“PROCESS FOR THE PREPARATION OF POLYPROPYLENE”

FIELD OF THE INVENTION

[0001] The present disclosure relates to a polymerization process for the preparation of a propylene polymer containing coloured compounds. The so obtained polymer have optimal visual appearance.

BACKGROUND OF THE INVENTION

[0002] Polyolefins such as polypropylene may be prepared into articles which can be made appealing by the use of so called additive package. This package, in addition to the conventional stabilizers, may include clarifying agents to increase transparency and colouring agent to impart a more or less intense colour.

[0003] The above-mentioned additives can be added in the form of an "additive package" pre blend which may contain also one or more of the following: antioxidant; acid scavengers, slip agents, light stabilizers, optical brighteners and UV light absorbers.

[0004] Sometimes the colouring agent (which may be in the form of a masterbatch pre-mixed with polymer) is added during or just prior to the forming process. A relatively high colorant loading of 500-1000 parts per million (ppm) may be mixed and adequately dispersed into a plastic in this manner. The conventional process is used for applying a high degree of colour to make brightly coloured plastic articles for everyday use.

[0005] It is more difficult to adequately disperse an additive into a plastic or polymer at extremely low additive concentration levels. For example, dispersing an additive into a polymer at very low loading levels can be made through several steps of successive dilutions. Thus, applying additives in a range of a few ppm involves discrete steps which are necessarily time consuming in polymer manufacturing applications.

[0006] On the other hand, adding small amounts of colouring agents to polyolefins, and in particular to propylene polymers, can improve visual appearance. EP 1989252 describes a method for dispersing low amounts of colouring agents into a polymer, in particular polypropylene, which comprises forming a first blend between said colouring agent and a clarifying agent. The so obtained first blend is then added, possibly together with additional stabilizer, to the molten polymer and then extruded. [0007] Although the dispersion result may be good, this method suffers from the problem that an additional stage of mixing is needed and of the fact that use of a clarifying agent becomes necessary even if optical properties are not strictly needed.

[0008] U.S. Patent 10,030, 121 describes a process for the preparation of UHMWPE in which a pigment, previously dispersed in a slurry is mixed with a ZN catalyst and the so obtained mixture contacted with ethylene in order to polymerize it. The pigment is used in an amount such that its final amount in the polymer ranges from 50 ppm to 5000 ppm. This technique may suffer from several drawbacks. For example, if not used immediately after its preparation, the suspension must be stored and, due to the hydrocarbon diluent flammability, effective and burdensome measures have to be taken. In addition, when the catalyst is to be fed in a dry form to the reactor, a further stage of diluent removal is needed.

[0009] US2016/289422 describes the formation of a catalyst by combining a catalyst precursor mixture with a colorant mixture and immediately injecting I the resulting product n the polymerization reactor.

[0010] Although small amounts of colorants can be dispersed in this way, it introduces the problem of a new and unknown catalyst aging profile deriving from the presence of the colorant. This would heavily impact on the possible commercial use of the colorant/catalyst mixture as it is common industrial practice to store the catalyst before use for a widely variable time. Once used after storage time, the catalyst performances and, as a consequence, the polymerization process would be no longer reliable.

[0011] There is therefore the need for a method to effectively disperse low amounts of colouring agents into a propylene polymer in a way that does not make burdensome the polymer treatment and that does not deteriorate the catalyst performance while maintaining smooth handling and reliability of the entire polymerization process.

SUMMARY OF THE INVENTION

[0012] The present disclosure presents a process for the preparation of a propylene polymer containing a colouring agent, comprising:

(i) forming a solid mixture (a-b) of (a) a ZN catalyst component which comprises Mg, Ti, halogen and an internal electron donor compound, and (b) a colouring agent comprising at least a pigment; said mixture being in a weight ratio (b):(a) ranging from 0.01 : 1 to 0.4: 1;

(ii) feeding the mixture (a-b) to a polymerization reactor and subjecting the reactor to polymerization conditions so as to produce the propylene polymer, said process being characterized in that the b:a weight ratio and the time in days elapsed between mixture formation and use in polymerization fall below the curve defined by the equation y=3+0.832x ^{1 17} where y is the time in days elapsed between mixture formation and use in polymerization and x is the (b):(a) weight ratio.

