Catalyst components for polymerisation of olefins

FIELD: chemistry.

SUBSTANCE: invention relates to polymerisation of CH₂=CHR olefins, where R is hydrogen or a C₁-C₁₂hydrocarbon group, and to catalysts therefor. A pre-polymerised catalyst component contains a solid component containing Mg, Ti, a halogen and an electron donor (ID), selected from alkyl esters of aromatic dicarboxylic acids. The molar ratio ID/Mg ranges from 0.025 to 0.065 and the molar ratio Mg/Ti is greater than 13. Said pre-polymerised catalyst component contains up to 50 g of an ethylene prepolymer per g of said solid catalyst component.

EFFECT: improved activity of the pre-polymerised catalyst and minimising problems associated with catalyst discharge.

9 cl, 2 tbl, 3 ex

The present invention relates to a pre-polymerized catalyst component for polymerization of olefins, in particular propylene, having specific chemical properties and comprising Mg, Ti and an electron donor selected from esters of aromatic dicarboxylic acids. The catalytic components of the invention are particularly suitable for use in gas-phase processes for the polymerization of olefins, in particular propylene.

The mode of operation of gas-phase reactor are well known in the art. With proper handling this type curing technology can give polymers endowed with satisfactory properties at relatively low investment costs. In gas-phase reactors performance (throughput) of the reactor is proportional to the amount of heat of polymerization, which can be removed from the fluidized bed. Heat transfer occurs by means of the recirculation gas, and in some processes there is a partial condensation, and the resulting liquid is injected into the polymer layer. In this case, we can say that the process operates in the mode of condensation.

The performance of the reactor is typically raised to a maximum value by increasing the flow rate of the gas mass up to the value allowed maximum speed gas for liquefaction. When this limit is exceeded, a significant part of the polymer particles is captured by a recirculating gas; this results in the accumulation layer (polymer particles) in the pipeline and the system fan is recirculated gases, clogged tube heat exchangers and distribution grid. As a consequence, the costs are higher, the production time is longer, and also included losses in manufacturing.

The speed trap is a direct function of the size and density of particles. Larger and/or denser particles allow a higher speed of the gas at fluidization and therefore to optimize gas polymer density should remain at the level up to the maximum permitted end use, while the fine fraction of the polymer should be avoided.

Small polymeric fraction, the so-called fines are generated in those cases where due to the high activity during the initial stages of the polymerization catalyst becomes irregularly fragmented. Specialists in this field of technology is known and described in many publications such as EP-A-541760 that to solve these problems it is proposed to apply the precursors of catalysts, which is pre-polymerized in continuous mode, a with the use of the device for preliminary polymerization mounted in the process of installation so as to continuously carry out the preliminary polymerization and to submit a pre-polymerized catalyst in the first polymerization reactor. Due to the preliminary polymerization catalyst particles become larger, and increases their stability in such a way that reduces the tendency to fracture under the conditions of polymerization. As a result, the catalyst is capable of producing larger polymer particles, and decreases the formation of stuff. Although this solution gives satisfactory results, it is applicable only to the polymerization plants, provided the setting for the preliminary polymerization is attached to the first reactor for polymerization. In fact, would be impossible or would involve a too high investment costs modification of plants, not yet equipped with a pre-polymerization. Therefore, these plants should be fed pre-polymerized catalyst, coming from a separate installation preliminary polymerization. However, the pre-polymerized catalysts used after storage, as a rule, are experiencing problems associated with aging. WO99/48929 describes n the applicatio component pre-polymerized catalyst, characterized in that it comprises a solid catalyst component comprising Ti, Mg, halogen and a compound, the electron donor, which is tentatively polymerized with ethylene to such an extent that the amount of ethylene prepolymer is up to 100 g per g of the specified solid catalytic component. The electron donor can be selected from various types of compounds belonging to the classes like the simple ethers and esters of aromatic mono - or dicarboxylic acids (benzoate, phthalates). According to this document, the preliminary polymerization of ethylene makes possible the reduction or complete elimination of loss of activity due to the effects of aging caused by storage of the catalyst. In General it is argued that the internal electron donor of any type is used in a molar ratio relative to the MgCl₂from 0.01 to 1, preferably from 0.05 to 0.5. The molar ratio Mg/Ti in the catalyst is not critical in any respect. Whereas examples 1-2 and comparative example 3, which relate to the catalytic systems based on esters of phthalic acid as internal donors, are the most widely used commercially, you can see that activity are not fully satisfactory.

