WO2009080568A2

WO2009080568A2 - Magnesium dichloride-alcohol adducts and catalyst components obtained therefrom

Info

Publication number: WO2009080568A2
Application number: PCT/EP2008/067450
Authority: WO
Inventors: Gianni Collina; Daniele Evangelisti; Giampiero Morini; Giuseppe Ferrara
Original assignee: Basell Poliolefine Italia S.R.L.
Priority date: 2007-12-21
Filing date: 2008-12-12
Publication date: 2009-07-02
Also published as: WO2009080568A3

Abstract

Spherical adducts comprising a MgCl2, an alcohol ROH in which R is a Cl-ClO hydrocarbon group, present in a molar ratio with MgCl2 ranging from 0.5 to 5 and less than 5% wt, based on the total weight of the adduct, of a solid inorganic compound selected from oxides or hydroxides of Si, Al, Mg, Ti and mixtures thereof. The catalyst components obtained from the said adducts generate during polymerization a reduced content of broken polymer particles in comparison with the catalyst obtained from adducts not containing the inorganic solid compound.

Description

TITLE:

"Magnesium dichloride-alcohol adducts and catalyst components obtained therefrom"

The present invention relates to magnesium dichloride/alcohol adducts containing specific amounts of inorganic compounds having a specific particle size. The adducts of the present invention are particularly useful as precursors of catalyst components for the polymerization of olefins.

MgCl₂*alcohol adducts and their use in the preparation of catalyst components for the polymerization of olefins is well known in the art.

Catalyst components for the polymerization of olefins, obtained by reacting MgCl₂-IiEtC)H adducts with halogenated transition metal compounds, are described for example in USP

4,399,054. The adducts are prepared by emulsifying the molten adduct in an immiscible dispersing medium and quenching the emulsion in a cooling fluid to collect the adduct in the form of spherical particles.

In WO98/44009 are disclosed MgCl₂«alcohol adducts having improved characteristics and characterized by a particular X-ray diffraction spectrum, in which, in the range of 2Θ diffraction angles between 5° and 15°, the three main diffraction lines are present at diffraction angles 2Θ of

8.8 ± 0.2°, 9.4 ± 0.2° and 9.8 ± 0.2°, the most intense diffraction lines being the one at 2Θ=8.8

± 0.2°, the intensity of the other two diffraction lines being at least 0.2 times the intensity of the most intense diffraction line. Said adducts can be of formula MgCl₂ •mEtOH«nH₂O where m is between 2.2 and 3.8 and n is between 0.01 and 0.6. These adducts are obtained by specific preparation methods involving the reaction between MgCl₂ and alcohol under specific conditions such as long reaction times, absence of inert diluents or use of vaporized alcohol. In all the cases, in order to produce a catalytic components a transition metal compound must be fixed on the support. This is obtained by contacting the supports with large amounts of titanium compounds, in particular TiCU, that causes removal of the alcohol and supportation of Ti atoms.

The so obtained catalysts show very high activities but their morphological stability is not always satisfactory because, under polymerization conditions, it often gives rise to a non negligible amount of broken polymer particle that contribute to generate the fine polymer particles which negatively affect the operation of the polymerization plant.

WO2006/036359 described the preparation of inorganic oxide nanoparticles coated with magnesium chloride/ethanol adducts. The inorganic oxide particles have dimension of less than 5 microns and preferably of less than 1 micron, specifically of less than 0.1 microns. The preparation of the final magnesium chloride support is described in vague terms. It is not mentioned in which form and dimension are the final particles obtained and the document is totally silent about the final alcohol content of the support. Moreover, the wording used in the specific examples says that the particles are expected to be uniform and to have large surface area, thus clearly demonstrating that no characterization has been carried out and therefore giving no basis for ascertaining whether or not the experiment was at least partially successful. In addition, no technical effect seems to be associated to the use of such a support. The catalyst therefrom obtained has been tested in the ethylene copolymerization where it displayed no prominent features.