[0013] The ZN solid catalyst component a) may be of granular, spheroidal irregular or spherical regular morphology. Preferably, it has a spherical regular morphology.

[0014] Granular or otherwise irregular catalyst particle may be obtained by reacting Ti-halides with precursors of general formula MgX _n (OR)2-nin which X is Cl or aCi-Cio hydrocarbon group, R is a Ci-Cs alkyl group and n ranges from 0 to 2. Such a reaction generates solid particles basically composed of MgCh on which Ti compound are fixed.

[0015] Catalyst components with a regular morphology may be obtained by reacting Ti-halides with precursors comprising adducts of formula MgCl2(R ¹ OH) _n where R is a C i-Cx alkyl group preferably, ethyl, and n is from 2 to 6.

[0016] Preferably, the amount of Mg in the solid catalyst component ranges from 8 to 30% more preferably from 10 to 25%wt with respect to the total weight of solid catalyst component.

[0017] Preferably, the amount of Ti ranges from 0.5 to 8% and more preferably from 0.7 to 5%wt and in particular from 1 to 3.5%wt with respect to the total weight of solid catalyst component.

[0018] The titanium atoms preferably belong to titanium compounds of formula Ti(OR ² )nX4-n in which n is comprised between 0 and 4; X is halogen and R ² is an hydrocarbon radical, preferably alkyl, radical having 1-10 carbon atoms. 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 TiCU, and Ti(OEt)Ch.

[0019] The catalyst component further comprises an electron donor compound (internal donor). Preferably, it is selected from esters, ethers, amines, silanes, carbamates and ketones or mixtures thereof.

[0020] The internal donor is preferably selected from the group consisting of alkyl and aryl esters of optionally substituted aromatic mono or polycarboxylic acids such as for example esters of benzoic and phthalic acids, and esters of aliphatic acids selected from malonic, glutaric, maleic and succinic acids. Specific examples of such esters are n-butylphthalate, di-isobutylphthalate, di-n-octylphthalate, ethyl-benzoate and p-ethoxy ethyl-benzoate. Also, the diesters disclosed in W02010/078494 and US7,388,061 can be used. Among this class, particularly preferred are the 2,4-pentanediol dibenzoate derivatives and 3 -methyl-5 -t-butyl catechol dibenzoates. In addition, the internal donor can be selected among diol derivatives chosen among dicarbamates, monoesters monocarbamates and monoesters monocarbonates. Moreover, can be used also the 1,3 di ethers of the formula:

wherein R, R ¹ , R ⁿ , R ⁱⁿ , R ^IV and R ^v equal or different to each other, are hydrogen or hydrocarbon radicals having from 1 to 18 carbon atoms, and R ^VI and R ^v ", 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 ^v " groups can be linked to form a cycle. The 1,3-diethers in which R ^VI and R ^v " are selected from C1-C4 alkyl radicals are particularly preferred.

It is also possible to use mixtures of the above mentioned donors. Specific mixtures are those constituted by esters of succinic acids and 1,3-diethers as disclosed in WO2011/061134.

[0021] In general, the final amount of electron donor compound in the solid catalyst component may range from 0.5 to 30% by weight preferably in the range from 1 to 20% by weight.

[0022] The preparation of the solid catalyst component can be carried out according to several methods. One method comprises the reaction between magnesium alcoholates or chloroalcoholates (in particular chloroalcoholates prepared according to U.S. Pat. No. 4,220,554) and an excess of TiCU in the presence of the electron donor compounds at a temperature of about 80 to 120°C.

