CATALYST AND PREPARATION THEREOF

Abstract

The present invention relates to a process for producing solid Ziegler-Natta catalyst component in the form of solid particles having a median particle size (D50.sub.vol) of 5 to 500 μm the process comprising steps I. providing a solution of a mixture of Group 2 metal compounds of i) a solution of a Group 2 metal dihalide and ii) at least one Group 2 metal alkoxide of the Periodic Table (IUPAC, Nomenclature of Inorganic Chemistry, 2005) II. contacting the solution of the mixture of Group 2 metal compounds of step I with a compound in a liquid form of a transition metal of Group 4 to 10, or of a lanthanide or actinide, preferably a transition metal of Group 4 to 6 of Periodic Table (IUPAC, Nomenclature of Inorganic Chemistry, 2005), and III. recovering the solid catalyst component, wherein the solution of a Group 2 metal dihalide i) is obtained by dissolving a solid Group 2 metal dihalide in an alcohol comprising at least a monohydric alcohol of formula ROH, where R is selected from hydrocarbyl of 3 to 16 C atoms, and wherein the amount of Group 2 metal originating from Group 2 metal dihalide in the solution of the mixture of Group 2 metal compounds is in the range of 5 to 90 mol-%. The invention further relates to a catalyst comprising the catalyst component and use thereof in olefin polymerisation process.

Claims

1: A process for producing solid Ziegler-Natta catalyst component in the form of solid particles having a median particle size (D50.sub.vol) of 5 to 500 μm the process comprising steps; I. providing a solution of a mixture of Group 2 metal compounds of: i) a solution of a Group 2 metal dihalide and ii) at least one Group 2 metal alkoxide of the Periodic Table (IUPAC, Nomenclature of Inorganic Chemistry, 2005), II. contacting the solution of the mixture of Group 2 metal compounds of step I with a compound in a liquid form of a transition metal of Group 4 to 10, or of a lanthanide or actinide of Periodic Table (IUPAC, Nomenclature of Inorganic Chemistry, 2005), and III. recovering the solid catalyst component, wherein the solution of a Group 2 metal dihalide i) is obtained by dissolving a solid Group 2 metal dihalide in an alcohol comprising at least a monohydric alcohol of formula ROH, where R is selected from hydrocarbyl of 3 to 16 C atoms, and wherein the amount of Group 2 metal originating from Group 2 metal dihalide in the solution of the mixture of Group 2 metal compounds is in the range of 5 to 90 mol %.

2: The process according to claim 1, wherein an internal donor selected from esters of carboxylic acids or di-acids, ethers, di-ethers and oxygen or nitrogen containing silicon compounds is added to the process before the recovery step III.

3: The process according to claim 1, wherein the Group 2 metal dihalide is MgCl.sub.2 and the Group 2 metal alkoxide is Mg alkoxide.

4: The process according to claim 1, wherein the transition metal compound of Group 4 to 10, or of a lanthanide or actinide is a Group 4 to 6 transition metal compound.

5: The process according to claim 1, wherein the amount of Group 2 metal originating from Group 2 metal dihalide is in the range of 10 to 85 mol %.

6: The process according to claim 1, wherein the Group 2 metal dihalide is dissolved in a mixture of alcohols comprising the monohydric alcohol of formula ROH (A1), where R is selected from a hydrocarbyl of 3 to 16 C atoms, and an alcohol (A2) comprising in addition to the hydroxyl group another oxygen containing functional group not being a hydroxyl group.

7: The process according to claim 1, wherein the Group 2 metal dihalide is dissolved in a mixture of alcohols comprising the monohydric alcohol of formula ROH (A1), where R is selected from a hydrocarbyl of 3 to 16 C atoms, and an alcohol (A2) comprising in addition to the hydroxyl group another oxygen containing functional group not being a hydroxyl group; and wherein in the alcohol (A2) another oxygen containing functional group not being a hydroxyl group is an ether group, wherein the ether moiety comprises from 2 to 18 carbon atoms.

8: The process according to claim 1, wherein the mol ratio of the monohydric alcohol (A1):alcohol (A2) is in the range of 10:0 to 1:9.

