FI104632B - Process for the polymerization of olefins, and polymers and copolymers thus produced - Google Patents

Description

104632

A process for polymerizing olefins and the polymers and copolymers thus obtained

Divided by application 902107.

This invention relates to a process for the polymerization of olefins and to polymers and copolymers thus obtained.

Catalysts suitable for the polymerization of olefins containing titanium halide supported on anhydrous magnesium silicon halides in active form have been extensively described in the patent literature.

The patent literature has grown tremendously since the use of magnesium halides in active form as carriers for Ziegler-Natta catalyst components was first described in U.S. Patent Nos. 4,298,718 and 4,495,338.

The most active forms of magnesium halides are characterized by X-ray spectra in which the reflection in the spectrum of inactive halides having a max-2 sim intensity is no longer present, but is replaced by a light phenomenon having a maximum intensity and shifted towards smaller angles intense reflection occurs in the spectrum of the inactive halide.

In less active forms of magnesium chloride, the maximum intensity reflection at d-value of 0.256 nm (2v = 35 °) is no longer present but has been replaced by a light phenomenon with maximum intensity of 33.5 ° and 35v angles. ° sometimes; a reflection of 2v of 14.95 30 always occurs.

The introduction of magnesium chloride supported catalysts for industrial use allowed for a significant simplification of polyolefin production processes. In particular, it is possible to obtain catalysts in the form of spherical particles 35 capable of producing polymers which mimic the shape of the catalyst and which have satisfactory morphological properties (flowability and bulk density) and which do not require granulation which is known to be expensive due to energy use.

Examples of catalysts having a controlled particle size are given in U.S. Patent No. 3,953,414.

The polymer (polyethylene) obtained with said catalysts has good morphological properties, but the ability of these catalysts to produce polymer 10 is not very good (generally 2000 - 15000 g / g catalyst). As the yield of the polymer rises above 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 aforementioned U.S. Patent 15 are obtained from an MgCl 2 * 6H 2 O addition product which is formed into small spheres in a dry cooling type device and then reacted with TiCl 4.

The US patent describes catalyst components suitable for polymerization of olefins which are capable of producing a polymer (polypropylene) having good flow and bulk properties. The ability of the catalyst to produce polymer is not very good (3000 to 9000 g / g catalyst; polymerization in heptane at 70 ° C with a poly-25 polymerization time of 4 hours and a propylene partial pressure of 7 bar).

The catalyst components are obtained from the addition products of MgCl 2 and alcohols in the form of spherical particles which generally contain 3 moles of alcohol per mole of MgCl 2.

·; Prior to reaction with TiCl 4, the alcohol content is reduced to 2-2.5 moles to make the catalysts suitable for the preparation of non-brittle spherical polymers. The alcohol content is never reduced to about 104632 le 2 moles (it drastically reduces the activity of the catalyst).

In the case of magnesium chloride, at least its less active forms (forms with two light-phenomena in the spectrum with intensity peaks between 30,45 ° and 31 ° and 33,5 ° and 35 ° respectively), there is still reflection which the magnesium chloride spectrum exhibits a 2v value of 14.95 °.

Catalyst components useful in the polymerization of olefins CH2 = CHR in which R is an alkyl or aryl group having 10 or 1 to 8 carbon atoms have now been found which are suitable for the preparation of catalysts capable of producing spherical particulate polymers ( fluidity and high bulk density). In addition, the catalysts have considerable catalytic activity and are stereospecific.

The invention relates to a process for the preparation of polymers and copolymers of olefins of the formula CH2 = CHR, wherein R is hydrogen or an alkyl or aryl radical containing from 1 to 8 carbon atoms. The process is characterized in that the process is carried out in the presence of a catalyst comprising a reaction product of an Al-trialkyl compound and a solid catalyst component a), wherein the solid catalyst component a) comprises a thiophene compound having at least one Ti-halo , wherein the catalyst component is in the form of spherical particles having an average diameter of 10 to 350 µτη, a surface area of 30 to 250 m2 / g and a porosity of more than 0.2 cm3 / g, and having - ·; is an X-ray spectrum in which (a) the reflections at 2v angles of 35 ° and 14.95 ° or (b) the reflection at 2v angles of 35 ° are no longer present but have been replaced by the maximum intensity light phenomenon of 2v angles 33.5 ° and 35 35 and no reflection at a 2v angle of 14.95 °, 4 104632 and wherein the catalyst component is prepared by reacting the titanium compound with a MgCl 2 / ROH addition product wherein R is an alkyl, cycloalkyl or aryl group containing 1 -12 carbon atoms, wherein the adduct 5 contains 0.15 to 2 moles of alcohol per mole of MgCl 2 and is obtained by melting magnesium chloride / alcohol adducts containing alcohol moles such that the adduct is solid at room temperature but melts at 100-130 ° C to obtain spherical particles, and partially removing alcohol from the addition product in the form of spherical particles until the desired aliquot is obtained. alcohol content.