[0023] According to a preferred method, the solid catalyst component can be prepared by reacting a titanium compound of formula Ti(OR ² )m-yXy, where m is the valence of titanium and y is a number between 1 and m and R ² has the same meaming as previously specified, preferably TiCU, with a magnesium chloride deriving from an adduct of formula MgCl2*pR ³ OH, where p is a number between 0.1 and 6, preferably from 2 to 3.5, and R ³ is a hydrocarbon radical having 1-18 carbon atoms. The adduct can be suitably prepared in spherical form by mixing alcohol and magnesium chloride in the presence of an inert hydrocarbon immiscible with the adduct, operating under stirring conditions at the melting temperature of the adduct (100-130°C). Then, the emulsion is quickly quenched, thereby causing the solidification of the adduct in form of spherical particles. Examples of spherical adducts prepared according to this procedure are described in U.S. Patent No. 4,399,054 and U.S. Patent No. 4,469,648. The so obtained adduct can be directly reacted with Ti compound or it can be previously subjected to thermal controlled dealcoholation (at a temperature in a range of about 80-130°C) so as to obtain an adduct in which the number of moles of alcohol is lower than 3, preferably between 0.1 and 2.5. The reaction with the Ti compound can be carried out by suspending the adduct (dealcoholated or as such) in cold TiCk (about 0°C); the mixture is heated up to 80-130°C and kept at this temperature for 0.5-2 hours. The treatment with TiCU can be carried out one or more times. The electron donor compound is preferably added during the treatment with TiCk. The preparation of catalyst components in spherical form are described for example in European Patent Applications EP-A-395083, EP-A- 553805, EP-A-553806, EPA601525 and WIPO Pat. App. Pub. No. W098/44009.

[0024] The colouring agent b) comprises at least one pigment. In some embodiments, the colouring agent may be a mixture containing a dye. In additional embodiments, the colouring agent may comprise a dye in combination with one or more pigments.

[0025] The pigment can be either organic or inorganic. An organic pigment according to the present disclosure contains at least a C-H bond in its structure. Conversely, an inorganic pigment is the one that does not contain C-H bonds in its structure.

[0026] Preferably pigments used according to the present disclosure have black or blue colour.

[0027] Preferred pigments are those based on Carbon Black, like Cabot Black, phthalocyanine metal derivatives like Cu-Phthalocyanine, Ultramarine Blue (inorganic), and quinacridone based pigments. Among them Cu-phtalocyanine is especially preferred.

[0028] Preferably, the colouring agent is used in step (i) in amount such that the weight ratio colouring agent b)/catalyst component a) ranges from 0.01 : 1 to 0.30: 1, more preferably from 0.01 : 1 to 0.25: 1 and especially from 0.01 : 1 to 0.20: 1.

[0029] The solid catalyst component a) and the coloring agent b) can be mixed using the available techniques for mixing solids paying attention to prevent the contact of the components with contaminants such as oxygen and water.

[0030] Typically, the solid dry mixture can be prepared using a closed device equipped with internal rotating means, like mechanical stirrers, or by using a closed rotating device in which components a) and b) are mixed without the use of a liquid medium.

[0031] The mixing time can range from 5 minutes to 24 hours preferably from 30 minutes to 4 hours. The temperature at which the mixing occurs may be in a range such that the mixing temperature is not close to the melting or degradation points of the solids a) and b); in particular, the mixing temperature can suitably range between 0 and 80°C. Preferably the mixing occurs at room temperature (about 23°C to about 25°C).

[0032] After mixing, the solid mixture can be used immediately in polymerization or it can be stored for a period of time respecting the equation y=3+0.832x ^{1 17} where y is the time in days elapsed between mixture formation and use in polymerization and x is the (b):(a) weight ratio.

[0033] In a specific embodiment, of the present disclosure the process is carried out in such a way that in step (i) the weight ratio (b):(a) ranges from 0.01 : 1 to 0.25: 1 and in step (ii) the mixture (a-b) is fed to the polymerization reactor within a maximum number of days ranging from 7 to 65.