9: A Ziegler-Natta catalyst component in the form of solid particles having a median particle size (D50.sub.vol) of 5 to 500 μm obtained by a process comprising steps: I. providing a solution of a mixture of Group 2 metal compounds of i) a solution of a Group 2 metal dihalide and ii) at least one Group 2 metal alkoxide of the Periodic Table (IUPAC, Nomenclature of Inorganic Chemistry, 2005) II. contacting the solution of the mixture of Group 2 metal compounds of step I with a compound in a liquid form of a transition metal of Group 4 to 10, or of a lanthanide or actinide of Periodic Table (IUPAC, Nomenclature of Inorganic Chemistry, 2005), and III. recovering the solid catalyst component, wherein the solution of a Group 2 metal dihalide i) is obtained by dissolving a solid Group 2 metal dihalide in an alcohol comprising at least a monohydric alcohol of formula ROH, where R is selected from hydrocarbyl of 3 to 16 C atoms, and wherein the amount of Group 2 metal originating from Group 2 metal dihalide in the solution of the mixture of Group 2 metal compounds is in the range of 5 to 90 mol %.

10: The Ziegler-Natta catalyst component according to claim 9, wherein the amount of Ti is in the range of 1-6 wt %, the amount of Mg is in the range of 10 to 20 wt % and the amount of the internal donor is in the range of 5 to 35 wt % in the catalyst component.

11: The Ziegler-Natta catalyst component according to claim 9, wherein the catalyst component has a surface area of less than 20 m.sup.2/g.

12: A process for producing polymers of α-olefins of 2 to 10 C atoms or copolymers thereof with C.sub.2 to C.sub.12 α-olefin comonomers in the presence of the Ziegler-Natta catalyst component in the form of solid particles having a median particle size (D50.sub.vol) of 5 to 500 μm obtained, by a process comprising steps: I. providing a solution of a mixture of Group 2 metal compounds of i) a solution of a Group 2 metal dihalide and ii) at least one Group 2 metal alkoxide of the Periodic Table (IUPAC, Nomenclature of Inorganic Chemistry, 2005) II. contacting the solution of the mixture of Group 2 metal compounds of step I with a compound in a liquid form of a transition metal of Group 4 to 10, or of a lanthanide or actinidee of Periodic Table (IUPAC, Nomenclature of Inorganic Chemistry, 2005), and III. recovering the solid catalyst component, wherein the solution of a Group 2 metal dihalide i) is obtained by dissolving a solid Group 2 metal dihalide in an alcohol comprising at least a monohydric alcohol of formula ROH, where R is selected from hydrocarbyl of 3 to 16 C atoms, and wherein the amount of Group 2 metal originating from Group 2 metal dihalide in the solution of the mixture of Group 2 metal compounds is in the range of 5 to 90 mol %.

13-14. (canceled)

15: The catalyst comprising the Ziegler-Natta catalyst component as claimed in claim 9, a cocatalyst and optionally an external electron donor.

Description

[0119] FIG. 1: Catalyst component in the form of spherical particles prepared according to Comparative example 3.

[0120] FIG. 2: Catalyst component in the form of spherical particles prepared according to Inventive example 4.

[0121] FIG. 3: Catalyst component in the form of spherical particles prepared according to Inventive example 5.

[0122] FIG. 4: Catalyst component in the form of spherical particles prepared according to Inventive example 6

[0123] FIG. 5: Volumetric Particle Size Distribution of catalyst component of Inventive example 6

EXPERIMENTAL PART

[0124] Measurement Methods

[0125] Ti, Mg and Al Content—ICP-OES

[0126] The sample consisting of dry catalyst powder is mixed so that a representative test portion can be taken. Approximately 20-50 mg of sample is sampled in inert atmosphere into a 20 ml volume crimp cap vial and exact weight of powder recorded.

[0127] A test solution of known volume (V) is prepared to a volumetric flask. Sample digestion is performed in the cooled vial by adding a small amount of freshly distilled (D) water (5% of V) followed by concentrated nitric acid (HNO.sub.3, 65%, 5% of V). The mixture is transferred to the volumetric flask. The solution diluted with D water up to the final volume, V, and left to stabilise for two hours.