For the interpretation of the X-ray spectrum of magnesium chloride, reference is made to ASTM D-3854. Spectrum registration 15 is performed using a copper counter cathode and Κα radiation.

The type a spectrum is characteristic of catalyst components having a surface area of less than 70-80 m2 / g and a porosity of greater than 0.4 cm3 / g. Type b spectrum-producing components having a surface area of less than 60 m 2 / g and a porosity of 0.25 to 0.4 cm 3 / g.

The pore size distribution is such that more than 50% of the pores have a radius greater than 10 nm. For components with a surface area of less than 100 m 2 / g, more than 70% of the pores have a radius greater than 10 nm.

v-25 As already mentioned, the catalyst components of the invention provide catalysts suitable for producing olefinic (co) polymers in the form of spherical particles with valuable morphological properties (high bulk density, castability and mechanical resistance). . The average particle size of the polymer particles is 50 - 5000 μπι.

In particular, catalysts obtained from components having a surface area of less than 100 m 2 / g and a porosity greater than 0.4 cm 3 / g are useful in the preparation of ethylene polymers (HDPE and LLDPE). The catalysts have very high activity and the resulting spherical polymer has intriguing morphological properties (high bulk density, flowability and mechanical resistance).

Catalysts obtained from components having a surface area greater than 60 to 70 m2 / g and a porosity of less than 0.4 cm3 / g are preferred for use in the preparation of crystalline propylene homopolymers and so-called copolymers. impact copolymers obtained by sequential polymerization of 1) propylene and 2) ethylene-propylene mixtures.

They are preferably used in the preparation of ethylene propylene rubbers (EP rubbers) or ethylene propylene diene rubbers (EPDM rubbers) and propylene polymer compositions containing said rubbers.

Surprisingly, the catalysts of this invention can provide these types of rubbers in the form of spherical particles having good flow and bulk density properties, since up to now it has not been possible to prepare elastomeric polymers of the above type in the form of flowable granule particles and because of insurmountable problems associated with particle agglomeration.

Particularly in the case of polypropylene is the stereosphere.

specific catalysts obtained from components having a surface area of about 60-70 m2, a porosity of less than 0.4 cm 3 / g and an X-ray spectrum of type b, it is possible to obtain crystalline propylene homopolymers and propylene-30 ethylene copolymers having a lower ethylene content. · Characterized by significantly elevated porosity values, which make them very attractive for the preparation of pigment and / or additive storage compositions.

6 104632

It is also surprising that the catalysts of the invention are highly active, even though the magnesium chloride contained therein produces an X-ray spectrum which is characteristic of the low-activity forms of the magnesium chloride itself.

Furthermore, it is still surprising and completely unexpected that magnesium chloride is in a crystalline form having an X-ray spectrum as mentioned in (b).

The preparation of the catalyst components is carried out in many different ways. The preferred process starts with magnesium chloride alcohol addition products containing so many moles of alcohol that the addition product is solid at room temperature but melts at 100-130 ° C.

The number of moles of alcohol varies according to the different types of alcohol.

Suitable alcohols have the formula ROH, wherein R is an alkyl, cycloalkyl or aryl group containing from 1 to 12 carbon atoms. It is also possible to use mixtures of said alcohols.

Examples of alcohols are methanol, ethanol, propanol, butanol, 2-ethylhexanol and mixtures thereof.

For alcohols such as ethanol, propanol and butanol, the number of moles is about 3

Per mole of MgCl 2. The alcohol and magnesium chloride are mixed in an inert liquid hydrocarbon which is immiscible with the addition product and heated to the melting point of the addition product. The mixture is stirred vigorously [using, for example, a ULTRA TURRAX T-45N rotary speed machine (Jonke & Kunkel, K.G. IKG Werkel) at 2,000-5,000 rpm.

