MXPA00012500A - Components and catalysts for the polymerization of olefins - Google Patents

Abstract

The present invention relates to a solid catalyst component for the polymerization of olefins CH2=CHR in which R is hydrogen or a hydrocarbon radical with 1-12 carbon atoms, comprising Mg, Ti, halogen and an electron donor selected from substituted succinates of a particular formula. Said catalyst components when used in the polymerization of olefins, and in particular of propylene, are capable to give polymers in high yields and with high isotactic index expressed in terms of high xylene insolubility

Description

COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINS DESCRIPTIVE MEMORY The present invention relates to catalyst components for the polymerization of olefins, to the catalyst obtained therefrom and to the use of said catalysts in the polymerization of olefins CH2 = CHR wherein R is hydrogen or hydrocarbyl radical with 1-12 carbon atoms . In particular, the present invention relates to catalyst components, suitable for the stereospecific polymerization of olefins, comprising Ti, Mg, halogen and an electron donor compound selected from substituted succinic acid esters (substituted succinates). Said catalyst components when used in the polymerization of olefins, and in particular of propylene, are capable of providing polymers in high yields and with high isotactic indexes expressed in terms of high xylene insolubility. The chemical class of succinates is known in the art. However, the specific succinates of the present invention have never been used as internal electron donors in catalysts for the polymerization of olefins. EP-A-86473 mentions the use of unsubstituted succinates as internal donors in catalyst components for polymerization of olefins. The use of diisobutyl succinate and di-n-butyl succinate is also exemplified. However, the results obtained in terms of isotactic index and yields are deficient. The use of polycarboxylic acid esters, including succinates, as internal donors in catalyst components for the polymerization of olefins, is generally described in EP 125911. Diethyl methylsuccinate and diallyl ethylsuccinate are mentioned in the description although not exemplified. In addition, EP263718 mentions, but does not exemplify, the use of diethyl methylsuccinate and di-n-butyl ethylsuccinate as internal donors. In order to verify the behavior of these succinates in accordance with the teaching of the technique, the applicant has carried out some polymerization tests using catalyst components containing diethyl methylsuccinate and diisobutyl ethylsuccinate respectively, as internal donors. As shown in the experimental section, both catalysts thus obtained provide an unsatisfactory activity / stereospecific balance very similar to that obtained with catalysts containing unsubstituted succinates. Therefore, it has been very surprising to discover that the specific substitution in the succinates of the invention generates compounds which, when used as internal donors, give catalyst components having excellent activity and stereospecificity. It is therefore an object of the present invention to provide a solid catalyst component for the polymerization of olefins CH2 = CHR, wherein R is hydrogen or a hydrocarbon radical with one 1-12 carbon atoms, comprising Mg, Ti halogen and an electron donor selected from succinates of the formula (I): wherein the radicals Ri and R2, equal to, or different from each other, are a linear or branched C1-C20 alkyl, alkenyl cycloalkyl, aryl, arylalkyl or alkylaryl group, optionally containing heteroatoms; the radicals R3 to Re equal to, or different from each other, are hydrogen or a linear or branched C1-C20 alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl group. which optionally contains heteroatoms and the radicals R3 to R6 which are attached to the same carbon atom can be joined to form a ring; with the proviso that when R3 to R5 are hydrogen at the same time, Re is a radical selected from primary, secondary or branched alkyl groups, cycloalkyl, aryl, arylalkyl or alkylaryl groups having from 3 to 20 carbon atoms. R1 and R2 are preferably alkyl, cycloalkyl, aryl, arylalkyl and C 8 alkylaryl groups. Particularly preferred are compounds in which R-i and R2 are selected from primary alkyls and particularly branched primary alkyls. Examples of suitable R-i and R2 groups are methyl, ethyl, n-propyl, n-butyl, isobutyl, neopentyl, 2-ethylhexyl.