The applicant has now found that magnesium chloride based adducts having a specific range of alcohol content and containing a specific amount of inorganic particles having a certain dimensional range are able to generate catalyst components with high polymerization activity and enhanced morphological stability.

The present invention therefore relates to spherical adducts comprising a MgC^, an alcohol ROH in which R is a Cl-ClO hydrocarbon group, present in a molar ratio with MgC^ ranging from 0.5 to 5 and less than 5% wt, based on the total weight of the adduct, of a solid inorganic compound selected from oxides or hydroxides of Si, Al, Mg, Ti and mixtures thereof. Preferably, R is chosen among C1-C8 linear or branched hydrocarbon groups and more preferably among the C1-C4 linear hydrocarbon groups. Ethanol is especially preferred. Preferably, the number of moles of alcohol per mole of MgCl2 ranges from 0.8 to 4 and more preferably from 1 to 3.5. The alcohol/Mg molar ratio from 1.5 to 3 is especially preferred. The solid inorganic compound is preferably added in amounts of less than 3% more preferably of less than 2 % and especially in the range of from 0.1 to 1 %wt based on the total weight of the adduct.

Preferably, the particle size of said inorganic compound is of higher than 1 micron preferably from 2 to 80 microns, more preferably from 5 to 50 microns.

Preferably, it is selected from silicates, phyllosilicates, Al oxides, hydroxides and mixtures thereof. Among silicates particularly preferred are the clay aluminium silicates such as kaolin, smectite, hormite and the phyllosilicates such as talc and pyrophillite. Also preferred are aluminum oxides-idroxides of formula AlO(OH) such as bohemite. Also usable are the various crystalline forms of Tiθ2. Certain clay minerals such like those belonging to smectite group such as sodium and calcium montmorillonite are composed of silicate layers can be treated with various types of swelling agents such as organic ammonium ions, to intercalate the swelling agent molecules between adjacent, planar silicate layers, thereby substantially increasing the interlayer spacing. The intercalated silicates can then be exfoliated, i.e. the silicate layers are separated, typically by shear mixing.

The smectite clay minerals include, for example, montmorillonite, nontronite, beidellite, volkonskoite, hectorite, saponite, sauconite, sobockite, stevensite, and svinfordite. Montmorillonite is preferred. The smectite clay mineral can be untreated, or it can be modified with a swelling agent containing organic cations by treating the clay with one or more organic cation salts to exchange the metal cations present in the spaces between the layers of the clay material with organic cations, thereby substantially increasing the interlayer spacing. The expansion of the interlayer distance of the layered silicate facilitates the intercalation of the clay with other materials. The organic cation salt swelling agents have an onium ion. Examples of an onium ion include ammonium ion, trimethylammonium ion, trimethyl phosphonium ion, and dimethyl sulfonium ion. The organic cations can be used alone or in combination. Suitable swelling agents include, for example, poly (propylene glycol) bis (2-aminopropyl ether), poly (vinylpyrrolidone), dodecylamine hydrochloride, octadecylamine hydrochloride, and dodecylpyrrolidone. The clay can be swelled with water before introducing the quaternary ammonium ion. Such treated clays are commercially available. Due to the possible swelling and exfoliation process it is also possible that the above mentioned inorganic compounds are present in the final adducts in forms of particles having an average particle size lower than the original one. It is also possible that in the final adduct such inorganic compound particles have at least one dimension of lower than 1 micron.

The adduct of the present invention can be prepared according to different techniques. In general the said adduct spherical comprising a MgC^, an alcohol ROH in which R is a Cl-ClO hydrocarbon group, present in a molar ratio with MgC^ ranging from 0.5 to 5 said adduct are obtained by adding to MgC^ and the alcohol less than 5% wt, based on the total weight of the adduct, of a solid inorganic compound selected from oxides or hydroxides of Si, Al, Mg, Ti and mixtures thereof. The said method comprises bringing into contact the suitable amount of magnesium chloride, inorganic compound and alcohol, heating the system until a molten adduct is formed and then rapidly cooling the system in order to solidify the particles preferably in spherical form.