The resulting emulsion is cooled in a very short time. This causes the addition product to solidify into spherical particles of desired size. The particles are dried, Ί 7 104632, and then part of the alcohol is removed by heating them, gradually raising the temperature from 50 ° C to 130 ° C.

The partially dealcoholated adduct is in the form of spherical particles of average heat-5 sphericity of 50 to 3 50 μτη with a surface area of 10 to 50 m2 / g and a porosity of 0.6 to 2 cm3 / g (as determined by a mercury porosity meter).

The higher the degree of alcohol removal, the greater the porosity. The pore size distribution is such that 10 in more than 50% of the pores have a radius greater than 10 nm.

The alcohol removal is continued until the alcohol content does not exceed 2 moles per mole of MgCl 2 and is preferably 0.15-1.5 moles, especially 0.3-1.5 moles.

Continuing the removal of the alcohol until less than 0.2 mole of alcohol per 15 moles of MgCl 2 significantly reduces the catalytic activity.

The partially dealcoholated adduct is then suspended in cold TiCl 4 such that the suspension contains 40 to 50 g of adduct / liter, and then the suspension is cooled to 80-135 ° C for 0.5 to 2 hours. Excess TiCl4 is filtered off or filtered while hot.

The treatment with TiCl4 is repeated once or more if the alcohol content is desired to be very low (generally less than 0.5% by weight).

In the preparation of the catalyst component containing the electron donating compound, the former is added to TiCl 4 in amounts corresponding to its molar ratio of MgCl 2 to 1: 6 to 1:16.

After treatment with TiCl4, the solid is washed with charcoal, hydrogen (e.g. hexane or heptane) and dried.

According to another method, the molten addition product, emulsified in an inert hydrocarbon, is passed through a suitable tube of length 35 and vortexed and then collected in β 104632 in an inert hydrocarbon at low temperature. Said method is disclosed in U.S. Patent 4,399,054, to which we refer to the description. In this case, the addition product particles are both dealololized into 5 parts and reacted with TiCl 4.

In one variation of the methods described above, the titanium compound, especially when solid at room temperature, such as TiCl 3, is dissolved in a molten addition product which is then de-alcoholized as described above and then reacted with a reactive halogenating agent such as SiCl.

The molten addition product used as a starting material may contain, in addition to the titanium compound and any other transition metal compounds, co-carriers such as AlCl 3;

AlBr or ZnCl2.

Titanium compounds suitable for the preparation of catalyst components include, in addition to TiCl 4 and TiCl 3 and other similar halides, other compounds containing at least one Ti halogen bond, such as haloalcoholates such as trichlorophenoxy titanium and trichlorobutoxy titanium.

Further, the titanium compound can be used in admixture with other transition metal compounds, such as V, Zr and Hf-halide logenides and haloalcoholates.

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

As the electron donating compounds, there are questionable ethers, esters, amines and ketones.

fiil 9 104-632

Preferred compounds are the alkyl, cycloalkyl and aryl esters of polycarboxylic acids such as phthalic and maleic acid, and ethers of the formula CH CH-OR111 5C1111 "^^ ^ --CH2-OR ORlv These ethers are disclosed in U.S. Patent Application No. 359,234 filed May 31, 1989.

Representative examples of such 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, 15 ni, 2,2-diisobutyl-1,3-dimethoxypropane and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane.

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

Al-alkyl compounds, in particular Al-trialkyls such as Al-triethyl, Al-triisobutyl and Al-tri-n-butyl are used as co-catalysts.

The ratio of aluminum to titanium (Al / Ti) is greater than 1 and generally from 20 to 800.

The stereoregular polymerization of alpha-olefins such as propylene and 1-butene utilizes, in addition to the Al-alkyl compound, an electron donating compound (external donor). This compound may be the same or different from the electron donating compound present as an internal donor.

- *. When the internal donor is an ester of a polycarboxylic acid, in particular phthalate, the external donor is preferably a silicon compound of the formula RxR2Si (OR2) wherein Rx and R2 are alkyl, cycloalkyl or aryl groups containing 1-18 carbon atoms , and R is an alkyl group having 1 to 10463210 4 carbon atoms. Examples of typical such silanes are methylcyclohexyldimethylsilane, diphenyldimethoxysilane and methyl (t-butyl) dimethoxysilane.

1,3-diethers of the above formula may also be used advantageously.