Particularly preferred are ethyl, isobutyl, and neopentyl. One of the preferred groups of the compounds described by the formula (I) is that in which R3 to R5 are hydrogen and RQ is a branched alkyl, cycloalkyl, aryl, arylalkyl and alkylaryl radical having 3 to 10 carbon atoms. Particularly preferred are compounds in which R6 is a branched primary alkyl group or a cycloalkyl group having from 3 to 10 carbon atoms. Specific examples of suitable monosubstituted succinate compounds are diethyl sec-butylsuccinate, diethyl methylsuccinate, diethyl cyclopropylsuccinate, diethyl norbornyl succinate, (10-) diethyl perhydronaphthyl succinate, diethyl trimethylsilyl succinate, diethyl methoxysuccinate, diethyl p-methoxyphenylsuccinate, diethyl chlorofenyl succinate, diethyl phenylsuccinate, diethyl cyclohexyl succinate, diethyl benzyl succinate, diethyl (cyclohexylmethyl) succinate, diethyl t-butyl succinate, diethyl isobutyl succinate, diethyl sopropylsuccinate, diethyl neopentyl succinate, diethyl isopentyl succinate, (1, 1, 1-trifluoro-2-propyl) diethyl succinate, diethyl (9-fluorenyl) succinate, diisobutyl phenylsuccinate, diisobutyl sec-butylsuccinate, diisobutyl texilsuccinate, diisobutyl cyclopropylsuccinate, diisobutyl (2-norbomyl) succinate, (IO-) diisobutyl perhydronaphthyl succinate, diisobutyl trimethylsilyl succinate, methoxy diisobutyl uccinate, diisobutyl p-methoxyphenylsuccinate, diisobutyl p-chlorophenylsuccinate, diisobutyl cyclohexyl succinate, diisobutyl benzylsuccinate, (cyclohexylmethyl) succinate diisobutyl, diisobutyl t-butylsuccinate, diisobutyl isobutylsuccinate, diisobutyl isopropylsuccinate, diisobutyl neopentylsuccinate, dussobutyl isopentylsuccinate, diisobutyl (1,1,1-trifluoro-2-propyl) succinate, diisobutyl (9-fluorenyl) succinate, dineopentyl sec-butylsuccinate, dineopentyl texilsuccinate, dineopentyl cyclopropyl succinate, dineopentyl (2-norbomyl) succinate, (10-) dineopentyl perhydronaphthyl succinate, dineopentyl trimethylsilyl succinate, dineopentyl methoxysuccinate, dineopentyl p-methoxyphenylsuccinate, dineopentyl p-chlorophenylsuccinate , dineopentyl phenylsuccinate, dineopentyl cyclohexyl succinate, dineopentyl benzisuccinate, dineopentyl (cyclohexylmethyl) succinate, dineopentyl t-butylsuccinate, dineopentyl sobutylsuccinate, dineopentyl isopropylsuccinate, dineopentyl neopentylsuccinate, dineopentyl isopentylsuccinate, (1, 1, 1- trifine-2-propyl) dineopentyl succinate, Dineopentyl (9-fluorenyl) succinate. Another preferred group of compounds within formula (I) is that in which at least two radicals of R3 to Re are different from hydrogen and are selected from the linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl group of C1-C20 which optionally contains heteroatoms. Particularly preferred are compounds in which the two radicals other than hydrogen are attached to the same carbon atom. Specific examples of suitable 2,2-disubstituted succinates are: diethyl 2,2-dimethylsuccinate, diethyl 2-ethyl-2-methylsuccinate, 2-benzyl-2- diethyl isopropylsuccinate, diethyl 2- (cyclohexylmethyl) -2-isobutylsuccinate, diethyl 2-cyclopentyl-2-n-propylsuccinate, diethyl 2,2-diisobutylsuccinate, diethyl 2-cyclohexyl-2-ethylsuccinate, 2-isopropyl- Diethyl 2-methylsuccinate, diethyl 2,2-diisopropyl, diethyl 2-isobutyl-2-ethylsuccinate, diethyl 2- (1,1,1-trifluoro-2-propyl) -2-methylsuccinate, 2-isopentyl- Diethyl 2-isobutylsuccinate, diethyl 2-phenyl-2-n-butylsuccinate, diisobutyl 2,2-dimethylsuccinate, diisobutyl 2-ethyl-2-methylsuccinate, diisobutyl 2-benzyl-2-isopropylsuccinate, 2- (cyclohexylmethyl) ) -2-diisobutyl isobutylsuccinate, 2-cyclopentyl-2-n-propylsuccinate of dussobutyl, Diisobutyl-2,2-diisobutylsuccinate, diisobutyl 2-cyclohexyl-2-ethylsuccinate, diisobutyl 2-isopropyl-2-methyl-succinate, diisobutyl-2-isobutyl-2-ethylsuccinate, 2- (1,1,1-trifluoro) -2-propyl) -2-diisobutyl methylsuccinate, 2-isopentyl-2-isobutylsuccinate diisobutyl, 2,2-diisopropylsilycinate diisobutyl, 2-phenyl-2-n-propylsuccinate diisobutyl, 2,2-dimethylsuccinate dineopentyl , Dineopentyl 2-ethyl-2-methyl-succinate, dineopentyl-2-benzyl-2-isopropylsuccinate, dineopentyl-2- (cyclohexylmethyl) -2-isobutylsuccinate, dineopentyl-2-cyclopentyl-2-n-propylsuccinate, 2,2-diisobutylsuccinate of dyneopentyl, 2-cyclohexyl-2-ethylsuccinate of dineopentyl, 2-isopropyl-2-methylsuccinate of dineopentyl, 2-isobutyl-2-ethylsuccinate of dineopentyl, 2- (1,1,1-trifluoro-2-propyl) -2 - dineopentylmethyl succinate, dineopentyl 2,2-diisopropylsuccinate, dineopentyl 2-isopentyl-2-isobutylsuccinate, dineopentyl 2-phenyl-2-n-butylsuccinate.