[0128] The elemental analysis of the aqueous samples are run at room temperature using a Thermo Elemental iCAP 6300 Inductively Coupled Plasma-Optical Emission Spectrometer (ICP-OES). The instrument is calibrated for Al, Ti and Mg using a blank (a solution of 5% HNO.sub.3), and 6 standards of 0.5 ppm, 1 ppm, 10 ppm, 50 ppm, 100 ppm and 300 ppm of Al, Ti and Mg in solutions of 5% HNO.sub.3 DI water. Curve linear fitting and 1/concentration weighting is used for the calibration curve.

[0129] Immediately before analysis the calibration is verified and adjusted (instrument function named ‘reslope’) using the blank and a 300 ppm Al, 100 ppm Ti, Mg standard. A quality control sample (QC; 20 ppm Al and Ti, 50 ppm Mg in a solution of 5% HNO.sub.3 in D water) is run to confirm the reslope. The QC sample is also run after every 5th sample and at the end of a scheduled analysis set.

[0130] The content of magnesium is monitored using the 285.213 nm and the content for titanium using 336.121 nm line. The content of aluminium is monitored via the 167.079 nm line, when Al concentration in test portion is between 0-10 wt-% and via the 396.152 nm line for Al concentrations above 10 wt-%. The reported values are an average of three successive aliquots taken from the same sample and are related back to the original catalyst sample by inputting the original mass of test portion and the dilution volume into the software.

[0131] Internal Electron Donor Content—GC-FID

[0132] The sample consisting of dry catalyst powder is mixed so that a representative test portion can be taken. Approximately 60-90 mg of sample is sampled in inert atmosphere into a 20 ml volume crimp cap vial and exact weight of powder recorded.

[0133] The test solution consisting of the internal donor in dichloromethane is prepared by liquid-liquid extraction of sample, water and organic solvent as follows: The test portion is dissolved in a volume of 5 ml of dichloromethane. A solution consisting of the internal standard dimethyl pimelate (0.28 V/V-%) and deionised water is added in a volume of 1 ml using a precision microsyringe. The suspension is sonicated for 20 min and let settle for phases to separate. The organic phase is sampled and filtered using a 0.45 μm filter to instrument vials.

[0134] The measurement is performed on an Agilent 7890B Gas Chromatograph equipped with flame ionisation detector. The column used is a ZB-5HT Inferno 15 m×320 μm×0.25 μm with midpoint backflush through a three channel of auxiliary EPC and a pre column restriction capillary of 1.5 m×320 μm×0 μm. The oven holds an initial temperature of 40° C. and hold time of 3 min. The ramp program consists of a first rate of 5° C./min to 70° C. and second ramp of 40° C./min to 330° C. and third ramp of 20° C./min to 350° C. with a hold time of 1 min.

[0135] The inlet operates in split mode. Injection volume is 1 μL, inlet temperature 280° C., pressure 2.941 psi, total flow 19.8 mL/min and split ratio 20:1. Carrier gas is 99.995% He with pre column flow of 0.8 mL/min and additional flow from backflush EPC to analytical column of 1 mL/min. The FID Detector operates at 370° C. with N.sub.2 makeup flow of 25 ml/min, synthesised air flow of 350 ml/min and hydrogen flow of 35 ml/min.

[0136] Signal from FID in chromatogram is integrated and calculated against a series of standardisation samples, using the response ratios between the signal for the internal donor and the internal standard dimethyl pimelate. Identity is determined by retention time. The standardisation for the internal donor has been performed with 4 standardisation solutions in a range of known masses of the internal donor corresponding to 7.68 mg to 19.11 mg normalised to 100 mg of sample and treated with the same sample preparation as the samples. The calibration curve for the response ratios is linear without sample concentration weighting. A quality control sample is used in each run to verify the standardisation. All test solutions are run in 2 replicate runs. The mass of the test portion is used for calculating the internal electron donor content for both replicates and the result reported as the average.

[0137] Particle Size Distribution—Automated Image Analysis

[0138] The sample consisting of dry catalyst powder is mixed so that a representative test portion can be taken. Approximately 50 mg of sample is sampled in inert atmosphere into a 20 ml volume crimp cap vial and exact weight of powder recorded. A test solution is prepared by adding white mineral oil to the powder so that the mixture holds a concentration of approximately 0.5-0.7 wt-%. The test solution is carefully mixed before taking a portion that is placed in a measuring cell suitable for the instrument. The measuring cell should be such that the distance of between two optically clean glasses is at least 200 μm.