If the internal donor is one of these dieters, it is not necessary to use an external donor because the stereospecificity of the catalyst itself is sufficiently high.

Internal donor containing catalysts are used in the preparation of LLDPE with a narrow molecular weight distribution. As already mentioned, the catalysts are used in the polymerization of olefins CH 2 = CHR where R is hydrogen or an alkyl or aryl group containing 1 to 8 carbon atoms or mixtures of said olefins in the presence or absence of diene.

The polymerization is carried out by known methods in the liquid phase, with or without an inert hydrocarbon diluent, or in the gas phase.

It is also possible to use liquid-gas mixed processes in which at least one stage of polymerization is carried out in a liquid phase and in one or more subsequent stages it is carried out in a gas phase.

The polymerization temperature is generally 20-150 ° C, preferably 60-90 ° C. The process is carried out at atmospheric pressure or higher.

The information given in the examples and in the text related to the following properties was obtained by the following assay methods: 30 Feature Method *. MIL Flow Index ASTM-D 1238 «MIE Flow Index ASTM-D 1238 MIF Flow Index ASTM-D 1238,

Xylene Soluble Fraction (See Examples for Assay 35 above) i 11 104632

Isotactic value (II) Percentage of polymer insoluble in xylene at 25 ° C. (Basically, it corresponds to a fraction (wt.%) Of the polymer insoluble in n-heptane.)

Surface Area B.E.T (SORPTO-MATIC 1800 - C. Erba Appliance Used) 10 Porosity The porosity is determined by the B. E. T. method (see above) unless otherwise stated. It is calculated from an intergal curve depicting the pore-15 deflection as a function of the pores themselves.

Porosity (mercury) Assay by immersing a known amount of sample into a known amount of mercury inside the dilatometer and gradually increasing the pressure of the mercury hydraulically. The pressure at which mercury penetrates the pores is a function of the diameter of the pores. The measurement is carried out using a porosimeter Poro-simeter 2000 Series (C. Erba). The total porosity is calculated from the values of mercury volume pie-30 and pressure used, *.

Bulk density DIN 51 194 12 104632

Flowability The time it takes for 100 g of polymer to flow through a funnel of 1.25 cm 5 outlet diameter with walls at an angle of 20 ° from the vertical.

Morfologia ASTM-D 1921-63

Determination of the xylene solubility (%) 10 g of the polymer are dissolved in 250 ml of xylene at 135 ° C with stirring. After 20 minutes, the solution is allowed to cool while stirring is continued until it reaches 25 ° C.

After 30 minutes, the precipitated material is filtered off with filter paper, the solution is evaporated in a stream of nitrogen and the residue is dried under reduced pressure at 80 ° C until its mass no longer changes.

Thus, the percentage by weight of polymer soluble in xylene at room temperature is calculated.

20 Examples

Preparation of MgCl 2 Alcohol Addition Products Spherical MgCl 2 addition products are prepared by following the procedure of Example 2 of U.S. Patent 4,399,054, but using a speed of 3000 rpm instead of a speed of 10,000 rpm.

A portion of the alcohol was removed by heating it in a stream of nitrogen, gradually raising the temperature from 30 ° C to 180 ° C.

Preparation of Solid Catalyst Component * To a 1 liter flask equipped with a condenser and a mechanical stirrer was added 625 mL of TiCl 4 under a stream of nitrogen. At 0 ° C and with stirring, 25 g of partially dealcoholated adduct 35 was added. The mixture was then heated at 100 ° C for 1 hour to 104632 and when the temperature reached 40 ° C, diisobutyl phthalate (DIBF) was added to give a molar ratio of Mg to DIBF of 8.

The temperature was maintained at 100 ° C for 2 hours, after which the mixture was allowed to settle and the hot solution was subsequently drained. 550 ml of TiCl 4 were added and the mixture was heated to 120 ° C for 1 hour. Finally, the mixture was allowed to settle and the liquid was drained while still hot; the remaining solid was washed with 200 mL of anhydrous hexane at 60 ° C and three times at room temperature.

The solid was then dried under reduced pressure.

Polymerization of Propylene

Stainless steel autoclave wine (4 dm 3) equipped with a stirrer and thermostat system fed with nitrogen for 1 hour at 70 ° C and then propylene was added at 30 ° C without stirring but maintaining a low propylene flow catalyst system which consisted of a suspension of the above-mentioned solid catalyst component in hexane (80 mL), Al-triethyl (0.76 g) and diphenyldimethoxysilane (DPMS, 8.1 mg). The suspension was prepared just before the experiment.