In addition, also compounds in which at least two different radicals of hydrogen are attached to different carbon atoms, i.e. R3 and R5 or R and Re, are particularly preferred. Specific examples of suitable compounds are: diethyl 2,3-bis- (trimethylsilyl) succinate, diethyl 2,2-sec-butyl-3-methylsuccinate, 2- (3,3,3-trifluoropropyl) -3- diethyl methylsuccinate, diethyl 2,3-bis (2-ethylbutyl) succinate, diethyl 2,3-diethyl-2-isopropylsuccinate, diethyl 2,3-diisopropyl-2-methylsuccinate, 2,3-dicyclohexyl-2- diethyl methylsuccinate, diethyl 2,3-dibenzylsuccinate, diethyl 2,3-diisopropylsuccinate, diethyl 2,3-bis (cyclohexylmethyl) succinate, diethyl 2,3-di-t-butylsuccinate, 2,3- diethyl diisobutylsuccinate, diethyl 2,3-dineopentylsuccinate, diethyl 2,3-diisopentylsuccinate, diethyl 2,3- (1-trifluoromethyl-ethyl) succinate, diethyl 2,3- (9-fluorenyl) succinate, 2- diethyl isopropyl-3-isobutylsuccinate, diethyl 2-t-butyl-3-isopropylsuccinate, diethyl 2-hydropropyl-3-cyclohexylsuccinate, diethyl 2-butyl-3-cyclohexyl succinate, 2-cyclohexyl-3- diethyl cyclopentyl succinate, 2,2,3,3-tetramethyl succinate diethyl, 2,2,3 , Diethyl 3-tetraethylsuccinate, diethyl 2,2,3,3-tetrapropyl succinate, diethyl 2,3-diethyl-2,3-diisopropylsuccinate, diisobutyl 2,3-bis (trimethylsilyl) succinate , 2,2-sec-butyl-3-diisobutyl methylsuccinate, diisobutyl 2- (3,3,3-trifluoropropyl) -3-methylsuccinate, 2,3-bis (2-ethylbutyl) diisobutyl succinate, 2,3 -diethyl-2-isopropilsucc¡nato diisobutyl 2,3-2-methylsuccinate di¡sopropil-diisobutyl 2,3-dicyclohexyl-2-metilsucc¡nato diisobutyl 2,3-diisobutyl dibencilsuccinato, 2.3 diisobutyl diisopropylsuccinate, diisobutyl 2,3-bis (cyclohexylmethyl) succinate, diisobutyl 2,3-di-t-butylsuccinate, 2,3-diisobutylsuccinate, diisobutyl 2,3-diisobutyl dineopentilsuccinato, 2,3-diisopentilsuccinato diisobutyl 2,3- (1, 1, 1-trifluoro-2-propyl) succinate, diisobutyl 2,3-n -diisobutyl propylsuccinate, diisobutyl 2,3- (9-fluorenyl) succinate, diisobutyl 2-isopropyl-3-ibutylsuccinate, diisobutyl 2-terbutyl-3-ipropylsuccinate, diisobutyl 2-isopropyl-3-cyclohexylsuccinate, 2- diisobutyl isopentyl-3-cyclohexyl succinate, diisobutyl 2-n-propyl-3- (cyclohexylmethyl) succinate, diisobutyl 2-cyclohexyl-3-cyclopentyl succinate, diisobutyl 2,2,3,3-tetramethyl succinate, 2.2 , 3,3-diisobutyl tetraetilsuccinato, 2,2,3,3-tetrapropilsuccinato diisobutyl 2,3-diethyl-2,3-diisobutyl düsopropilsuccinato, 2) 3-bis (trimethylsilyl) succinate, dineopentyl 2,2 dineopentyl di-sec-butyl-3-methylsuccinate, dineopentyl 2- (3,3,3-trifluoropropyl) -3-methylsuccinate, dineopentyl 2,3-bis (2-ethylbutyl) succinate, 2 , 3-diethyl-2-isopropylsuccinate from dineopent ilo, 2,3-diisopropyl-2-methylsuccinate, dineopentyl, 2,3-dicyclohexyl-2-methylsuccinate, dineopentyl, 2,3-dibenzylsuccinate, dineopentyl, 2,3-diisopropylsuccinate, dineopentyl, 2,3-bis (cyclohexylmethyl) dineopentyl succinate, dineopentyl 2,3-di-t-butylsuccinate, dineopentyl 2,3-diisobutylsuccinate, dineopentyl 2,3-dinaenopentyl succinate, 2,3-diinepentyl succinacrylate, 2,3- (1, 1, 1) trifluoro-2-propyl) succinate, dineopentyl 2,3-n-propylsuccinate, dineopentyl 2,3 (9-fluorenyl) succinate, dineopentyl 2-isopropyl-3-isobutylsuccinate, dineopentyl 2-t-butyl-3 -isopropilsuccinato, dineopentyl 2-isopropyl-3-ciclohexilsuccinato, dineopentyl 2-¡sopentil-3-ciclohexilsuccinato, dineopentyl 2-n-propyl-3- (cyclohexylmethyl) succinate dineopentyl 2-cyclohexyl-3-ciclopentilsuccinato, dineopentyl 2,2,3,3-tetrametilsuccinato, dineopentyl 2,2,3,3-tetraetilsuccinato, dineopentyl 2,2,3, 3-tetrapropilsuccinato, dineopentyl 2 Dineopentyl 3-diethyl-2,3-diisopropylsuccinate. As mentioned above, the compounds according to formula (I) are also preferred in which two or four of the radicals R3 to Re that bind to the same carbon atom join to form a ring. Specific examples of suitable compounds are 1- (ethoxycarbonyl) -l- (ethoxyacetyl) -2, 6-dimethylcyclohexane, 1- (ethoxycarbonyl) -l- (ethoxyacetyl) -2,5-dimethylcyclopentane, 1- (ethoxycarbonyl) -l- (ethoxyacetylmethyl) -2-methycyclohexane, 1- (ethoxycarbonyl) -l- (ethoxy ( cyclohexyl) acetyl) cyclohexane. Those skilled in the art know that all of the aforementioned compounds can be used either in the form of pure stereoisomers or in the form of mixtures of enantiomers, or mixtures of diastereomers and enantiomers. When a pure isomer is to be used, it is usually isolated using common techniques known in the art. In particular, some of the succinates of the present invention can be used as pure rae or meso forms, or mixtures thereof, respectively. As explained above, the catalyst components of the invention comprise, together with the above electron donors, Ti, Mg and halogen. In particular, the components of catalysts comprise a titanium compound, having at least one titanium-halogen bond and the aforementioned electron-donor compound supported on a magnesium halide. The magnesium halide preferably is MgC in active form which is widely known from the patent literature as a support for the Ziegler-Natta catalyst. The patents of E.U.A. 4,298,718 and 4,495,338 were the first to describe the use of these compounds in Ziegler-Natta catalysts. It is known from these patents that magnesium dihalides in active form used as a support or co-carrier in catalyst components for the polymerization of olefins are characterized by the X-ray spectrum in which the most intense diffraction line appearing in the Non-active halogenide spectrum is decreased in intensity and amplified to form a halogen. The preferred titanium compounds used in the catalyst components of the present invention are TiCU and TÍCI3; in addition, the Ti-haloalcoholates of the formula Ti (OR) n- and Xy- can also be used where n is the valence of titanium, X is halogen and y is a number between 1 and n. The preparation of the solid catalyst component can be carried out in accordance with various methods. According to one of these methods, the magnesium dichloride in an anhydrous state and the succinate of formula (I) are milled together under conditions in which the activation of magnesium dichloride occurs. The product thus obtained can be treated one or more times with an excess of TiCl4 at a temperature between 80 and 135 ° C.

This treatment is followed by a process of washing with hydrocarbon solvents until the chloride ions disappear. According to a further method, the product obtained by co-grinding the magnesium chloride in an anhydrous state, the titanium compound and the β-substituted succinate is treated with halogenated hydrocarbons such as 1,2-dichloroethane, chlorobenzene, dichloromethane, etc. The treatment is carried out for a time between 1 and 4 hours and at a temperature of about 40 ° C at the boiling point of the halogenated hydrocarbon. Subsequently, the obtained product is generally washed with inert hydrocarbon solvents such as hexanes. According to another method, the magnesium dichloride is pre-activated according to well-known methods and treated with an excess of TiCl at a temperature of about 80 to 135 ° C containing, in solution, a succinate of formula (I) . The TlCl treatment is repeated and the solid is washed with hexane to remove any TiCl that has not reacted. A further method comprises the reaction between magnesium alcoholates or chloroalcoholates (in particular chloroalcoholates prepared in accordance with the US patent 4,220,554) and an excess of TiCl 4, which comprises the succinate of formula (I) in solution at a temperature of about 80 at 120 ° C. According to a preferred method, the solid catalyst component can be prepared by reacting a titanium compound of the formula Ti (OR) n-yXy, where n is the valence of titanium and y is a number between 1 and n, preferably TiCl 4, with a magnesium chloride which is derived from an adduct of formula MgCl 2 * pROH wherein p is a number between 0.1 and 6, preferably from 2 to 3.5, and R 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 inmissible with the adduct, operating under stirring conditions at the adduct melting temperature (100-130 ° C). Subsequently, the emulsion is rapidly quenched, thereby causing the adduct to solidify in the form of spherical particles. Examples of spherical adducts prepared in accordance with this procedure are described in the U.S.A. 4,339,054 and 4,469,648. The adduct thus obtained can react directly with the Ti compound or can be previously subjected to thermally controlled dealcoholization (80-130 ° C) to obtain an adduct in which the number of moles of alcohol is generally less than 3, preferably between 0.1 and 2.5. . The reaction with the Ti compound can be carried out by suspending the adduct (dealcoholizing it or as such) in cold TiCl (generally 0 ° C); The mixture is heated to 80-130 ° C and maintained at this temperature for 0.5-2 hours. The treatment with TiCl4 can be carried out one or more times. The succinate of formula (I) can be added during the treatment with TiCl. The treatment with the electron donor compound can be repeated one or more times.