[0139] The image analysis is run at room temperature on a Malvern Morphologi 3G system. The measuring cell is placed on a microscopy stage with high precision movement in all directions. The physical size measurement in the system is standardised against an internal grating or by using an external calibration plate. An area of the measuring cell is selected so that the distribution of the particles is representative for the test solution. This area is recorded in partially overlapping images by a CCD camera and images stored on a system specific software via a microscope that has an objective sufficient working distance and a magnification of five times. Diascopic light source is used and the illumination intensity is adjusted before each run. All images are recorded by using a set of 4 focal planes over the selected area. The collected images are analysed by the software where the particles are individually identified by comparison to the background using a material predefined greyscale setting. A classification scheme is applied to the individually identified particles, such that the collected population of particles can be identified to belong to the physical sample. Based on the selection through the classification scheme further parameters can be attributed to the sample.

[0140] The particle diameter is calculated as the circular equivalent (CE) diameter. The size range for particles included in the distribution is 6.8-200 μm. The distribution is calculated as a numerical moment-ratio density function distribution and statistical descriptors calculated based on the numerical distribution. The numerical distribution can for each bin size be recalculated for an estimate of the volume transformed distribution.

[0141] All graphical representations are based on a smothering function based on 11 points and the statistical descriptors of the population are based on the unsmothered curve. The mode is determined manually as the peak of the smothered frequency curve. Span is calculated as the (CE D[x, 0.9]−CE D[x, 0.1])/CE D[x, 0.5].

[0142] The following particle size and particle size distribution indicators have been used in the experiments:

[0143] D90.sub.vol=particle diameter at 90% cumulative volume,

[0144] D10.sub.vol=particle diameter at 10% cumulative volume,

[0145] D50.sub.vol=particle diameter at 50% cumulative volume (median particle size, vol)

[0146] SPAN.sub.vol=(D90.sub.vol−D10.sub.vol)/D50.sub.vol

[0147] Melt Flow Rate

[0148] MFR.sub.2: 230° C., 2.16 kg load

[0149] The melt flow rate is measured in accordance with ISO 1133 and is indicated as g/10 min.

EXAMPLES

[0150] Raw Materials

[0151] TiCl.sub.4 (CAS 7550-45-90) was supplied by commercial source.

[0152] 20% solution in toluene of butyl ethyl magnesium (Mg(Bu)(Et)), provided by Crompton

[0153] 2-ethylhexanol, provided by Merck Chemicals

[0154] 3-Butoxy-2-propanol, provided by Sigma-Aldrich

[0155] bis(2-ethylhexyl)citraconate, provided by Contract Chemicals

[0156] Viscoplex® 1-254, provided by Evonik

[0157] Heptane, provided by Chevron

[0158] MgCl.sub.2— Anhydrous magnesium dichloride was provided by Sigma-Aldrich

EXAMPLES

Comparative Example 1 CE1—Preparation of Soluble Mg-Alkoxide

[0159] 3.4 litre of 2-ethylhexanol (Alcohol A1) and 810 ml of propylene glycol butyl monoether (Alcohol A2) (in a molar ratio A1/A2 of 4/1) were added to a 20 I steel reactor. Then 7.8 litre of a 20% solution in toluene of BEM (butyl ethyl magnesium), were slowly added to the well stirred alcohol mixture. During the addition the temperature was kept at 10° C. After addition the temperature of the reaction mixture was raised to 60° C. and mixing was continued at this temperature for 30 minutes. Finally, after cooling to room temperature the obtained Mg-alkoxide was transferred to a storage vessel. Mg content of 2.75 wt-% was found by ICP. Alcohol to BEM molar ratio was 2.2.

Comparative Example 2 CE2—Preparation of Mg Complex

[0160] 21.2 g of Mg alkoxide prepared in CE1 was mixed with 4.0 ml of electron donor (bis(2-ethylhexyl)citraconate) for 5 min. After mixing, the obtained Mg complex was used immediately in the preparation of the catalyst component.