The autoclave was then sealed and "25 1 dm 3 (NTP) H 2" was introduced. 1.2 kg of liquid propylene was added with stirring and the temperature was raised to 70 ° C for 5 minutes and held at this value for 2 hours.

At the end of the experiment, stirring was stopped and any unreacted propylene was removed. After the autoclave had cooled to room temperature, the polymer was recovered and. then dried at 70 ° C under a stream of nitrogen in a heat oven and then analyzed. t Copolymerization of ethylene with 1-butene (LLDPE)

The autoclave described above was fed with propane instead of 35 propylene. A catalyst system consisting of 104632 14 hexane (25 mL), Al-triisobutyl (1.05 g) and the above catalyst component was fed to the autoclave at room temperature while maintaining a low propane flow. The pressure was increased with 5.5 bar H2 and then with 5 2 bar ethylene and prepolymerized with ethylene until 15 g ethylene (45 ° C) had passed.

Propane and hydrogen were removed and, after washing the autoclave with H 2, a gas phase was formed using 37.0 g of ethylene, 31.9 g of 1-butene and 10 bar of H2 (total pressure 15 atm).

A mixture of ethylene and 1-butene was then fed in a weight ratio of 9: 1 at 70 ° C for 2 hours.

Finally, the autoclave was degassed and rapidly cooled to room temperature.

The recovered copolymer was dried under nitrogen at 70 ° C for 4 hours.

Copolymerization of ethylene

The stainless steel autoclave (2.5 dm 3) equipped with a stirrer and thermostat system was flushed as described above in the propylene test but using ethylene instead of propylene.

At 45 ° C, 900 ml of a solution of 0.5 g / l Al-triisobutyl in anhydrous hexane was added in a stream of H2, followed immediately by the catalyst component suspended in the above solution (100 ml).

The temperature was raised rapidly to 70 ° C and H2 was added until the pressure reached 3 bar, and then 30 ethylene to 10.5 bar. These conditions were maintained for 3 hours, continuously supplying new ethylene to replace the dead one. Upon completion of the polymerization reaction, the autoclave was rapidly evacuated and cooled to room temperature.

The polymerization suspension was filtered and the solid residue was dried under nitrogen at 60 ° C for 8 hours.

15 104632

Example 1

The spherical MgCl 2 -3EtOH addition product (prepared as described in the general procedure) was alcohol deprived until a molar ratio of EtOH to 5 MgCl 2 of 1.7 was reached.

A product was obtained which had the following characteristics: - porosity (mercury) = 0.904 cm3 / g - surface area 9.2 m2 / g 10 - bulk density = 0.607 g / cm3.

From this addition product, as described in the general method, a solid spherical catalyst was prepared which had the following characteristics: 15 - Ti = 2.5% by weight - DIBF = 8.2% by weight - Porosity = 0.405 cm 3 / g - Surface area = 24 9 m2 / g - bulk density = 0.554 g / cm3.

The X-ray spectrum of this component showed no reflections at a 2v angle of 14,958; instead, it showed a light phenomenon with a maximum intensity of 34.72 ° at 2v.

This catalyst component was used to polymerize propylene following the procedure described in the general section. Using 0.01 g of the component gave 430 g of a polymer having the following characteristics: - fraction soluble in xylene at 25 ° C = 2.4%. · · MIL = 2.5 g / 10 min - bulk density = 0.48 g / cm 3 4-shape: 100% spherical particles with a diameter of 1000 - 5000 μ 35 - flow rate = 10 s.

16 104632

Example 2

By partial removal of the alcohol (as in Example 1) from the spherical MgCl2 * 3EtOH addition product, similarly prepared by the procedure of Example 1, an addition product having a molar ratio of EtOH to MgCl2 of 1.5 having the following characteristics was prepared. : - porosity (mercury) = 0.946 cm3 / g - surface area = 9.1 m2 / g 10 - bulk density = 0.564 g / cm3.

From this addition product, a spherical catalyst component was prepared by the TiCl4 treatment described above, having the following characteristics: - Ti = 2.5% by weight 15 - DIBF = 8.0% by weight - Porosity = 0.389 cm3 / g - Surface area 221 m2 / g - bulk density = 0.555 g / cm 3.