The contact between magnesium chloride, transition metal compound and alcohol can occur in the presence or in the absence of an inert liquid immiscible with and chemically inert to the molten adduct. If the inert liquid is present it is preferred that the desired amount of alcohol is added in vapour phase. This would ensure a better homogeneity of the formed adduct. The liquid in which the adduct is dispersed can be any liquid immiscible with and chemically inert to the molten adduct. For example, aliphatic, aromatic or cycloaliphatic hydrocarbons can be used as well as silicone oils. Aliphatic hydrocarbons such as vaseline oil are particularly preferred. After the MgC^ particles, the alcohol and the transition metal compound are dispersed in the liquid phase the mixture is heated at a temperature at which the adduct reaches its molten state. This temperature depends on the composition of the adduct and generally ranges from 100 to 150⁰C. As mentioned before the temperature is kept at values such that the adduct is completely melted. Preferably the adduct is maintained in the molten state under stirring conditions, for a time period equal to or greater than 10 hours, preferably from 10 to 150 hours, more preferably from 20 to 100 hours.

In order to obtain solid discrete particles of the adduct with suitable morphology it is possible to operate in different ways. One of the preferred possibilities is the emulsification of the adduct in a liquid medium which is immiscible with and chemically inert to it followed by the quenching carried out by contacting the emulsion with an inert cooling liquid, thereby obtaining the solidification of the particles of the adduct in spherical form.

Another preferred method for obtaining the solidification of the adduct consists in adopting the spray-cooling technique. When this option is pursued it is preferred that in the first step the magnesium chloride the inorganic compound and the alcohol are contacted to each other in the absence of an inert liquid dispersant. After having been melted the adduct is sprayed, through the use of the proper devices that are commercially available, in an environment having temperature so low as to cause rapid solidification of the particles. In a preferred aspect, the adduct is sprayed in a cold liquid environment and more preferably in a cold liquid hydrocarbon. By way of these methods and in particular of the method comprising the emulsification, it is possible to obtain adduct particles in spherical or spheroidal form. Such spherical particles have a ratio between maximum and minimum diameter lower than 1.5 and preferably lower than 1.3.

The adduct of the invention can be obtained in a broad range of particle size, namely ranging from 5 to 150 microns preferably from 10 to 100 microns and more preferably from 15 to 80 microns. While the specific particle dimension depends strictly on the energy provided during either the emulsifying step (extent of stirring) or the spraying step, it has been found that the use of the said inorganic compound often allows obtaining adduct particles having smaller particle size than the adduct not containing the inorganic compound prepared under the same conditions. Without wanted to be bound to any theory or scientific explanation, it is possible that the said reduction in particle size is due to the fact that a molten adduct having a reduced viscosity is obtained when the inorganic compound is used.

Preferably, the adducts obtained according to the general method are further characterized by a DSC profile in which the highest melting Temperature (Tm) peak is higher than 95°C, preferably higher than 100⁰C and more preferably in the range 105-125⁰C and has an associated fusion enthalpy (ΔH) lower than 103 J/gr preferably in the range 70-100 J/gr. It is also possible, but not strictly required, that also the adducts of the present invention are characterized by an X-ray diffraction spectrum in which, in the range of 2Θ diffraction angles between 5° and 15°, the three main diffraction lines are present at diffraction angles 2Θ of 8.8 ± 0.2°, 9.4 ± 0.2° and 9.8 ± 0.2°, the most intense diffraction line being the one at 2Θ=8.8 ± 0.2°, the intensity of the other two diffraction lines being at least 0.2 times the intensity of the most intense diffraction line. Moreover, the said adduct show an X-ray diffraction spectrum in which in the range of 2Θ diffraction angles between 5° and 50° the characteristic diffraction lines of the (X-MgCl₂ are not present.