Comparative Example 3 CE3—Preparation of the Catalyst Component

[0161] Preparation of catalyst component was performed in a jacketed thermostated 100 mL glass reactor equipped with a pitched blade impeller. The reactor was charged with 13.0 ml of TiCl.sub.4 and tempered at 15° C. Mixing speed was adjusted to 500 rpm. 16.8 g of Mg-complex prepared in Example CE2 was added to TiCl.sub.4 within 20 minutes keeping the temperature at 15° C. 0.7 ml of Viscoplex® 1-254 and 21.0 ml of heptane were then added, whereby an emulsion was formed. Mixing (700 rpm) was continued for 30 minutes at 15° C., after which the reactor temperature was raised to 90° C. within 45 minutes. The reaction mixture was stirred for a further 30 minutes at 90° C. at 700 rpm. Afterwards stirring was stopped and the reaction mixture was allowed to settle for 15 minutes at 90° C. The solid material was washed 5 times: Washings were made at 80° C. under stirring for 20 min with 500 rpm with toluene, TiCl.sub.4/donor mixture, toluene and twice with heptane. After stirring was stopped the reaction mixture was allowed to settle for 10-30 minutes and followed by siphoning between the washes.

[0162] After the last wash the temperature was decreased to 70° C. with subsequent siphoning, followed by N.sub.2 purge for 60 minutes to yield an air sensitive powder.

[0163] The catalyst component was isolated in the form of spherical microparticles, as presented in FIG. 1. Catalyst analysis and morphological properties are disclosed in Table 4.

Inventive Example 1/E1—Preparation of Soluble Mg-Alkoxide with 33% of Mg Originating from MgCl.SUB.2

[0164] Mg-alkoxide was prepared using MgCl.sub.2 as additional source for magnesium.

[0165] MgCl.sub.2 was dissolved in an alcohol mixture of 2-ethylhexanol (A1) and butoxypropanol (A2) at a temperature of 120° C. for 3 hours. The amounts and ratios of MgCl.sub.2 and alcohols are disclosed in Table 1.

TABLE-US-00001 TABLE 1 Dissolving MgCl.sub.2 to alcohol mixture according to IE1 g ml mol Mol ratio Alcohol/Mg MgCl.sub.2 9.96 0.104 2-ethylhexanol 47.0 56.4 0.357 3.43 4.3 butoxypropanol 11.9 13.4 0.089 0.86

[0166] 9.96 g of MgCl.sub.2 was placed in a 300 ml glass reactor equipped with a stirrer. Temperature was kept at 25° C. by keeping the reactor in a cooling bath when adding a mixture of 56.4 ml of 2-ethyl hexanol (2-EHA) and 13.4 ml of butoxypropanol. After addition of the alcohol mixture, the reactor temperature was increased to 120° C. After about 3 hours all MgCl.sub.2 was dissolved (MgCl2 alcohol solution). The total yield was 68.12 g and the calculated composition comprised 14.6% MgCl.sub.2 (3.7% Mg), 68.3% 2-EHA and 17.2% butoxypropanol. 24.46 g of the diluted MgCl.sub.2 solution was obtained by mixing together 20.13 g of the previously prepared MgCl.sub.2 alcohol solution and 5 ml (4.33 g) toluene to result in 24.5 g of Solution1-1. The magnesium alkoxide solution was prepared by adding 20% butyl ethyl magnesium (BEM) in toluene to the Solution1-1 prepared above according to the procedure as described below: 31.2 ml (49.0 mmol) 20% BEM in toluene was slowly added to 19.83 g of Solution1-1 while keeping the temperature below 25° C. After the addition was completed, a milky solution was obtained which became again clear after the temperature was increased to 60° C. After mixing for 1 hour at 60° C. the solution was cooled down to room temperature (Mg solution mixture). The composition of the magnesium alkoxide solution contained 2.36 g of MgCl.sub.2 and 1.19 g of Mg in form of the respective alkoxides, 1.3 g of free alcohol and about 26 g toluene. Consequently, the total amount of Mg in the solution of Mg compound mixture was 1.79 g (4.1 wt %) with 33% of the Mg from added MgCl2, as indicated in Table 2.