The X-ray spectrum of this component showed no reflections at a 2v angle of 14.95 °; it only showed a light phenomenon with a maximum intensity of 2V of 2.5780 °.

This catalyst was used to polymerize propylene according to the procedure of Example 1.

Using 0.015 g of catalyst yielded 378 g of '25 polypropylene having the following characteristics: - fraction soluble in xylene at 25 ° C = 2.6% - MIL = 2.8 g / 10 min 30 - bulk density = 0.395 g / cm 3 - morphology = 100% spherical particles with diameter between 1000 and 5000 μτη - flowability = 12 s. ΐ 17 104632

Example 3

Partial removal of the alcohol (as in Example 1) from a spherical MgCl2 * 3EtOH addition product, similarly prepared by the procedure described in the preceding Examples, gave the addition product (EtOH: MgCl2 = 1) having the following characteristics: - porosity (mercury) = 1.208 cm / g - under the surface 11.5 m2 / g - bulk density = 0.535 g / cm 3.

From said addition product, a spherical catalyst component was prepared by the method described in the preceding examples by TiCl 4 reaction, having the following characteristics: - Ti = 2.2% by weight 15 - DIBF = 6.8% by weight - Porosity = 0.261 cm3 / g - Surface area = 66.5 m2 / g - apparent density = 0.440 g / cm3.

The X-ray spectrum of this catalyst component showed 20 reflections at 2v of 14.95 ° as well as 2v at 35 °.

Using 0.023 g of this catalyst component in the polymerization of propylene using the conditions of Example 1 gave 412 g of polypropylene having the following characteristics:. Fraction soluble in 25 xylene at room temperature = 3.0% - MIL = 3.2 g / 10 min - bulk density - 0.35 g / cm 3 - shape = 100% spherical particles with a diameter in the range of 500 - 5,000 μτα • - Flow rate 12 sec.

m

Following the general procedure described above, 0.0238 g of the catalyst component was used to copolymerize ethylene and butene to give 240 g of a copoly-35 mer having the following characteristics: 18 104632 - bound butene = 8.3% by weight - fraction soluble in xylene at room temperature = 12.2% - MIE = 12 g / 10 min 5 - MIF = 12 g / 10 min '- MIF: MIE = 30 shape: 100% spherical particles with a diameter of 500-5000 μτη.

EXAMPLE 4 Partial removal of alcohol (according to Example 1) from a spherical MgCl 2 * 3EtOH addition product prepared as described in the preceding Examples gave the addition product (EtOH: Mg = 0.4) having the following characteristics: 15-porosity (mercury) - 1.604 cm3 / g - surface area = 36.3 m2 / g - apparent density = 0.410 g / cm3.

Treatment of this support with TiCl4 at 135 ° C at 50 g / l and three treatments for 20 hours gave a spherical catalyst component which, after removal, washing and drying of excess TiCl4, had the following characteristics: - Ti = 2, 6% by weight; 25 - porosity = 0.427 cm3 / g - surface area = 66.5 m2 / g.

The X-ray spectrum of this component showed a reflection at a 2v angle of 14.95 ° as well as a 2v angle of 35 °.

Using 0.012 g of this catalyst component 30 in the polymerization of ethylene by the procedure described in the general section, 400 g of polyethylene was obtained with the following characteristics: - MIE = 0.144 g / 10 min - MIF = 8.87 g / 10 min 35 - MIF / MIE = 61 , 6 19 104632 - Shape = 100% spherical particles with a diameter in the range of 1000 to 5000 μιη - Flowability = 12 s - Apparent density = 0.38 g / cm3.

Example 5

Partial removal of the alcohol (as in Example 1) from the spherical MgCL2 -3EtOH addition product prepared as described in the preceding Examples gave an addition product having a 0.1 molar ratio of EtOH to MgCl2 having the following characteristics: - porosity (mercury) = 1.613 cm3 / g - Surface area = 22.2 m2 / g The X-ray spectrum of this component exhibited a hi-15 reflection at a 2v angle of 14.95 ° and a 2v angle of 35 °.