The adduct of the invention may also contain some water, preferably in an amount lower than 3%wt. The amount of water can be controlled by paying particular attention to the water content of the reactants. Both MgCl₂ and EtOH are in fact highly hygroscopic and tend to incorporate water in their structure. As a result, if the water content of the reactants is relatively high, the final MgCl₂-EtOH adducts may contain a too high water content even if water has not been added as a separate component. Means for controlling or lowering the water content in solids or fluids are well known in the art. The water content in MgCl₂ can be for example lowered by drying it in an oven at high temperatures or by reacting it with a compound which is reactive towards water. As an example, a stream of HCl can be used to remove water from MgCl₂. Water from the fluids can be removed by various techniques such as distillation or by allowing the fluids to become in contact with substances capable to subtract water such as molecular sieves. Once this precautions have been taken, the reaction between the magnesium chloride the ethanol and the inorganic compounds to produce the adducts of the invention can be carried out according to the methods reported above. The adducts of the invention are converted into catalyst components for the polymerization of olefins by reacting them with a transition metal compound of one of the groups IV to VI of the Periodic Table of Elements.

Among transition metal compounds particularly preferred are titanium compounds of formula Ti(OR)_nX_y-_n in which n is comprised between 0 and y; y is the valence of titanium; X is halogen and R is an alkyl radical having 1-8 carbon atoms or a COR group. Among them, particularly preferred are titanium compounds having at least one Ti-halogen bond such as titanium tetrahalides or halogenalcoholates. Preferred specific titanium compounds are TiCl3, TiCU, Ti(OBu)₄, Ti(OBu)Cl₃, Ti(OBu)₂Cl₂, Ti(OBu)₃Cl. Preferably the reaction is carried out by suspending the adduct in cold TiCL (generally O⁰C); then the so obtained mixture is heated up to 80-130⁰C and kept at this temperature for 0.5-2 hours. After that the excess of TiCL is removed and the solid component is recovered. The treatment with TiCL can be carried out one or more times.

The reaction between transition metal compound and the adduct can also be carried out in the presence of an electron donor compound (internal donor) in particular when the preparation of a stereospecific catalyst for the polymerization of olefins is to be prepared. Said electron donor compound can be selected from esters, ethers, amines, silanes and ketones. In particular, the alkyl and aryl esters of mono or polycarboxylic acids such as for example esters of benzoic, phthalic, malonic and succinic acid are preferred. Specific examples of such esters are n- butylphthalate, di-isobutylphthalate, di-n-octylphthalate, diethyl 2,2-diisopropylsuccinate, diethyl 2,2-dicyclohexyl-succinate, ethyl-benzoate and p-ethoxy ethyl-benzoate. Moreover, can be advantageously used also the 1,3 diethers of the formula:

wherein R, R¹, R^π, R^ffl, R^ and R^v equal or different to each other, are hydrogen or hydrocarbon radicals having from 1 to 18 carbon atoms, and R^ and R^w, equal or different from each other, have the same meaning of R-R^v except that they cannot be hydrogen; one or more of the R-R^ groups can be linked to form a cycle. The 1,3-diethers in which R^ and R™ are selected from C₁-C₄ alkyl radicals are particularly preferred. The electron donor compound is generally present in molar ratio with respect to the magnesium comprised between 1 :4 and 1 :20.

Preferably, the particles of the solid catalyst components have substantially the same size and morphology as the adducts of the invention generally comprised between 5 and 150μm. Before the reaction with the transition metal compound, the adducts of the present invention can also be subjected to a dealcoholation treatment aimed at lowering the alcohol content and increasing the porosity of the adduct itself. The dealcoholation can be carried out according to known methodologies such as those described in EP-A-395083. Depending on the extent of the dealcoholation treatment, partially dealcoholated adducts can be obtained having an alcohol content generally ranging from 0.1 to 2.6 moles of alcohol per mole of MgCl₂. After the dealcoholation treatment the adducts are reacted with the transition metal compound, according to the techniques described above, in order to obtain the solid catalyst components. The solid catalyst components according to the present invention show a surface area (by B.E.T. method) generally between 10 and 500 m²/g and preferably between 20 and 350 m²/g, and a total porosity (by B.E.T. method) higher than 0.15 cffiVg preferably between 0.2 and 0.6

CffiVg.