[0034] In general, the activity of the solid catalyst mixture (a-b) expressed as Kg polymer/g mixture fed is lower than that of the component (a) alone which may range from 30 to 100 Kg polymer/g catalyst. This is at least partially due to the dilution effect provided by the pigment. Therefore, in order to take into account this effect, the polymerization activity of the solid mixture is always referred to the amount of component (a) of the mixture. However, it is also clear that an accelerated aging of the catalyst may be brought by the colouring agent. In particular, it has been noted that if, for a given weight ratio, the time elapsed from preparation to use exceeds the value given by the equation the catalyst performances are degraded to an extent that the catalyst activity becomes too low and the plant productivity is impacted. Preferably, the propylene polymers of the present disclosure are characterized by an amount of coloring agent ranging from 0.2 to 15, preferably from 0.3 to 10 ppm, and especially from 0.3 to 8 ppm referred to the weight of propylene polymer. These propylene polymers may allow to produce objects with improved visual appearance. This is shown by the fact that the yellowness index of the polymer is reduced with respect to that of the polymer not containing the coloring agent. If a catalyst provides an unexpectedly too low polymerization activity, the final amount of coloring agent may become too high thereby imparting a too pronounced coloration of the polymer. Under this situation, the final object may not show the desired visual appearance. However, respecting the guidance given by the above equation ensures that the catalyst activity remains at a satisfactory level to give the proper final amount of coloring agent while maintaining interesting values of polymer properties like stereoregularity (measured through Xylene Insolubility) and bulk density (which is directly linked to the polymer morphology).

[0035] The solid mixture of the present disclosure is used in polymerization together with an aluminium alkyl cotatalyst and, optionally, an external electron donor compound. [0036] The alkyl-Al compound is preferably chosen among the trialkyl aluminum compounds such as for example triethylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum. It is also possible to use mixtures of trialkylaluminum's with alkylaluminum halides, alkylaluminum hydrides or alkylaluminum sesquichlorides such as AlEt2Cl and AbEhCb.

[0037] Preferred external electron-donor compounds include silicon compounds, ethers, esters such as ethyl 4-ethoxybenzoate, amines, heterocyclic compounds and particularly 2, 2,6,6- tetramethyl piperidine, ketones and the 1,3-diethers. Another class of preferred external donor compounds is that of silicon compounds of formula Ra ⁵ Rb ⁶ Si(OR ⁷ ) _c , where a and b are integer from 0 to 2, c is an integer from 1 to 3 and the sum (a+b+c) is 4; R ⁵ , R ⁶ , and R ⁷ , are alkyl, cycloalkyl or aryl radicals with 1-18 carbon atoms optionally containing heteroatoms. Particularly preferred are methylcyclohexyldimethoxysilane, diphenyldimethoxysilane, methyl- t-butyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-t- butyldimethoxysilane and l,l,l,trifluoropropyl -2-ethyl piperidinyl-dimethoxy silane and l,l,l,trifluoropropyl-metil-dimethoxysilane. The external electron donor compound is used in such an amount to give a molar ratio between the organo-aluminum compound and said electron donor compound of from 5 to 500, preferably from 7 to 400 and more preferably from 10 to 200.

[0038] Optionally a prepolymerization step can be carried out before the main polymerization step. The prepolymerization step can be carried out in a first reactor selected from a loop reactor or a continuously stirred tank reactor. The prepolymerization can be carried out either in gas- phase or in liquid-phase. Preferably it is carried out in liquid-phase. The liquid medium comprises liquid alpha-olefin monomer(s), optionally with the addition of an inert hydrocarbon solvent. Said hydrocarbon solvent can be either aromatic, such as toluene, or aliphatic, such as propane, hexane, heptane, isobutane, cyclohexane and 2,2,4-trimethylpentane. The amount of hydrocarbon solvent, if any, is lower than 40% by weight with respect to the total amount of alpha-olefins, preferably lower than 20% by weight. Preferably, the pre-polymerization step is carried out in the absence of inert hydrocarbon solvents.

[0039] The average residence time in this reactor may range from 2 to 40 minutes, preferably from 10 to 25 minutes. The temperature ranges from 10°C to 50°C, preferably from 20°C to 40°C. Adopting these conditions allows to obtain a pre-polymerization degree in the preferred range from 60 to 800g per gram of solid catalyst component, preferably from 150 to 500 g per gram of solid catalyst component.