In addition, it is noted that it is sometimes n is possible to completely unload the drums for storage, containing oil suspension of pre-polymerized catalyst as a certain part of the catalyst remains stuck or to the walls or to the bottom of the drum. This, of course, makes the unloading process more complex or partially impossible, and both lack unacceptable in commercial plant.

Now it was unexpectedly found that when the molar ratio Mg/Ti and the molar ratio of internal donor/Mg remain within a narrow and well-defined interval, it is possible to significantly improve the activity of the pre-polymerized catalyst, especially in gas-phase polymerization of olefins, and at least to minimize the aforementioned problems associated with the unloading. Accordingly, the present invention is a pre-polymerized catalyst component for polymerization of olefins CH₂=CHR, where R represents hydrogen or C₁-C₁₂acyclic hydrocarbon group comprising a solid catalytic component, characterized in that it comprises Mg, Ti, halogen and an electron donor (ID)selected from alkyl esters of aromatic dicarboxylic acids in an amount such that the molar ratio of ID/Mg ranged from 0.025 to 0,065 and the molar ratio Mg/Ti is higher, che is 13, moreover, the specified solid catalytic component contains ethylene polymer in the amount of up to 50 g per g of the specified solid catalytic component.

Preferably, the molar ratio of ID/Mg is in the range from 0.030 to 0,055 and most preferably from 0.035 to 0,050. In a preferred embodiment, the molar ratio Mg/Ti is higher than 14, and most preferably higher than 15. Especially it is in the range from 15 to 30.

Preferably the amount of ethylene polymer is in the range from 0.1 to 15 g, more preferably specified number is in the range from 0.5 to 5 g and in particular from 0.5 to 3 g per g of solid catalytic component.

A solid component of catalyst in his pre-polymerized form is also characterized by a porosity, measured by the mercury method, due to pores with radius equal to or lower than 1 μm, ranging from 0.45 cm³/g up to 1 cm³/g, preferably from 0.5 cm³/g to 0.9 cm³/g and more preferably from 0.6 to 0.9 cm³/year

Electron-donating compound (ID) is preferably selected from C₁-C₂₀alkyl esters of phthalic acid, possibly substituted. Especially preferred are₁-C₆linear or branched alkyl esters. Spiral the examples are diethylphthalate, di-n-propietat, di-n-butylphthalate, di-n-interftet, di-and-interftet, bis(2-ethylhexyl)phthalate, utilizability, ethyl-n-butylphthalate, di-n-hexylphthalate, di-isobutylphthalate.

In the solid catalytic component of the invention, Mg, Ti and halogen atoms are preferably derived from compounds of titanium, containing at least one link Ti-halogen and halide Mg. The magnesium halide is preferably MgCl₂in the active form, which is widely known from the patent literature as a substrate for catalysts of the Ziegler-Natta. Patents USP 4298718 and USP 4495338 were the first who described the use of these compounds in catalysis Ziegler-Natta. Of these patents, it is known that dihalogenide magnesium in the active form, used as a substrate or co-substrate in the components of catalysts for the polymerization of olefins, characterized by the x-ray spectrum in which the most intense diffraction line which appears in the spectrum of active halide, decreases in intensity and is replaced by a halo whose maximum intensity is shifted to lower angles relative angles more intense lines.

The preferred titanium compounds used in the catalyst component of the present invention are selected from compounds of the formula Ti(OR)_n-yX_ywhere is the valence of titanium, y is a number between 1 and n, X is halogen and R is a hydrocarbon radical containing from 1 to 10 carbon atoms. Of these the most preferred are TiCl₄and TiCl₃.

Preparation of solid catalyst component can be performed according to several methods.

According to a preferred method, the solid catalyst component can be obtained by reaction of titanium compounds of the formula described above, preferably TiCl₄with magnesium chloride, derived from the adduct having the formula MgCl₂d, where p is a number between 0.1 and 6, preferably from 2 to 3.5, and R is a hydrocarbon radical containing 1-18 carbon atoms, preferably ethyl. The adduct can be obtained in a suitable spherical form by mixing alcohol and magnesium chloride in the presence of an inert hydrocarbon immiscible with the adduct, operating in terms of mixing with the melting temperature of the adduct (100-130°C). Then the emulsion is rapidly cooled, causing the solidification of the adduct in form of spherical particles. The desired average particle size gain by regulating the energy supplied to the system due to shear stresses. In General, smaller particles can be obtained by increasing the shear stress and, consequently, the degree lane is masiania at the stage of mixing the adduct MgCl ₂-alcohol with an inert hydrocarbon.