The amount of the titanium compound in the final catalyst component ranges from 0.1 to 10% wt, preferably from 0.5 to 5%wt.

The catalyst components of the invention form catalysts for the polymerization of alpha-olefrns CH₂=CHR, wherein R is hydrogen or a hydrocarbon radical having 1-12 carbon atoms, by reaction with Al-alkyl compounds. The alkyl-Al compound can be of the formula A1R₃__ZX_Z above, in which R is a Cl-Cl 5 hydrocarbon alkyl radical, X is halogen preferably chlorine and z is a number 0<z<3. The Al-alkyl compound is preferably chosen among the trialkyl aluminum compounds such as for example trimethylaluminum triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum. It is also possible to use alkylaluminum halides, alkylaluminum hydrides or alkylaluminum sesquichlorides such as AlEt₂Cl and Al₂Et₃CIs optionally in mixture with said trialkyl aluminum compounds.

The Al/Ti ratio is higher than 1 and is generally comprised between 20 and 800. It is possible to use in the polymerization system an electron donor compound (external donor) which can be the same or different from the compound that can be used as internal donor disclosed above. In case the internal donor is an ester of a polycarboxylic acid, in particular a phthalate, the external donor is preferably selected from the silane compounds containing at least a Si-OR link, having the formula R_a ¹Rb²Si(OR³)_c, where a and b are integer from O to 2, c is an integer from 1 to 3 and the sum (a+b+c) is 4; R¹, R², and R³, are alkyl, cycloalkyl or aryl radicals with 1-18 carbon atoms. Particularly preferred are the silicon compounds in which a is 1, b is 1, c is 2, at least one of R¹ and R² is selected from branched alkyl, cycloalkyl or aryl groups with 3-10 carbon atoms and R³ is a Ci-Cio alkyl group, in particular methyl. Examples of such preferred silicon compounds are methylcyclohexyldimethoxysilane, diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane. Moreover, are also preferred the silicon compounds in which a is 0, c is 3, R² is a branched alkyl or cycloalkyl group and R³ is methyl. Examples of such preferred silicon compounds are cyclohexyltrimethoxysilane, t-butyltrimethoxysilane and thexyltrimethoxysilane. Also the cyclic ethers such as tetrahydrofurane, and the 1,3 diethers having the previously described formula can be used as external donor.

As previously indicated the components of the invention and catalysts obtained therefrom find applications in the processes for the (co)polymerization of olefins of formula CH₂=CHR in which R is hydrogen or a hydrocarbon radical having 1-12 carbon atoms. The catalysts of the invention can be used in any of the olefin polymerization processes known in the art. They can be used for example in slurry polymerization using as diluent an inert hydrocarbon solvent or bulk polymerization using the liquid monomer (for example propylene) as a reaction medium. Moreover, they can also be used in the polymerization process carried out in gas-phase operating in one or more fluidized or mechanically agitated bed reactors. The polymerization is generally carried out at temperature of from 20 to 120⁰C, preferably of from 40 to 80⁰C. When the polymerization is carried out in gas-phase the operating pressure is generally between 0.1 and 10 MPa, preferably between 1 and 5 MPa. In the bulk polymerization the operating pressure is generally between 1 and 6 MPa preferably between 1.5 and 4 MPa.