[0040] The slurry containing the prepolymerized catalyst is discharged from the pre polymerization reactor and fed to the reactor where the main polymerization step takes place. [0041] The main polymerization stage can be carried out either in gas-phase or in liquid phase. The gas-phase process can be carried out in a fluidized or stirred, fixed bed reactor or in a gas- phase reactor comprising two interconnected polymerization zones one of which, working under fast fluidization conditions and the other in which the polymer flows under the action of gravity. The liquid phase process can be either in slurry, solution or bulk (liquid monomer). This latter technology is the most preferred and can be carried out in various types of reactors such as continuous stirred tank reactors, loop reactors or plug-flow ones. The polymerization is may be carried out at temperature of from 20 to 120°C, preferably of from 40 to 85°C. When the polymerization is carried out in gas-phase the operating pressure is may range between 0.5 and 10 MPa, preferably between 1 and 5 MPa. In the bulk polymerization the operating pressure may range between 1 and 6 MPa preferably between 1.5 and 4 MPa. Preferably, the main polymerization stage is carried out by polymerizing in liquid monomer, preferably in loop reactor, propylene, optionally in mixture with ethylene and/or Ch-Cio alpha olefins, to give the cristalline propylene polymer.

[0042] Hydrogen can be used as a molecular weight regulator. The propylene polymer obtained in this stage has a xylene insolubility preferably higher than 90% and more preferably higher than 95%, an isotactic index in terms of content of isotactic pentads (determined with C ¹³ -NMR on the whole polymer) higher than 93% and preferably higher than 95%. The Melt Flow Rate value according to ISO 1133 (230°C, 2.16 Kg) can vary within a wide range going from 0.01 to 300 g/lOmin and particularly from 0.1 250 g/lOmin. The polymer bulk density may range from 0.40 to 0.50 g/cm ³ .

[0043] In case of production of heterophasic propylene copolymers (also called impact copolymers) a second polymerization stage in a different reactor is carried out for the preparation of a propylene/ethylene copolymer. The second stage may be carried out in a conventional fluidized-bed gas-phase reactor in the presence of the polymeric material and the catalyst system coming from the preceding polymerization step. The polymerization mixture is discharged from the first reactor to a gas-solid separator, and subsequently fed to the fluidized-bed gas-phase reactor operating under conventional conditions of temperature and pressure.

[0044] The polymer produced in this second stage is preferably an ethylene copolymer containing from 15 to 75% wt of a C3-C 10 alpha olefin, optionally containing minor proportions of a diene, being for at least 60% soluble in xylene at room temperature. Preferably the alpha olefin is selected from propylene or butene-1 and its content ranges preferably from 20 to 70%wt. [0045] The final propylene polymer obtained through the process of the present disclosure can be obtained as reactor grade with a Melt Flow Rate value according to ISO 1133 (230°C, 2.16 Kg) ranging from 0.01 to 100 g/lOmin, preferably from 0.1 to 70 and more preferably from 0.2 to 60. If desired, it can be chemically degraded in order to reach the final MFR value suited for the selected application.

[0046] The so obtained propylene polymers can also be added with additives employed in the art, such as antioxidants, light stabilizers, heat stabilizers, clarifying agents and nucleating agents.

[0047] In particular, the addition of nucleating agents may bring about an improvement in physical-mechanical properties, such as Tensile Modulus which may range from 800 to 1800 MPa, tensile strength at yield which may range from 20 to 50 MPa, and transparency.

[0048] Typical examples of nucleating agents are the p-tert. -butyl benzoate, dibenzylidene sorbitol derivatives and talc.

[0049] The nucleating agents are preferably added to the compositions of the present disclosure in quantities ranging from 0.05 to 2% by weight, more preferably from 0.1 to 1% by weight with respect to the total weight. The effect of nucleation can be seen by the increase of the crystallization temperature of the polymer. On the other hand, it is also possible that the coloring agent used according to the present disclosure provides the same effect. In particular, it has been observed that the small amount of Cu-phthalocyanine used as coloring agent also has a nucleating effect by increasing the crystallization temperature to 120°-125°C.