Depending on the energy supplied to the system, the average size of the spherical particles of the adduct may vary from 5 to 100 μm, while in the most typical case, the particle size is in the range from 10 to 90 microns depending on the desired use of the final catalyst.

The grain size distribution (SPAN) of the adduct as a rule is lower than 1.5, when calculating according to the formula$$\frac{P90-P10}{P50}$$where in the distribution curve of the particle size determined according to the same method in which the P90 is the value of such a diameter that 90% of the total volume of particles have a diameter less than this value; P10 is the value of such a diameter that 10% of the total volume of particles have a diameter less than this value, and P50 is the value of such a diameter that 50% of the total volume of particles have a diameter less than this value. The average particle size (APS) of the particles of the adduct unpolymerized pre-catalyst component and a pre-polymerized catalyst component, and the distribution of the size of the particles, determined using the method described in the characteristic section, which is based on the opt the political diffraction.

The particle size distributions can in fact make narrow, following the recommendations WO 02/051544. However, this alternative manner or for a more narrow SPAN the largest and/or most of the fine fraction can be removed by appropriate means, such as mechanical screening and/or otmuchivanie in the fluid flow.

The particles of the adduct can interact directly with the compound of Ti, or you can expose thermally controlled dealcoholization (80-130°C.) to obtain an adduct in which the number of moles of alcohol is generally lower than 3, preferably between 0.1 and 2.5. Interaction with connection Ti can be done by suspension of the particles of the adduct (dealcoholizing or as such) in cold TiCl₄(usually 0°C); the mixture is heated up to 80-130°C and maintained at this temperature for 0.5-2 hours. Processing using TiCl₄you can carry out one or more times, and it is preferably carried out at least twice. The connection of the electron donor can be added during processing using TiCl₄. It can be added together in the same processing using TiCl₄or separately in two or more treatments. In any case, at this stage should be used by the donor in such quantity in relation to the MgCl₂d to obtain the ratio ID/Mg, oscillating in the range from 0.08 to 0.14, and more preferably from 0.09 to 0.13.

The solid components of the catalyst obtained according to the above method, show a surface area (by means of the method according to BET) typically between 20 and 500 m²/g and preferably between 50 and 400 m²/g and a total porosity (by means of the method according to BET) higher than 0.2 cm³/g, preferably between 0.2 and 0.6 cm³/year

In the above-mentioned methods of obtaining esters of aromatic dicarboxylic acids can be added as such, or alternatively, you can get themin situusing an appropriate precursor capable to be transformed in the desired electron-donor compound by means, for example, of known chemical reactions such as esterification, transesterification, etc.

The preliminary polymerization is usually carried out in the presence of compounds of the alkyl-Al. Connection (In) alkyl and Al is preferably selected from trialkylated aluminum compounds, such as, for example, triethylamine, triisobutylaluminum, tri-n-butylamine, tri-n-hexylamine, tri-n-octylamine. It is also possible to use mixtures trialkylamine and halides alkylamine, hydrides alkylamine or sesquichloride alkylamine, such as AlEt₂Cl and Al₂Et₃Cl₃. Especially prepact the tion is the use of tri-n-octylamine.

Found that particularly advantageous to carry out preliminary polymerization with the use of small quantities of alkyl-Al compounds. In particular, the specified number may be such as to have a mass ratio of Al/catalyst, in the range of from 0.001 to 10, preferably 0.005 to 5 and more preferably from 0.01 to 2.5. You can also use the external donor is selected from silicon compounds, ethers, esters, amines, heterocyclic compounds, ketones and simple 1,3-diesters of the General formula (I), reported previously. However, it was found advantageous to maintain the catalyst activity for longer periods of time, to carry out preliminary polymerization without the use of an external donor.

The preliminary polymerization can be carried out in the liquid phase (slurry or solution) or in the gas phase at temperatures generally lower than 50°C., preferably between -20 and 40°C and more preferably between -10 and 30°C. Preferably it is conducted in a liquid solvent, in particular selected from liquid hydrocarbons. Of them, preferred are pentane, hexane and heptane. Pre-polymerized catalyst of the invention is additionally characterized by a bulk density in the range from 0.30 to 0.45 g/cm³preferably from 0.35 to 0.40 g/cm³measured as the description is but under measurement characteristics. Found that the pre-polymerized catalyst of the invention in addition to the very high activity also shows improved behavior from the point of view of operations, expressed as a very small amount of catalyst remaining in the drum after unloading. Pre-polymerized catalysts with a bulk density get through the impact of the solid catalytic components specific ID/Mg, and the molar ratio Mg/Ti can be obtained by conducting operations under carefully controlled conditions prior to polymerization from the viewpoint of reactor loading, temperature, concentration alkylamine and mixing speeds. In particular, the conduct of operations at a relatively low loading of the reactor, a relatively high speed stirring, at a low concentration alkylamine and ethylene over long time periods of interaction allows to avoid or minimize the formation of aggregated particles, which lowers the bulk density. In particular, it is preferable to load the whole amount of the monomer, which should polimerizuet, in a period of time longer than 8 hours, preferably longer than 10 hours and especially longer than 15 hours.