The preparation of the catalyst components in spherical form is described, for example, in European patent applications EP-A-395083, EP-A-553805, EP-A-553806, EPA-601525 and WO98 / 44009. The solid catalyst components obtained in accordance with the above method show a surface area (by the method B.E.T.) generally between 20 and 500 m2 / g and preferably between 50 and 400 m2 / g, and a total porosity (by the method B.E.T.) greater than 0.2 cm3 / g, preferably between 0.2 and 0.6 cm3 / g. The porosity (Hg method) due to the pores with a radius of up to 10000 A generally varies between 0.3 and 1.5 cm3 / g, preferably from 0.45 to 1 cm3 / g. A further method for preparing the solid catalyst component of the invention comprises halogenating magnesium dihydrocarbyloxide compounds, such as dialkoxide or magnesium diaryloxide, with a solution of TiCl 4 in aromatic hydrocarbon (such as toluene, xylene, etc.) at temperatures between 80 and 130 ° C. The treatment with TiCl in aromatic hydrocarbon solution can be repeated one or more times, and the β-substituted succinate is added during one or more of these treatments. In any of these preparation methods the desired succinate of formula (I) can be added as such, or in an alternative form, can be obtained in situ by using an appropriate precursor capable of being transformed into the desired electron donor compound by means of • example, known chemical reactions such as esterification, transesterification, etc. Generally, the succinate of formula (I) is used in molar ratio in relation to the MgC of about 0.01 to 1, preferably 0.05. to 0.5. In addition, this constitutes another object of the present invention, it has been found that interesting results are obtained when other internal electron donor compounds are used together with the succinates of formula (I). The additional electron donor compound can be the same as the electron donor (d) described below. In particular, very good results have been obtained when the 1,3-diethers of formula (II) which are presented below are used as internal donors together with a succinate of formula (I). The solid catalyst components according to the present invention are converted into catalysts for the polymerization of olefins by reacting them with organoaluminum compounds according to known methods. In particular, it is an object of the present invention a catalyst for the polymerization of olefins CH2 = CHR, wherein R is hydrogen or a hydrocarbyl radical with 1-12 carbon atoms, comprising the product of the reaction between: (a) a solid catalyst component comprising an Mg, Ti and halogen or an electron donor selected from succinates of formula (I); (b) an alkylaluminum compound and, optionally, (c) one or more electron donating compounds (external donor).

The alkylaluminum compound (b) is preferably selected from trialkylaluminum compounds such as for example triethylalumino, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum. It is possible to use trialkylaluminum mixtures with alkylaluminum halides, alkylaluminium hydrides or alkylaluminum sesquichlorides such as AIEt2CI and AI2Et3CI3. Alkylalumoxanes can also be used. It is a particularly interesting aspect of the invention that the catalysts described above are capable of providing polymers with high isotatic rates even when the polymerization is carried out in the absence of an external donor (c). In particular, when operating for example in accordance with the working examples described below, propylene polymers having an isotactic index around 96% are obtained without using an external donor compound. This type of products are very interesting for applications in which the crystallinity of the polymer should not be at its maximum level. This particular behavior is very surprising in view of the fact that the esters of dicarboxylic acids known in the art, when used as internal donors, they give polymers with a poor isotactic index when the polymerization is carried out in the absence of an external electron donor compound. For applications in which a very high isotactic index is required, it is usually advisable to use an external donor compound. The external donor (c) may be of the same type or may be different from the succinate of formula (I). Preferred external electron donor compounds include silicon compounds, ethers, esters, such as 4-ethoxybenzoate, amines, heterocyclic compounds and particularly 2,2,6, 6-tetramethylpiperidine, ketones and the 1, 3-diethers of general formula (II): wherein R1, R ", R1"; R? V, RV and Rv? are they the same or different from each other, are they hydrogen or hydrocarbon radicals having 1 to 18 carbon atoms, and Rv "and Rv?", equal or different from each other, have the same meaning as R-Rv? except that they can not be hydrogen; ? One or more of the R'-Rv groups. "May join to form a cycle Particularly preferred 1, 3-diethers in which Rv" and Rv "are selected from alkyl radicals of C? -? - C4) R, M and R? V form a condensed unsaturated cycle and R1, R ", Rv and Rv? they are hydrogen. The use of 9,9-bis (methoxymethyl) fluorene is particularly preferred. Another class of preferred external donor compounds is that of the silicon compounds of the formula Ra7Rb8Si (OR9) C) where a and b are integers from 0 to 2, c is an integer from 1 to 3 and the sum of (a + b + c ) is 4; R7, R8 and R9 are C1-C18 hydrocarbon groups optionally containing heteroatoms. Particularly preferred are the silicon compounds in the which a is 1, b is 1, c is 2, at least one of R7 and R8 is selected from alkyl, alkenyl, alkylene, cycloalkyl or aryl branched 3-10 carbon atoms optionally containing heteroatoms and R9 is a C1-C10 alkyl group, in particular methyl. Examples of such preferred silicon compounds are cyclohexylmethyldimethoxysilane, diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-t-butyldimethoxysilane and (1, 1, 1-trifluoro-2-propyl) -2-etilpiperidinildimetoxisilano and (1 , 1.l-trifluoro ^ -propi -metildimetoxisilano. in addition, the silicon compounds in which are also preferred a is 0, c is 3, R8 is a branched alkyl group or cycloalkyl, optionally containing heteroatoms, and R9 is methyl preferred. Examples of such silicon compounds are cyclohexyltrimethoxysilane, t-butyltrimethoxysilane and dexiltrimetoxisilano. the electron donor compound (c) is used in such an amount to give a molar ratio between the organoaluminum compound and said electron donor compound (c) of 0.1 to 500, preferably from 1 to 300 and more preferably from 3 to 100. As previously indicated, when used in the (co) polymerization of olefins, and in particular r of propylene, the catalysts of the invention make it possible to obtain, with high yields, polymers with a high isotactic index (expressed by insolubility in xylene high X.I.), thus showing an excellent balance of properties. This is particularly surprising since, as can be seen from the comparative examples shown below, the use as Internal electron donors of unsubstituted or unsubstituted succinate compounds give worse results in terms of yield and / or insolubility in xylene. As mentioned above, the succinates of formula (I) can also be used as external donors with good results. In particular, it has been found that they are able to give very good results even when they are used as external electron donor compounds together with catalyst components containing an internal donor different from the succinates of formula (I). This is very surprising since the dicarboxylic acid esters known in the art are usually able to give satisfactory results when used as external donors. In contrast, the succinates of formula (I) are capable of providing polymers that still have a good balance between isotactic index and yields. It is therefore another object of the present invention, a catalyst system for the polymerization of olefins CH2 = CHR, wherein R is hydrogen or a hydrocarbyl radical with 1-12 carbon atoms, comprising the product of the reaction between: (i) a solid catalyst component comprising Mg, Ti and halogen and a electrons (d); (I) an alkylaluminum compound and, (iii) a succinate of formula (I). The alkylaluminum compound (ii) has the same meanings as the aluminum compound (b) mentioned above. He The electron donor compound (d) can be selected from ethers, esters of organic mono or bicarboxylic acids, such as phthalates, benzoates, glutarates, succinates having a structure different from those of formula (I), amines. Preferably, it is selected from 1,3-propanediomers of formula (II) and esters of organic mono or bicarboxylic acids, in particular phthalates. As mentioned above all of these catalysts can be used in the process for the polymerization of olefins CH2 = CHR, wherein R is hydrogen or a hydrocarbyl radical with 1-12 carbon atoms. The preferred α-olefins which are to be (co) polymerized are ethene, propene, 1-butene, 4-methyl-1-pentene, 1 -hexene and 1-octene. In particular, the catalysts described above have been used in the (co) polymerization of propene and ethylene to prepare different types of products. For example, the following products can be prepared: high density ethylene polymers (HDPE, having a density greater than 0.940 g / cm 3), which comprise ethylene homopolymers and copolymers of ethylene with α-olefins having 3-12 carbon atoms. carbon; linear low density polyethylenes (LLDPE, which have a density of less than 0.940 g / cm3) and very low density and ultra low density (VLDPE and ULDPE, which have a density of less than 0.920 g / cm3, at 0.880 g / cm3) they consist of ethylene copolymers with one or more α-olefins having from 3 to 12 carbon atoms, which have a molar content of units derived from ethylene greater than 80%; ethylene and propylene elastomeric copolymers and terpolymers elastomeric ethylene and propylene with smaller proportions of a diene having a weight content of units, derived from ethylene comprised between about 30% and 70%, sotactic polypropylenes and crystalline copolymers of propylene and ethylene and / or other olefins having a content of propylene-derived units greater than 85% by weight (random copolymers); impact-resistant polymers of propylene obtained by sequential polymerization of propylene and mixtures of propylene with ethylene, containing up to 30% by weight of ethylene; copolymers of propylene and 1-butene having a number of units derived from 1-butene comprised between 10 and 40% by weight. Particularly interesting are the propylene polymers obtained with the catalyst of the invention which exhibit broad coupled MWD with high isotactic index and high modulus. In fact, said polymers have a polydispersity index greater than 5, a content of isotactic units expressed in terms of pellets greater than 97% and a flexural modulus of at least 2000 MPa. Preferably, the polydispersity index is greater than 5.1, the flexural modulus is greater than 2100 and the percentage of propylene units in the form of pentadids is greater than 97.5%. One type of polymerization process can be used with the catalysts of the invention which are very versatile. The polymerization can be carried out for example in suspension using as diluent an inert hydrocarbon solvent, or in bulk using the liquid monomer (for example propylene) as a reaction medium. In addition, it is possible to carry The gas phase polymerization process operates in one or more fluidized or mechanically stirred bed reactors. The catalyst of the present invention can be used in the polymerization process by introducing it directly into the reactor. In the alternative, the catalyst can be pre-polymerized before being introduced into the first polymerization reactor. The term "pre-polymerized," as used in the art, means a catalyst that has been subjected to a polymerization step at a low degree of conversion. In accordance with the present invention a catalyst is considered pre-polymerized when the amount of polymer produced is from about 0.1 to about 1000 g per gram of the solid catalyst component. The pre-polymerization can be carried out with the α-olefins selected from the same group of olefins described above. In particular, it is especially preferred to pre-polymerize ethylene or mixtures thereof with one or more α-olefins in an amount of up to 20 mole%. Preferably, the conversion of the pre-polymerized catalyst component is from about 0.2 g to about 500 g per gram of the solid catalyst component. The pre-polymerization step can be carried out at temperatures of about 0 to 80 ° C, preferably about 5 to about 50 ° C in the liquid or gas phase. The prepolymerization step can be carried out on-line as a part of a continuous polymerization process or in a separated form in an intermittent process. Is particularly preferred is the intermittent pre-polymerization of the catalyst of the invention with ethylene to produce an amount of polymer ranging from 0.5 to 20 g per gram of the catalyst component. The polymerization is generally carried out at a temperature of about 20 to 120 ° C, preferably about 40 to 80 ° C. When the polymerization is carried out in the gaseous phase the operating pressure is generally between 0.5 and 10 MPa, preferably between 1 and 5 MPa. In bulk polymerization the operating pressure is generally between 1 and 6 MPa, preferably between 1.5 and 4 MPa. Hydrogen or other compounds capable of acting as chain transfer agents can be used to control the molecular weight of the polymer. The following examples are given to better illustrate the invention without limiting it.