The catalysts of the invention are very useful for preparing a broad range of polyolefm products. Specific examples of the olefinic polymers which can be prepared are: high density ethylene polymers (HDPE, having a density higher than 0.940 g/cc), comprising ethylene homopolymers and copolymers of ethylene with alpha-olefins having 3-12 carbon atoms; linear low density polyethylenes (LLDPE, having a density lower than 0.940 g/cc) and very low density and ultra low density (VLDPE and ULDPE, having a density lower than 0.920 g/cc, to 0.880 g/cc) consisting of copolymers of ethylene with one or more alpha-olefins having from 3 to 12 carbon atoms, having a mole content of units derived from the ethylene higher than 80%; isotactic polypropylenes and crystalline copolymers of propylene and ethylene and/or other alpha-olefins having a content of units derived from propylene higher than 85% by weight; copolymers of propylene and 1-butene having a content of units derived from 1-butene comprised between 1 and 40% by weight; heterophasic copolymers comprising a crystalline polypropylene matrix and an amorphous phase comprising copolymers of propylene with ethylene and or other alpha-olefins.

In particular, it has been noticed that the catalyst components obtained from the said adducts generate during polymerization a very reduced content of broken polymer particles in comparison with the catalyst obtained from adducts not containing the inorganic solid compound. This reduced content of broken polymer particles greatly facilitates the run of the polymerization plants avoiding the formation of fines.

The following examples are given to further illustrate without limiting in any way the invention itself.

CHARACTERIZATION

The properties reported below have been determined according to the following methods: Fraction soluble in xylene. (XS) The solubility in xylene at 25°C was determined according to the following method: About 2.5 g of polymer and 250 ml of o-xylene were placed in a round-bottomed flask provided with cooler and a reflux condenser and kept under nitrogen. The mixture obtained was heated to 135°C and was kept under stirring for about 60 minutes. The final solution was allowed to cool to 25°C under continuous stirring, and was then filtered. The filtrate was then evaporated in a nitrogen flow at 140⁰C to reach a constant weight. The content of said xylene-soluble fraction is expressed as a percentage of the original 2.5 grams. Average Particle Size of the adduct and catalysts

Determined by a method based on the principle of the optical diffraction of monochromatic laser light with the "Malvern Instr. 2600" apparatus. The average size is given as P50. Average Particle Size of the polymers

Determined through the use Tyler Testing Sieve Shaker RX-29 Model B available from Combustion Engineering Endecott provided with a set of six sieves, according to ASTM E-11-87, of number 5, 7, 10, 18, 35, and 200 respectively.

EXAMPLES EXAMPLE 1

A sample of Cloisite 15 A (organoclay by Sourthern Clay) was prepared free of water by drying under vacuum for 6 hrs at 110⁰C. The average particle size was 8.4 μm. A 5 litre reactor was loaded with 315.8 g of anhydrous MgCl₂, 469.8g of EtOH, and the 4 g of Cloisitel5A. The temperature was raised up to 125°C and kept at this value for 3 hours. After that, the resulting melt was emulsified with ROL OB55 AT vaseline oil continuously introduced at 125°C in an emulsifier, the stirring was brought to 2800 rpm and kept at that value for five minutes while continuously feeding the obtained emulsion into a stirred reactor containing cold hexane under stirring at 500 rpm.

The solid spherical catalyst support is then crystallized washed and dried, collecting a material having a composition of 58%EtOH, 10,2% Mg, 29.7%C1 by weight and a P50 of 55 micron.

The solid catalyst component was prepared by following the procedure below. Preparation of the solid catalyst component