The degree will prefix Inoi polymerization is such, the amount of the ethylene polymer is up to about 50 grams per gram of solid component of catalyst. Therefore, in accordance with the present invention, the term "prepolymer" means the ethylene polymer produced in the amount of 50 grams per gram of solid component of catalyst, preferably from 0.1 to 15 g, more preferably specified number is in the range from 0.5 to 5 g, and particularly from 0.5 to 3 g per gram of solid catalyst component.

The degree of pre-polymerization can be easily controlled by monitoring, in accordance with known methods, the number of monomer, which is polymerized. In accordance with the present invention, a solid component of catalyst must be pre-polymerized with ethylene, but also together with him can be polymerized minor amounts of C3-C10 olefin comonomers, although their number in the final ethylene polymer should be less than 15 wt.%.

Due to the preliminary polymerization, the final average particle size of the pre-polymerized catalyst component may be larger than for the original pre unpolymerized solid component of catalyst and preferably is in the range from 15 to 150 μm, preferably from 20 to 100 microns.

Particles indicated the s catalyst components in a pre-unpolymerized form preferably have a spherical morphology, which means that the ratio between the maximum and the minimum diameter is less than 1.5 and preferably less than 1.3.

Components are pre-polymerized solid catalyst in accordance with the present invention is used in the polymerization of olefins by means of their interaction with ORGANOMETALLIC compounds, in accordance with known methods.

Specifically, the present invention is a catalyst for polymerization of olefins CH₂=CHR, where R represents hydrogen or C₁-C₁₂hydrocarbon radical, containing the reaction product between:

(i) a pre-polymerized solid component of catalyst, as disclosed above and

(ii) connection alkylamine.

The alkyl-Al compound (ii) is preferably chosen among compounds trialkylamine, such as, for example, triethylamine, triisobutylaluminum, tri-n-butylamine, tri-n-hexylamine, tri-n-octylamine. It is also possible to apply the halides alkylamine, hydrides alkylamine or sesquichloride alkylamine, such as AlEt₂Cl and Al₂Et₃Cl₃possibly in a mixture with the above-mentioned compounds trialkylamine.

When used in propylene polymerization, to obtain high values of isotacticity and insolubility in xylene, to aliticheskaja system, the above may be used in combination with an external donor (iii).

Suitable external electron-donor compounds include silicon compounds, ethers, esters, amines, heterocyclic compounds and particularly 2,2,6,6-tetramethylpiperidine, ketones and 1,3-diesters of General formula (I)above.

The class a preferred external electron-donor compounds are silicon compounds of the formula R_a⁵R_b⁶Si(OR⁷)_cwhere a and b are integers from 0 to 2, p is an integer from 1 to 3 and the sum (a+b+c) is 4; R⁵, R⁶and R⁷represents radicals of alkyl, cycloalkyl or aryl with 1 to 18 carbon atoms, optionally containing heteroatoms. Particularly preferred are the silicon compounds in which a is 1, b is 1, C is 2, at least one of R⁵and R⁶selected from branched alkyl, cycloalkyl or aryl groups with 3-10 carbon atoms, optionally containing heteroatoms, and R⁷represents a C₁-C₁₀alkyl group, specifically methyl. Examples of such preferred silicon compounds are methylcyclohexanecarboxylic, diphenylmethylsilane, methyl-tert-butyldimethylsilyl, dicyclopentadienyliron, (2-ethylpiperidine)-tert-butoxyethoxyethanol, (2 atelp pyridinyl)hexylammonium, 3,3,3-Cryptor-n-propyl)(2-ethylpiperidine)dimethoxysilane, methyl(3,3,3-Cryptor-n-propyl)dimethoxysilane. In addition, also preferred are the silicon compounds in which a is 0, C is 3, R⁶represents a branched alkyl or cycloalkyl group, optionally containing heteroatoms, and R⁷is stands. Examples of such preferred silicon compounds are cyclohexyltrichlorosilane, tert-butyldimethylsilyl and hexyltrimethoxysilane.