GENERAL PROCEDURES AND CHARACTERIZATIONS Preparation of succinates: general procedures Succinates can be prepared according to known methods described in the literature. The descriptive examples of processes for the synthesis of succinates exemplified in Table 1 are given below.

Alkylation For literature see for example: N. Long and M.W. Rathke, Synth. Commun., 11 (1981) 687; W.G. Kofron and L.G. Wideman, J. Org. Chem., 37 (1972) 555.

Diethyl 2,3-Diethyl-2-isopropylsuccinate (Example 23) To a mixture of 10 mL (72 mmol) of diisopropylamine in 250 mL of tetrahydrofuran (THF) were added 28.6 mL (72 mmol) of BuLi ( 2.5 molar in cyclohexanes) at -20 ° C. After 20 minutes of stirring, 9.2 grams (86% pure) (28.3 mmoles) of diethyl 2,3-diethylsuccinate were added at -40 ° C and after the addition, the mixture was stirred for 2 hours at room temperature. Subsequently, this mixture was cooled to -70 ° C and a mixture of 4.3 ml (43 mmol) of 2-iodopropane and 7.4 ml (43 mmol) of hexamethylphosphoramide (HMPA) was added. After the addition, the mixture was left to cool and the mixture was stirred for 4 days. The volatiles were removed and 250 ml of ether was added. The organic layer was washed twice with 100 ml of water. The organic layer was isolated, dried over MgSO 4, filtered and concentrated in vacuo to yield an orange-colored oil. This oil is chromatographed on silica with CH2Cl2 yielding 2.3 g (30%) of a 96% pure product. According to gas chromatography (GC) only one isomer was present.

Oxidative coupling For the literature see for example: T.J. Brocksom, N. Petragnani, R. Rodrigues and H. La Scala Teixeira, Synthesis, (1975) 396; IN. Jacobsen, G.E. Totten, G. Wenke, A.C. Karydas, Y.E. Rhodes, Synth. Commun., (1985) 301. 2,3-Diethyl dipropylsuccinate (example 18) To a mixture of 46 ml (0.33 mole) of diisopropylamine in 250 ml THF were added 132 ml (0.33 mole) of BuLi (2.5 molar in cyclohexanes) at -20 ° C. After 20 minutes of stirring, 39 g (0.3 mol) ethyl pentanoate was added at -70 ° C and after the addition, the mixture was stirred for 1 hour at this temperature. Subsequently, this mixture was added to a mixture of 33 ml (0.30 mol) of TlCI4 and 200 ml of CH2CI2 at -70 ° C keeping the temperature below -55 ° C. After the addition and subsequent stirring for 1 hour, the reaction mixture was quenched with 10 ml of water and subsequently the temperature was raised slowly to room temperature. The volatiles were removed and 250 ml of ether was added. The organic layer was washed twice with 100 ml of water. The organic layer was isolated, dried over MgSO 4, filtered and concentrated in vacuo to yield an orange-colored oil (yield content was 77%). The oil was distilled which gave two fractions. The best fraction obtained was 13.5 g (35%) and 98% pure. The second fraction was 7.5 g and 74% pure.