Into a 2 litre steel reactor provided with stirrer, 1500 cm³ of TiCU at 0⁰C were introduced; at room temperature and whilst stirring 45 g of the above adduct were introduced together with an amount of diisobutylphthalate (DIBP) as internal donor so as to give a donor/Mg molar ratio of 7. The whole was heated to 100⁰C over 90 minutes and these conditions were maintained over 120 minutes. The stirring was stopped and after 30 minutes the liquid phase was separated from the settled solid maintaining the temperature at 100⁰C. Two further treatments of the solid were carried out adding 1500 cm³ of TiCU and heating the mixture at 120⁰C over 10 min. and maintaining said conditions for 60 min under stirring conditions (500 rpm). The stirring was then discontinued and after 30 minutes the liquid phase was separated from the settled solid maintaining the temperature at 120⁰C. Thereafter, 3 washings with 1500 cm³ of anhydrous hexane at 60⁰C and 3 washings with 1500 cm³ of anhydrous hexane at room temperature were carried out. The solid catalyst component obtained was then dried under vacuum in nitrogen environment at a temperature ranging from 40-45⁰C. The analysis showed a titanium content of 2.7%, a Mg content of 18.3%, and a DIBP content of 10.7%, and a P50 of 52 microns. Propylene polymerization test

A 4 litre steel autoclave equipped with a stirrer, pressure gauge, thermometer, catalyst feeding system, monomer feeding lines and thermostatting jacket, was used. The reactor was charged with 0.01 gr. of solid catalyst component 0,76 g of TEAL, 0.076g of dicyclopentyldimetoxy silane, 3.2 1 of propylene, and 1.5 1 of hydrogen. The system was heated to 70⁰C over 10 min. under stirring, and maintained under these conditions for 120 min. At the end of the polymerization, the polymer was recovered by removing any unreacted monomers and was dried under vacuum. The results are reported in table 1.

Example 2

The same procedure described fore the preparation of the support of example 1 was repeated with the difference that commercially available bohemite PURAL SCF55 having P50 of 11.5 μm was used instead of Cloesite 15A. The final adduct had P50 particle size of 51.6 μm. The catalyst was prepared and the polymerization test was carried out as described in Example 1.

The polymerization results are reported in table 1.

Example 3

The same procedure described fore the preparation of the support of example 1 was repeated with the difference that bohemite TH60 was used instead of Cloesite 15 A. The final adduct had

P50 particle size of 51.6 μm. The catalyst was prepared and the polymerization test was carried out as described in Example 1. The polymerization results are reported in table 1.

Comparison example 1

The same procedure described fore the preparation of the support of example 1 was repeated with the difference that cloesite 15A was not used. The final adduct had P50 particle size of 67 μm. The catalyst was prepared and the polymerization test was carried out as described in

Example 1. The polymerization results are reported in table 1.

TABLEl

Claims

1. Spherical adducts comprising a MgCl₂, an alcohol ROH in which R is a Cl-ClO hydrocarbon group, present in a molar ratio with MgCl₂ ranging from 0.5 to 5 and less than 5% wt, based on the total weight of the adduct, of a solid inorganic compound selected from oxides or hydroxides of Si, Al, Mg, Ti and mixtures thereof.

2. The spherical adducts according to claim 1 in which R is chosen among C1-C8 linear or branched hydrocarbon groups.

3. The spherical adducts according to claim 1 in which the number of moles of alcohol per mole of MgC^ ranges from 0.8 to 4.

4. The spherical adducts according to claim 1 containing the solid inorganic compound in amounts of less than 3%wt.

5. The spherical adducts according to claim 1 in which the particle size of said inorganic compound is of higher than 1 micron.

6. The spherical adducts according to claim 5 in which the particle size of said inorganic compound ranges from 2 to 80 microns.

7. The spherical adducts according to claim 1 in which the solid inorganic compound is selected from silicates, phyllosilicates, Al oxides, hydroxides and mixtures thereof.

8. Catalyst components for the polymerization of olefins obtained by reacting the spherical adducts of anyone of claims 1-7 with a transition metal compound of one of the groups IV to VI of the Periodic Table of Elements.

9. Catalyst for the polymerization of alpha-olefins CH₂=CHR, wherein R is hydrogen or a hydrocarbon radical having 1-12 carbon atoms, obtained by reacting the catalyst components of claim 8 with Al-alkyl compounds optionally in the presence of an external electron donor compound.

10. Process for the polymerization of olefins carried out in the presence of the catalyst of claim 9.