Electron-donating compound (iii) is used in such a quantity to obtain a molar ratio between alyuminiiorganicheskikh connection and the specified electron-donor compound (iii) in the range from 3 to 100.

Therefore, an additional objective of the present invention is a method of (co)polymerization of olefins, CH₂=CHR, where R represents hydrogen or C₁-C₁₂hydrocarbon group, carried out in the presence of a catalyst containing reaction product between:

(i) a pre-polymerized solid component of the catalyst described above;

(ii) connection alkylamine and

(iii) optional electron-donor compound (external donor).

The polymerization process can be carried out in accordance with known methods, for example, suspension polymerization, with what ispolzovaniem as a diluent inert hydrocarbon solvent, or bulk polymerization using a liquid monomer (e.g., propylene) as a reaction medium. However, as mentioned above, has been found particularly advantageous use of such catalytic systems in the way that gas-phase polymerization, where they provide higher yields in combination with different morphological properties expressed by high values of bulk density. Also, the various stages of polymerization can be applied sequentially, for example, by first obtaining a Homo - or copolymer of propylene with relatively high crystallinity on stage with the liquid phase, and then on subsequent gas-phase stage, carried out in the presence of the product coming from the first stage can be obtained propylene with relatively low crystallinity. This kind of products are also commonly referred to as the heterophase propylene copolymers.

Gas-phase process or stage can be carried out when conducting operations in one or more reactors with a fluidized bed or layer with mechanical stirring. Usually in the fluidized bed reactor fluidization is achieved by using flow pseudoviruses gas, the speed of which does not exceed the transport speed. As a result, the layer of fluidized particles can be found in more or is the Eney limited zone of the reactor. Also, these catalysts are applicable in devices for gas-phase polymerization containing at least two interconnected polymerization zone. This method of polymerization is described in European patent EP 782587.

It is worth mentioning that the use of pre-polymerized catalyst according to the invention is particularly advantageous in the fluidized bed reactor, not provided with a section of the preliminary polymerization with upward flow. Despite this, it is providing polymers, specifically propylene polymer with a bulk density of more than 0,43 g/cm³in combination with activities, approximately 20 kg/g of solid catalyst component.

The polymerization is usually carried out at a temperature from 40 to 120°C., preferably from 40 to 100°C. and more preferably from 50 to 90°C. the Polymerization is carried out in the gas phase when the pressure is generally between 0.5 and 5 MPa, preferably between 1 and 4 MPa. In bulk polymerization, the operating pressure is generally between 1 and 8 MPa, preferably between 1.5 and 5 MPa.

The following examples are given in order to better illustrate the invention without its limitations.

MEASUREMENT CHARACTERISTICS

Definition X.I. (insoluble in xylene)

2.5 g of polymer was dissolved in 250 ml of o-xylene under stirring n and 135°C for 30 minutes, then the solution was cooled to 25°C and after 30 minutes the insoluble polymer was filtered. The resulting solution was evaporated under a stream of nitrogen and the residue was dried and weighed to determine the percentage of soluble polymer, and then, by difference, the content of insoluble polymer X.I.%

The average particle size of the adduct and catalysts

Determined by a method based on the principle of optical diffraction of monochromatic light through the device “Malvern Instr. 2600”. The average size is given as P50.

The average particle size of the polymers

Determined by applying shaker for sieves Tyler (Tyler Testing Sieve Shaker) RX-29 model, available from Combustion Engineering Endecott, equipped with a set of six sieves in accordance with ASTM E-11-87, with the numbers 5, 7, 10, 18, 35 and 200, respectively.

Determination of bulk density

100 g butter Winog 70 produced Tudapetrol, is introduced into a graduated cylinder. Consistently give the weighted number (30-40 g) sample pre-polymerized catalyst and allowed to settle for 24 hours. After this time, the height of the dense layer of the catalyst is measured and its occupied volume are determined by geometric calculation. Bulk density gain by dividing the sample mass of the catalyst on the amount of space.