[0050] Among clarifying agents, Dibenzylidene sorbitol derivatives are the preferred ones.

[0051] These are sold in particulate form. Compounds such as l,3-0-2,4-bis(3,4- dimethylbenzylidene) sorbitol (hereinafter "DMDBS"), available from Milliken and Company under the trade name Millad® 3988, provide nucleation and clarification characteristics for polypropylene. Other DBS-based clarifying compounds can be employed, including those with other groups substituted on the sorbitol portion of the molecule, or upon the benzene ring portion of the molecule. Other clarifying agent compounds could be employed, such as aluminum bis[2,2’-methylene-bis-(4,6-di-tertbutylphenyl) phosphate] (from Adeka Palmarole SAS of France, commercialized as "NA-21™").

[0052] The so obtained polymers can be used in the preparation of finished articles according to the customarily techniques such as injection molding, extrusion blow molding, injection stretch blow molding and thermoforming.

EXAMPLES [0053] The data of the propylene polymer materials were obtained according to the following methods:

Xylene-soluble faction

[0054] 2.5 g of polymer and 250 mL of o-xylene are introduced in a glass flask equipped with a refrigerator and a magnetical stirrer. The temperature is raised in 30 minutes up to the boiling pint of the solvent. The so obtained solution is then kept under reflux and stirring for further 30 minutes. The closed flask is then kept for 30 minutes in a bath of ice and water and in thermostatic water bath at 25°C for 30 minutes as well. The solid thus obtained is filtered on quick filtering paper and the filtered liquid is divided into two 100 ml aliquots. One 100 ml aliquot of the filtered liquid is poured in a previously weighed aluminum container, which is heated on a heating plate under nitrogen flow, to remove the solvent by evaporation. The container is then kept on an oven at 80°C under vacuum until constant weight is obtained. The residue is weighed to determine the percentage of xylene-soluble polymer.

Melt flow rate (MFR)

[0055] Determined according to ISO 1133 (230°C, 2.16 Kg)

Yellowness Index

[0056] The determination of the yellowness index (YI) is obtained by directly measuring the X, Y and Z tristimulus coordinates on pellets using a tristimulus colorimeter capable of assessing the deviation of an object color from a pre-set standard white towards yellow in a dominant wavelength range between 570 and 580 nm. The geometric characteristics of the apparatus should allow perpendicular viewing of the light reflected by two light rays that hit the specimen at 45°, at an angle of 90° to each other, coming from a“Source C” according to CIE standard. After calibration, the glass container is filled with the pellets to be tested and the X, Y, Z coordinates are obtained to calculate the yellowness index according to the following equation:

YI= 100 * (1.274976795 * X - 1.058398178 * Z)/Y

EXAMPLES

General procedure for the polymerization of propylene

[0057] A 4-liter steel autoclave equipped with a stirrer, pressure gauge, thermometer, catalyst feeding system, monomer feeding lines and thermostating jacket, was purged with a nitrogen flow at 70°C for one hour. A suspension containing 75 ml of anhydrous hexane, 0.6 g of triethyl aluminum (AlEt3, 5.3 mmol) and 0.006 to 0.010 g of solid catalyst component, previously pre-contacted for 5 minutes with 10 wt% of total AlEt3 and an amount of dicyclopentyldimethoxysilane in order to have a molar ratio between Al/ dicyclopentyldimethoxysilane of 20 in a glass-pot, was charged. The autoclave was closed and the desired amount of hydrogen was added (4500cc). Then, under stirring, 1.2 kg of liquid propylene was fed. The temperature was raised to 70°C in about 10 minutes and the polymerization was carried out at this temperature for 2 hours. At the end of the polymerization, the non-reacted propylene was removed; the polymer was recovered and dried at 70°C under vacuum for 3 hours. The resulting polymer was weighed and characterized.

General procedure for the preparation of MgC12 ^» (EtOH)m adducts.