Reduction meso 2,3-dicyclohexylsuccinate diethyl ester (example 22) A stainless steel autoclave was charged with a mixture of 6.7 grams (0.02 moles) of meso 2,3-diphenylsuccinate diethyl ester, 180 ml of isopropanol, and 0.23 g of a catalyst Rh / C of 5% by weight. The mixture was hydrogenated for 18 hours at 70 ° C under a hydrogen pressure of 20 bar. The mixture was filtered over Celite and concentrated under reduced pressure yielding 6.8 g (97% yield) of the 99% pure product.

Esterificación For literature see for example: "Vogel's textbook of practical organic chemistry", 5th Edition (1989), pages 695-707. 2-Diethyl phenylsuccinate (example 1) A mixture of 50 g of DL-phenylsuccinate acid (0.257 moles), 90 ml (1.59 moles) of ethanol, 46 ml of toluene and 0.39 g of concentrated H2SO4 was heated to 115 ° C. . An azeotropic mixture of ethanol, toluene and water was distilled on a 10 cm column. When the distillation was stopped, the same amounts of ethanol and toluene were added. To obtain a complete conversion this was repeated twice. The resulting oil was distilled at 114 ° C (2'10 ~ 2 mbar); producing 60.82 g (95%), 100% purity.

Coupling of SN2 For the literature see for example: N. Petragnani and M. Yonashiro, Synthesis, (1980) 710, J. L. Belletire, E.G. Spletzer, and A.R. Pinhas, Tetrahedron Lett., 25 (1984) 5969. 2,2,3-Diisobutyl trimethylsuccinate (example 14) Isobutyric acid (14.6 ml, 157 mmol) was added to a solution of freshly prepared lithium diisopropylamide (LDA) (see succinate synthesis example 23.41 ml, 314 mmol diisopropylamine and 125 ml of BuLi (2.5 M in hexanes: 314 mmoles) and 1 I of THF) at 0 ° C. The mixture was stirred at 0 ° C for 15 minutes and subsequently for 4 hours at 45 ° C. Meanwhile in a separate reaction vessel, a mixture of 14.1 ml (157 mmoles) of 2-bromopropionic acid and 28 g (157 mmoles) of HMPA was added to a suspension of 3.8 g (157 mmoles) of NaH in 500 ml. of THF at 0 ° C while controlling for gas formation. After the addition the mixture was stirred for 15 minutes at 0 ° C. The mixture was then added to the lithium salt mixture of isobutyric acid (described above) at 0 ° C. After the addition, the mixture was stirred for 2 hours at 35 ° C. The mixture was quenched with 150 ml of a saturated 1 N HCl solution at 0 ° C. This mixture was extracted 2 times with 100 ml of diethyl ether and the combined ether layers were extracted with 50 ml of a saturated NaCl solution. The organic layer was dried over MgSO4 and concentrated in vacuo producing a yellow oil. This oil was dissolved in 150 ml of isobutanol, 100 ml of toluene and 2 ml of concentrated H2SO4. This mixture was heated under reflux with a Dean Stark apparatus to remove the water. After two days the conversion was completed. The reaction mixture was concentrated in vacuo and the resulting oil was distilled at 155 ° C (75 mbar); yield 5.1 grams (12%), purity 98%.

Combined methods Most succinates were prepared by a combination of methods described above. The different methods used for the synthesis of the succinates exemplified in Table 1 are further specified in Table A. The sequential order in which the methods were used is indicated alphabetically by means of a, b, c.

TABLE A POLYMERIZATION Polymerization of propylene: general procedure In a 4 liter autoclave, purged with nitrogen flow at 70 ° C for 1 hour, 75 ml of anhydrous hexane containing 800 mg of AIEt.3, 79.8 mg of dicyclopentyl dimethoxysilane and 10 mg of the solid catalyst component in propylene flow at 30 ° C. The autoclave closed. 1.5 NL of hydrogen were added and then, under agitation, 1.2 kg of liquid propene were fed. The temperature was raised to 70 ° C in 5 minutes and the polymerization was carried out at this temperature for two hours. The unreacted propylene was removed, the polymer was collected, dried at 70 ° C under vacuum for 3 hours, weighed, and fractionated with o-xylene to determine the amount of xylene insoluble fraction (XI) at 25 ° C. C.

Ethylene / 1-butene polymerization: general procedure A 4.0-liter stainless steel autoclave equipped with a magnetic stirrer, temperature and pressure indicator, feeding line for ethene, propane, 1-butene, hydrogen, and a steel flask for catalyst injection, it was purified by low flow to pure nitrogen at 70 ° C for 60 minutes. It was then washed with propane, heated to 75 ° C and finally loaded with 800 g of propane, 1-butene (as reported in table 4), ethene (7.0 bar, partial pressure) and hydrogen (2.0 bar, pressure partial). 100 ml of anhydrous hexane, 9.6 ml of TEAL / hexane solution at 10% w / v, optionally an external donor (ED, as reported in a 100 ml three-necked glass flask) were introduced in the following order. Table 4) and the solid catalyst. They were mixed and stirred at room temperature for 20 minutes and then introduced into the reactor through the steel bottle by using an overpressure of nitrogen.

Under continuous agitation, the total pressure was kept constant at 75 ° C for 120 minutes when feeding ethene. At the end, the reactor was depressurized and the temperature decreased to 30 ° C. The collected polymer was dried at 70 ° C under nitrogen flow and weighed.

Determination of the insoluble fractions in xylene (Xl) 2.5 g of polymer were dissolved in 250 ml of o-xylene under stirring at 135 ° C for 30 minutes, then the solution was cooled to 25 ° C and after 30 minutes the insoluble polymer. The resulting solution was evaporated in nitrogen flow and the residue was dried and weighed to determine the percentage of soluble polymer and subsequently, by differentiating the fraction insoluble in xylene (%).

Determination of the comonomer content in the copolymer: 1-butylene was determined by means of infrared spectrometry.

