% spherical particles with a diameter between 100 and 5000pm, flowability = 12sec, apparent density = 0.38 g / cm³.

Example V. By partial de-alcoholization (as described in Example I) of the spherical MgCl2 adduct^-3EtOH prepared according to the method indicated in the previous examples, an adduct with a molar ratio of EtOH / MgCl2 0.15 was obtained, which had the following characteristics:

porosity (mercury) = 1.613 cm³/ g, specific surface area = 22 m2 / g.

The X-ray spectrum of this component showed reflex at 2 v 14.95 ° as well as at 2 v35 °.

Using 0.03 g of this component in ethylene polymerization as described in Example 4, 380 g of polyethylene were obtained with the following characteristics:

MIE = 0.205 g / 10 ',

MFI = 16.42 g / 10 ',

MIF / MIE = 80.1, flowability = 12 seconds, bulk density = 0.40 g / cm³.

Example VI. The MgCl2 * 1EtOH adduct was prepared as described in Example 3, but using the alcohol diluted water used to prepare the starting MgCl2'3EtOH in an amount of 2% by weight. The de-alcoholized adduct contained 20% water by weight. From this adduct, after treatment with TiCl2 and diisobutyl phthalate (DIBF) as described in Example 1, a spherical catalyst component was obtained with the composition: Ti = 2.35%, DIBF = 6.9%. Using 0.025 g of this component for propylene polymerization as described in Example 1, 410 g of polymer was obtained in the form of spherical particles having the following characteristics:

xylene soluble fraction at 25 ° C = 3.1%,

MIL = 3.0g / 10 ', apparent specific gravity = 0.35g / cm³, morphology = 100% of the spherical particles have a diameter between 100 and 5000pm, flowability = 13sec.

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