Using 0.03 g of this component in the polymerization of ethylene as described in Example 4 gave 380 g of polyethylene having the following characteristics: 20 - MIE = 0.205 g / 10 min - MIF = 16.42 g / 10 min - MIF / MIE = 80.1 - Flow rate 12 sec - apparent density = 0.40 g / cm 3 * 25 Example 6

The MgCl2 -EtOH addition product was prepared according to the procedure described in Example 3 but using 2% by weight of water in the alcohol used to prepare the starting material, MgCl2 * 3EtOH.

After the alcohol was removed, the adduct contained 3% by weight of water. Said addition product gave TiCl4 treatment and DIBF treatment as in Example 1, a spherical catalyst component having the following composition by weight: 35 - Ti = 2.35% - DIBF = 6.9%.

104632 Using 0.025 g of this component, the polymerization of propylene according to Example 1 gave 410 g of a spherical polymer having the following characteristics: 5 - Fraction soluble in xylene at 25 ° C = 3.1% - MIL = 3.0 g / 10 min - apparent density = 0.35 g / cm 3 - shape = 100% spherical particles having a diameter in the range 100-5000 µτη - flowability = 13 s.

• (• «%

Claims (8)

A process for preparing polymers and copolymers of olefins of formula CH 2 = CHR, wherein formula R is hydrogen or an alkyl or aryl radical, which contains from 1 to 8 carbon atoms, characterized in that the process is carried out in the presence of a catalyst comprising a reaction product of an A 1 trialkyl compound and a solid catalytic component a), the solid catalytic component a) comprising a titanium compound containing at least one Ti-halogen bond, on an anhydrous magnesium chloride support, wherein is in the form of spherical particles having an average diameter of 10 - 350 μιη, a surface area of 20 - 250 m 2 / g and a porosity of over 0.2 cmVg / and having an X-ray spectra which a) exhibit reflections at 2v angle values 35 ° and 14.95 ° or b) a reflection at the value of 2v angle is no longer present, but is replaced by a light phenomenon with maximum intensity between the values of 2v angle 33.5 ° and 35 ° and a r eflection at the 2v angle value 14.95 ° is absent, and wherein the catalytic component is prepared by reacting a titanium compound with an MgCl 2 / ROH addition product, where R is an alkyl, cycloalkyl or. aryl group containing 1-12 carbon atoms, wherein the addition product contains 0.15 - 2 moles of alcohol per mole of MgCl 2 and it is obtained by melting magnesium chloride / alcohol addition products containing such an amount of alcohol mols that the addition product is solid at room temperature, but melts at a temperature of 100 ° C to 130 ° C, whereby spherical particles are obtained, and by partially removing alcohol from the addition product, which is in the form of spherical particles, until a desired alcohol content is obtained. 2. A process according to claim 1, characterized in that the solid catalytic component a) further comprises an electron-donating compound, the molar ratio of the electron-donating compound to magnesium chloride being 1: 4 - 1.20. 3. A process according to claim 2, characterized in that the electron-donating compound is selected from alkylcycloalkyl or aryl esters of phthalic acid. 4. A process according to claim 2, characterized in that the electron-donating compound is selected from 1,3-dieters of the formula: CH2 -Orm ch2-oriv wherein R1 and R11, which may be the same or different, are alkyl, cycloalkyl or aryl groups containing from 1 to 18 carbon atoms; and R111 and RIV, which may be the same or different, are alkyl groups containing 1-4 carbon atoms. 5. A process according to claim 1 or 2, characterized in that an electron donating compound (an outer donor) is used in the preparation of the catalytic converter. 6. A process according to claim 5, characterized in that the solid catalytic component a) contains an electron-donating compound selected from alkyl, cycloalkyl and aryl esters, and the outer donor is a silicon compound of the formula R2R2 (Si (OR) 2, wherein Rx and R2, which may be the same or different, are alkyl, cycloalkyl or aryl groups containing 1-18 carbon atoms and R 30 is an alkyl group containing 1-4 carbon atoms. Process according to claim 5, characterized in that the outer donor is selected from 1,3-diets of the formula: Wherein R 1 and R 11, which may be the same or different, are alkyl, cycloalkyl or aryl groups containing 1 to 18 carbon atoms; and R111 and RIV which may be the same or different, are 5 alkyl groups containing 1-4 carbon atoms. Crystalline propylene horopolymer or propylene-ethylene copolymer having a smaller ethylene content, characterized in that said polymer or copolymer is in the form of spherical particles having an average diameter of 50-5000 μιη and a substantial porosity, and having obtained by a method according to any of claims 1-7. m * - »