TABLE-US-00002 TABLE 2 Amount and calculated composition of the magnesium alkoxide solution Yield MgCl2 Mg MgCl2 Mg(OR)2 Mg(OR)2 Mgtot Mgtot Mgtot (g) (g) (g) (mmol) (g) (mmol) (g) (wt-%) (mmol) 43.3 2.36 0.6 24.8 1.19 49 1.79 4.1 74.8

Inventive Example 2 IE2—Preparation of Soluble Mg-Alkoxide with 50% Mg Originating from Magnesium Dichloride

[0167] Mg-alkoxide was prepared using MgCl.sub.2 as additional source for magnesium.

[0168] 25.08 g of MgCl.sub.2 was placed into the 300 ml glass reactor equipped with a stirrer. Temperature was kept around 25° C. by keeping the reactor in cooling bath when slowly adding the mixture of 70.5 ml of 2-ethyl hexanol and 16.7 ml of butoxypropanol. Addition took 75 minutes. The temperature was increased to 135° C. and mixing was continued for 8 hours. During cooling down 25 ml of toluene was added to result in Solution 1-2. Table 3 shows the actual amounts and the MgCl.sub.2 to alcohols molar ratio.

TABLE-US-00003 TABLE 3 Dissolving MgCl.sub.2 to alcohol mixture according to IE2 g ml mol Mol ratio Alcohol/Mg MgCl.sub.2 25.08 0.262 2-ethylhexanol 58.9 70.5 0.446 1.7 2.2 butoxypropanol 14.9 16.7 0.111 0.4 Toluene — 25 —

[0169] The magnesium alkoxide solution was prepared by adding 20% butyl ethyl magnesium (BEM) in toluene to the Solution1-2 prepared above according to the procedure as described below: 162.5 ml of BEM solution (20% in toluene) was very slowly added to the Solution 1-2 keeping the temperature below 25° C. Addition took 3.5 hours. During addition off gas was released and also foam was formed on top of the solution which prevented faster addition. Viscosity of the solution was significantly decreasing during addition. After BEM was fed, the temperature was slowly increased to 60° C. Foaming was continued during heating up. After one hour mixing at 60° C. the solution was cooled down to room temperature. Alcohol to BEM molar ratio was 2.2, which is the same as in comparative example CE1. The obtained composition of the Mg alkoxide solution was a clear solution having 5.2 wt-% of Mg. Half (50%) of the Mg content originates from MgCl.sub.2.

Inventive Example 3 IE3—Preparation of Soluble Mg Alkoxide—with 33% Mg Originating from Magnesium Dichloride

[0170] MgCl.sub.2 alcohol solution was prepared by using 10.02 g of MgCl.sub.2 dispersed in 15 ml of toluene. Then 56.4 ml of 2-ethyl hexanol and 13.4 ml of butoxypropanol were added to the reactor. Addition time of alcohols was one hour. Temperature was then increased to 125° C. After 90 min mixing all MgCl.sub.2 was dissolved and a clear solution was obtained. Viscosity of the obtained solution (Solution1-3) was 210 mPas at room temperature.

[0171] The magnesium alkoxide solution was prepared by adding 20% butyl ethyl magnesium (BEM) in toluene to the Solution1-3 as follows: BEM solution (133 ml) (20% in toluene) was added under stirring over several minutes. The temperature was then slowly increased to 80° C. and mixing at this temperature was continued for one hour. During the temperature increase and mixing at 80° C. a significant amount of gas was formed. The temperature was then increased to 90° C. and mixing was continued for another 4 hours. The obtained magnesium alkoxide solution was a clear viscous solution with 33% of magnesium coming from MgCl.sub.2 and a calculated magnesium content was 4.2 wt. %.

Inventive Example 4 IE4—Preparation of the Catalyst Component

[0172] Catalyst component was prepared following the procedure of comparative examples CE2 and CE3, but using the solution of the mixture of Mg compounds of inventive example IE1.