EXAMPLES/p>

Example 1

Preparation of solid catalyst component

The initial number of microspherical MgCl₂·2, 8C₂H₅OH was obtained in accordance with the method described in example 2, WO98/44009, but when conducting operations on a larger scale and setting conditions of mixing so as to obtain the adduct having an average particle size equal to 25 microns. In chetyrehosnuju round bottom flask 500 ml, purged with nitrogen, was introduced 250 ml of TiCl₄at 0°C, with stirring, 15 g of the resulting adduct, obtained as described above. The flask was heated to 40°C. and added diisobutylphthalate (DIBP) in an amount such that the ratio of DIBP/Mg was equal 0,111. The temperature was raised to 100°C. and maintained for two hours, then stirring was discontinued, the solid product was allowed to precipitate and supernatant fluid was collected by siphon.

Then the processing of TiCl₄repeated two more times, omitting the use of DIBP, at a temperature of 120°C. the Obtained solid was washed six times with anhydrous hexane (6×100 ml) at 60°C and then dried under vacuum. Characteristics of the catalyst components and the results of the test methods propylene polymerization are shown in table 1.

Obtaining a pre-polymerized catalyst

In the reactor of stainless steel with a volume of 60 liters, is 35 liters of hexane at 20°C, while mixing at about 80 rpm./minutes, was administered to 1500 g of spherical catalyst obtained as described above. While maintaining a constant internal temperature in the reactor (slowly) was administered 24 g of tri-n-octylamine (TNOA) in hexane. Then gently introduced into the reactor with ethylene at the same temperature, at constant flow for 18 hours the Polymerization was interrupted when the thought achieved a theoretical conversion of 1 g of polymer in grams of catalyst. After 3 washes with hexane at T=20°C (50 g/l), the resulting pre-polymerized catalyst was dried and analyzed. It contained 1.3 g of polyethylene in g of the solid catalyst, and its bulk density was 0,390 g/cm³.

Comparative example 1

Was carried out by the same procedure described in example 1 with the difference that utilized a large number of DIBP, resulting molar ratio ID/Mg to about 0.15. Characteristics of the final catalyst are shown in Table 1.

Comparative example 2

Pre-polymerized catalyst was obtained in accordance with example 1 WO99/48929. Characteristics of the final catalyst are shown in Table 1. Characteristics of the final catalyst are shown in Table 1.

Gas-phase polymerization of propylene

The method of polymerization for obtaining heterophase copolymers of propylene/p>

Heterophase copolymers of propylene was obtained in the pilot unit comprising two series connected gas-phase reactor. Polymerization begins by separate feeding in a continuous and constant flow of pre-polymerized catalyst component in the propylene stream, triethylaluminum (TEAL), dicyclopentadienyliron (DCPMS) as external donor, hydrogen (used as molecular weight regulator), and monomers in amounts and under conditions shown in Table 2.

The polymer particles exiting the second reactor, is subjected to a steam treatment to remove the reactive monomers and volatile substances, and then dried.

1. Pre-polymerized catalyst component for polymerization of olefins containing a solid component of catalyst, which contains Mg, Ti, halogen atoms and the electron donor (ID)selected from alilovic esters of aromatic dicarboxylic acids in an amount such that the molar ratio of ID/Mg ranged from 0.025 to 0,070 and the molar ratio Mg/Ti is higher than 13, and the specified pre-polymerized component catalysis the Torah contains the amount of the ethylene polymer up to 50 g per g of the specified solid catalyst component.

2. Pre-polymerized catalyst component according to claim 1, where the molar ratio of ID/Mg is in the range from 0.030 to to 0.060.

3. Pre-polymerized catalyst component according to claim 1, where the molar ratio Mg/Ti is more than 14.

4. Pre-polymerized catalyst component according to claim 1, in which the amount of polymer is in the range from 0.1 to 15 g per g of solid catalyst component.

5. Pre-polymerized catalyst component according to claim 1, having a bulk density in the range of from 0.30 to 0.45 g/cm³.

6. Pre-polymerized catalyst component according to claim 1, in which the electron-donating compound (ID) selected from C₁-C₂₀alilovic esters of phthalic acid.

7. Pre-polymerized catalyst component according to claim 1, where Mg, Ti and halogen atoms are derived from compounds of titanium with at least a link Ti-halogen and halide Mg.

8. Catalytic system for polymerization of olefins CH₂=CHR, in which R represents hydrogen or a hydrocarbon radical with 1-12 carbon atoms, containing the reaction product between:
(i) a pre-polymerized solid component of catalyst according to any one of claims 1 to 7;
(ii) connection alkylamine and, optionally,
(iii) an external electron-donor soy is inanam.

9. Gas-phase method for the polymerization of olefins CH₂=CHR, where R represents hydrogen or C₁-C₁₂hydrocarbon group, carried out in the presence of a catalytic system of claim 8.