Thermal analysis: The calorimetric measurements were made using a DSC Mettier differential scanning calorimeter. The instrument was calibrated with Indian and tin standards. The heavy sample (5-10 ml), obtained from the determination of the melt index, was sealed on the aluminum trays, heated to 200 ° C and maintained at that temperature for a sufficient time (5 minutes) to allow a complete fusion of all the crystallites. Successively, after cooling to 20 ° C / minutes at -20 ° C, the peak temperature was assumed as the crystallization temperature (Te). After standing for 5 minutes at 0 ° C, the mixture was heated to 200 ° C at a rate of 10 ° C / minute. In this second heating, the peak temperature was assumed as the melting temperature (Tf) and the area as the global heat enthalpy (? H).

Determination of the melting index (MI): The melt index was measured at 190 ° C following ASTM D-1238 on a load of: 2.16 kg, MI E = M12.16 21.6 kg, MI F = M121.6 The ratio: F / E = MI F / MI E = MI21.6 / MI2.16 was then defined as the melt flow ratio (MFR).

Determination of the density: The density was determined in the homogenized polymers (from the determination of M.l.) when using a gradient column and following the procedure of ASTM-D-1505.

Determination of the polydispersity index (P.l.) This property is strictly connected to the molecular weight distribution of the polymer under examination. In particular, it is inversely proportional to the resistance to deformation of the polymer in the molten state. Said resistance called module separation at a lower module value (500 PA) was determined at a temperature of 200 ° C when using a parallel plate rheometer model RMS-800 sold by RHEOMETRICS (USA), which operates at an oscillation frequency which increases from 0.1 rad / sec to 100 rad / sec. From the separation value of the module, one can derive the P.l. by means of an equation: Pl = 54.6 * (module separation) "1, 76 in which the module spacing is defined as: module spacing = frequency at G '= 500Pa / frequency at G' = 500Pa where G 'is storage module and G' is the lost module.

EXAMPLES EXAMPLES 1-27 AND COMPARATIVE EXAMPLES 28-30 Preparation of solid catalyst components In a 500 ml four-necked round flask, flushed with nitrogen, 250 ml of TiCl were introduced at 0 ° C. While stirring, 10.0 g of microspheroidal MgCl2 * 2.8C2H5OH (prepared according to the method described in Example 2 of the US patent 4,399,054 but operating at 3000 rpm instead of 10,000 rpm) and 7.4 mmol of succinate were added. The temperature was raised to 100 ° C and maintained for 120 minutes. Subsequently, the stirring was discontinued, the solid product allowed to settle and the supernatant liquid siphoned. Subsequently, 250 ml of fresh TiCl were added. The mixture was reacted at 120 ° C for 60 minutes and, subsequently, the supernatant liquid was siphoned. The solid was washed six times with anhydrous hexane (6 x 100 mL) at 60 ° C. Finally, the solid was dried under vacuum and analyzed. The type and amount of succinate (% by weight) and the amount of Ti (% by weight) contained in the solid catalyst component was reported in table 1. The polymerization results were reported in table 2. The polymer obtained in Example 10 was characterized and showed a polydispersity index of 6, a content of isotactic units expressed in terms of pentanes of 98% and a flexural modulus of 2150 MPa.

TABLE 1 TABLE 2 15 twenty EXAMPLE 31 The procedure of examples 1-27 and comparative examples 28-30 were used, however, in preparing the solid catalyst component, rae 2,3-diisopropylsuccinate diethyl ester was added as succinate. The resulting solid catalyst component contained: Ti = 4.8% by weight, rae 16.8% by weight diethyl 2,3-diisopropylsuccinate. The aforementioned solid catalyst component was polymerized according to the general polymerization process but without using dicyclopentyl dimethoxysilane. The yield of the polymer was 65 kg of propylene / grams of the solid catalyst component with X.l. = 96.1%.

EXAMPLES 32-38 The solid catalyst component of Example 10 was polymerized according to the general polymerization process but instead of dicyclopentyldimethoxysilane the electron donors of Table 3 were used. The amount and type of the electron donor and the polymerization results are reported in the box 3 COMPARATIVE EXAMPLE 39 The procedure of examples 1-27 and comparative examples 28-30 were used, but, in preparing the solid catalyst component, 14 mmoles of ethyl benzoate was added in place of the succinate compound. The resulting solid catalyst component contained: Ti = 3.5% by weight, 9.1% by weight ethyl benzoate. The aforementioned solid catalyst component was polymerized with the same procedure as in Example 38. The polymerization result was reported in Table 3.

TABLE 3 EXAMPLE 40 The procedure of examples 1-27 and comparative examples 28-30 were used, but, in preparing the solid catalyst component, 7.4 mmoles of diethyl 2,3-dusopropylsuccinate and 7.4 mmoles of 9,9-bis were added ( methoxymethyl) fluorene. The resulting solid catalyst component contained: Ti = 3.5% by weight, 2,3-diisopropylsuccinate diethyl = 11.5% by weight and 9,9-bis (methoxymethyl) fluorene = 6.9% by weight. The aforementioned solid catalyst component was polymerized as in the general polymerization process. The yield of the polymer was 74 kg of polypropylene / grams of the solid catalyst component with X.l. = 99.3%.

EXAMPLE 41 The solid catalyst component of Example 40 was polymerized according to the general polymerization process without using dicyclopentyl dimethoxysilane. The yield of the polymer was 100 kg of polypropylene / grams of the solid catalyst component with X.l. = 98.6%.

EXAMPLE 42 The procedure of examples 1-27 and comparative examples 28-30 were used, but, in preparing the solid catalyst component, 7.4 mmoles of 9,9-bis (methoxymethyl) fluorene was added in place of the succinate compound. The resulting solid catalyst component contained: Ti = 3.5% by weight, 9,9-bis (methoxymethyl) fluorene = 18.1% by weight. The aforementioned solid catalyst component was polymerized according to the general polymerization process but instead of dicyclopentyl dimethoxysilane, 0.35 mmoles of diethyl 2,3-diisopropylsuccinate were used. The yield of the polymer was 84 kg of polypropylene / grams of the solid catalyst component with X.l. = 98.6%.