[0173] A 100 ml glass reactor equipped with a mechanical stirrer was charged with 13.0 mL of titanium tetrachloride at 15° C. Mixing speed was adjusted to 500 rpm. Mg-complex prepared by mixing 12.7 g of the solution of Mg compound mixture (Mg-alkoxide) of IE1 and 3.3. ml donor (bis(2-ethylhexyl) citraconate) for 5 min was added to TiCl.sub.4 within 20 minutes keeping the temperature at 15° C. 1.0 ml of Viscoplex®1-254 and 15.0 ml of heptane was added, whereby an emulsion was formed. Mixing (700 rpm) was continued for 30 minutes at 15° C., after which the reactor temperature was raised to 90° C. within 45 minutes. The reaction mixture was stirred for a further 30 minutes at 90° C. at 700 rpm. Afterwards stirring was stopped and the reaction mixture was allowed to settle for 15 minutes at 90° C. The solid material was washed 5 times: Washings were made at 80° C. under stirring for 20 min with 500 rpm with toluene, TiCl.sub.4/donor mixture, toluene and twice with heptane. After stirring was stopped the reaction mixture was allowed to settle for 10-30 minutes and followed by siphoning between the washes.

[0174] Analytical results of the composition of the catalyst component are disclosed in Table 4. The obtained spherical particles are shown in FIG. 2.

Inventive Example 5 IE5—Preparation of the Catalyst Component

[0175] Catalyst component was prepared according to the procedure of inventive example IE4, but using the Mg alkoxide solution of inventive example IE2. Catalyst morphology and composition was on a good level.

[0176] Analytical results of the composition of the catalyst component are disclosed in Table 4 and the obtained spherical particles are shown in FIG. 3.

Inventive Example 6 IE6—Preparation of the Catalyst Component

[0177] The preparation was done as in IE4, except Mg alkoxide solution of IE3 (12.7 g, diluted with 3 mL toluene) was used.

[0178] Catalyst was isolated in the form of microspheres. Analytical results of the composition of the catalyst component are disclosed in Table 4. The obtained spherical particles are shown in FIG. 4 and volumetric particle size distribution is disclosed in FIG. 5.

TABLE-US-00004 TABLE 4 Catalyst composition of inventive examples IE4 to IE6 and Comparative example CE3 Catalyst Ti Mg Donor Hydrocarbon Mg yield component wt-% wt-% wt-% wt-% D50.sub.vol % IE4 2.35 13.5 21.2 9.9 NA 77 IE5 3.08 14.3 21.3 6.2 NA 92 IE6 2.55 14.3 26.8 3.3 53 72 CE3 2.64 13.2 17.3 11.5 61 77

[0179] Polymerisation

[0180] A 5 litre stainless steel reactor was used for propylene polymerisations.

[0181] About 0.9 ml triethyl aluminium (TEA) (from Witco, used as received) as a co-catalyst, ca 0.13 ml dicyclopentyl dimethoxy silane (DCDS) (from Wacker, dried with molecular sieves) as an external donor and 30 ml n-pentane were mixed and allowed to react for 5 minutes. Half of the mixture was then added to the polymerisation reactor and the other half was mixed with about 20 mg of a catalyst. After additional 5 minutes the catalyst/TEA/donor/n-pentane mixture was added to the reactor. The Al/Ti ratio was 250 mol/mol and the AI/DCDS ratio was 10 mol/mol. 200 mmol hydrogen and 1400 g propylene were introduced into the reactor and the temperature was raised within ca 20 minutes to the polymerisation temperature (80° C.). The polymerisation time after reaching polymerisation temperature was 60 minutes, after which the polymer formed was taken out from the reactor. Polymerisation results are disclosed in Table 5.

[0182] Polymerisation results show that catalyst activities and melt flow rates remain, as was desired, on the same level in inventive examples and comparative examples 1 and 2, which shows that catalyst of the invention with excellent particle size distribution fulfils the polymerisation criteria. In comparative example 3 the values differ from the other examples, however, the catalyst differs essentially in morphological point of view, and the chemistry of said catalyst is different. As explained in the specification, reactor fouling and plugging will not be seen in the small scale polymerisation tests.

TABLE-US-00005 TABLE 5 Polymerisation results Activity kg MFR2, BD, XS, Catalyst PP/g cat h dg min kg/m3 wt. % CE3 35.4 15.3 427 1.9 IE4 31.0 14.0 NA 1.6 IE5 21.5 15.7 NA NA IE6 22.2 13.7 NA 1.9