[0058] An microspheroidal MgCk 2.8C2H5OH was prepared according to the method described in Example 2 of USP 4,399,054. The resulting adduct had an average particle size of 25 pm.

Example 1 (comparative)

Preparation of a 9,9-bis(methoxymethyl)fluorene containing solid catalyst component.

[0059] Into a 2.0 L round bottom glass reactor, equipped with mechanical stirrer, cooler and thermometer, 1.0 L of TiCU was introduced at room temperature under a nitrogen atmosphere. After cooling to -5°C, while stirring, 13.2 g of microspherical complex of MgCb and EtOH (prepared as disclosed in the general procedure) were introduced. The temperature was then raised from -5°C up to 40°C and when this temperature was reached, 9,9- bis(methoxymethyl)fluorene, used as an internal electron donor, was introduced in such an amount to produce a Mg/9, 9-bis(methoxymethyl)fluorene molar ratio of 6.

[0060] At the end of the addition, the temperature was increased up to 100°C and maintained at this value for 30 minutes. Thereafter, stirring was stopped, and the solid product was allowed to settle. Then the supernatant liquid was siphoned off, leaving a fixed residual volume in the reactor of 300 cm ³ , while maintaining the temperature at 75°C. After the supernatant was removed, fresh TiCU and an additional amount of donor such as to have a Mg/9, 9-bis(methoxymethyl)fluorene molar ratio of 20 were added. The whole slurry mixture was then heated at 109°C and kept at this temperature for 30 minutes. The stirring was interrupted; the solid product was allowed to settle and the supernatant liquid was siphoned off, while maintaining the temperature at 109°C. A third treatment in fresh TiClr (1 L of total volume) was repeated, keeping the mixture under agitation at 109°C for 15 minutes, and then the supernatant liquid was siphoned off. [0061] The solid was washed with anhydrous i-hexane five times (5 x 1.0 L) at 50°C and one time (1.0 1) at room temperature

The solid was finally dried under vacuum, weighted and analyzed.

Catalyst composition: Mg= 12.5wt%; Ti= 3.7wt%; I.D.=20.7 wt%.

The so obtained catalyst was used in the polymerization of propylene according to the above described general procedure. Results are shown in Table 1.

Example 2 and comparative examples 3-5

Preparation of the coloring agent/ solid catalyst component dry mixture at weight ratio 0.2

[0062] Into a 50cc recipient, were introduced 3 grams of the catalyst component prepared as described in Example 1 and 0.6 grams of Cu-phthalocyanine. The solids were mixed for for 30 minutes and then discharged. Several aliquots of the mixture were tested at different times in the polymerization of propylene according to the above described general procedure. Conditions and results are shown in Table 1.

Examples 6-7 amd comparative examples 8-9

Preparation of the coloring agent/ solid catalyst component dry mixture at weight ratio 0.1

[0063] Into a 50cc recipient, were introduced 3 grams of the catalyst component prepared as described in Example 1 and 0.3 grams of Cu-phthalocyanine. The solids were mixed for 60 minutes and then discharged. Several aliquots of the mixture were tested at different times in the polymerization of propylene according to the above described general procedure. Conditions and results are shown in Table 1.

Examples 10-12 and comparative example 13

Preparation of the coloring agent/ solid catalyst component dry mixture at weight ratio 0.05

[0064] Into a 50cc recipient, were introduced 3 grams of the catalyst component prepared as described in Example 1 and 0.15 grams of Cu-phthalocyanine. The solids were mixed for 120 minutes and then discharged. Several aliquots of the mixture were tested at different times in the polymerization of propylene according to the above described general procedure. Conditions and results are shown in Table 1.

Examples 14-16.

Preparation of the coloring agent/ solid catalyst component dry mixture at weight ratio 0 025

[0065] Into a lOcc recipient, were introduced 3 grams of the catalyst component prepared as described in Example 1 and 0.075 grams of Cu-phthalocyanine. The solids were mixed for 60 minutes and then discharged. Several aliquots of the mixture were tested at different times in the polymerization of propylene according to the above described general procedure. Conditions and results are shown in Table 1. Table 1

Nd= not determined