EXAMPLE 43 Preparation of the solid catalyst component The spherical support, prepared in accordance with the general method described in Example 2 of the US patent. 4,399,054 (but operating at 3000 rpm instead of 10,000 rpm) was subjected to thermal treatment, under nitrogen flow, within the temperature range of 50-150 ° C, until the spherical particles with an alcohol content were obtained residual of about 35% (1.1 moles of alcohol per mole of MgCb). 16 g of this support was charged, under stirring at 0 ° C, to a 750 ml reactor containing 320 ml of pure TiCU. 3.1 ml of diethyl 2,3-diisopropylsuccinate were added slowly and the temperature was raised to 100 ° C in 90 minutes and kept constant for 120. The stirring was discontinued, sedimentation was allowed to occur and the liquid phase was removed at a temperature of 80 ° C. In addition, 320 ml of fresh TiCU was added and the temperature was raised to 120 ° C and remained constant for 60 minutes. After a 10-minute sedimentation, the liquid phase was stirred at a temperature of 100 ° C. The residue was washed with an anhydrous heptane (300 ml) at 70 ° C, then 3 times (250 ml each) subsequently with anhydrous hexane. at 60 ° C. The spherical component was dried under vacuum at 50 ° C. The composition of the catalyst was as follows: Ti 2.9% by weight 2,3-diethyl 3-diisoprilsuccinate 3.8% by weight Solvent 13.5% by weight Ethylene polymerization: A 4.0-liter stainless steel autoclave equipped with a magnetic stirrer, temperature and pressure indicator, feed line for ethane, propane, hydrogen, and a steel bottle for catalyst injection was used and purified at the put pure nitrogen flow at 70 ° C for 60 minutes and then wash it with propane.

In the following order, 50 ml of anhydrous hexane, 5 ml of TEAL / hexane solution at 10% w / v, and 0.019 g of the solid catalyst at room temperature were mixed, aged 20 minutes and introduced into the empty reactor. in propane flow. The autoclave was closed and 800 g of propane was introduced, then the temperature was raised to 75 ° C and ethylene (7.0 bar, partial pressure) and hydrogen (3.0 bar, partial pressure) were added. Under continuous agitation, the total pressure was maintained at 75 ° C for 180 minutes by feeding ethene. At the end the reactor was depressurized and the temperature dropped to 30 ° C. The collected polymer was dried at 70 ° C under a nitrogen flow. 375 g of polyethylene were collected. The chaeristics of the polymer were reported in table 5.

EXAMPLE 44 The solid catalyst of Example 43 was used in the copolymerization of ethylene / 1-butene as reported in the general procedure but without using any external donor. The other polymerization conditions were reported in Table 4 while the chaeristics of the polymer were collected in Table 5.

EXAMPLE 45 The solid catalyst of Example 43 was used in the copolymerization of ethylene / 1-butene as reported in the general procedure but using 0.56 mmoles of cyclohexylmethyldimethoxysilane as external donor. The other polymerization conditions were reported in Table 4 while the chaeristics of the polymer were collected in Table 5.

EXAMPLE 46 The solid catalyst of Example 43 was used in the copolymerization of ethylene / 1-butene as reported in the general procedure but using 0.56 mmoles of 2,3-diethylpropyl succinate as an external donor. The other polymerization conditions were reported in Table 4 while the chaeristics of the polymer were collected in Table 5.

EXAMPLE 47 The solid catalyst of Example 43 was used in the copolymerization of ethylene / 1-butene in a fluidized gas phase reactor as described below. A 15.0 liter stainless steel fluidized reactor equipped with gas circulation system, cyclone separator, heat exchanger, temperature and pressure gauge, feed line for ethylene, propane, 1-butane, hydrogen and a steel reactor was used. of one liter for the prepolymerization of the catalyst and the injection of the prepolymer. The gas phase apparatus was purified by running pure nitrogen at 40 ° C for 12 hours and then circulating a propane mixture (10 bar, partial pressure) containing 1.5 g TEAL at 80 ° C for 30 minutes. Subsequently, it was depressurized and the reactor was washed with pure propane, heated to 75 ° C and finally loaded with propane (2 bar, partial pressure), 1-butane (as reported in table 4), ethylene (7.1 bar, partial pressure) and hydrogen (2.1 bar, partial pressure). 100 ml of anhydrous hexane, 9.6 ml of 10% w / v TEAL / hexane solution and the solid catalyst of example 43 were added to a 100 ml three-neck glass flask in the following order (in the amount reported in table 4). They were mixed and stirred at room temperature for 5 minutes and then introduced into the prepolymerization reactor and kept in a propane stream.

The autoclave was closed and 80 g of propane and 90 g of propene were introduced at 40 ° C. The mixture was allowed to stir at 40 ° C for 30 minutes. Subsequently the autoclave was depressurized to eliminate excess propene that did not react, and the prepolymer obtained was injected into the gas phase reactor by using a propane overpressure (an increase of 1 bar in the gas phase reactor). The final pressure, in the fluidized reactor, was kept constant at 75 ° C for 180 minutes by feeding a 10% by weight mixture of 1-butene / ethene. At the end, the reactor was depressurized and the temperature decreased to 30 ° C. The collected polymer was dried at 70 ° C under nitrogen flow and weighed. The characteristics of the polymer were collected in table 5.

EXAMPLE 48 Preparation of the solid catalyst component The procedure of Example 43 was repeated but diisobutyl phthalate (11.8 mmol) was used instead of diethyl 2,3-diisopropylsuccinate. The characteristics of the dry catalyst were as follows: Ti 2.3% by weight Diisobutyl phthalate 4.4% by weight Solvent 5.5% by weight.

The solid catalyst was subsequently used in the copolymerization of ethylene / 1-butene as reported in the general procedure but using diethyl 2,3-diisopropylsuccinate as E.D. The other polymerization conditions were reported in table 4 while the characteristics of the polymer were collected in table 5.

TABLE 4 (Co) ethylene polymerization CHMMS = Cyclohexyl-methyl-dimethoxysilane TABLE 5 Characterization of copolymer n.d. = not determined

Claims (37)

1. NOVELTY OF THE INVENTION CLAIMS 1. - A solid catalyst component for the polymerization of olefins CH2 = CHR, wherein R is hydrogen or hydrocarbyl radical with 1-12 carbon atoms, comprising Mg, Ti, halogen and an electron donor selected from succinates of formula (I): wherein the radicals R-i and R2, equal or different from each other, are a linear or branched C1-C20 alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl group optionally containing heteroatoms; R3 to R6 radicals which are identical or different from each other are hydrogen or a linear or branched C1-C20 alkylaryl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl group optionally containing heteroatoms, and the radicals R3 to Re which are attached to the same carbon atom can join to form a cycle; with the proviso that when R3 to R5 are at the same time hydrogen Re is a radical selected from branched primary, secondary or tertiary alkyl groups, cycloalkyl, aryl, arylalkyl or alkylaryl groups having from 3 to 20 carbon atoms. 2. - The catalyst component according to claim 1, further characterized in that the electron donor compound of formula (I) is selected from those in which Ri and R2 are alkyl, cycloalkyl, aryl, arylalkyl and alkylaryl groups of Ci -Cß. 3. The catalyst components according to claim 2, further characterized in that Ri and R2 are selected from primary alkyls. 4 - The catalyst component according to claim 1, further characterized in that the electron donor compound of formula (I) is selected from those in which R2 and R5 are hydrogen and R is a branched alkyl, cycloalkyl, aryl, arylalkyl and alkylaryl radical having from 3 to 10 carbon atoms. 5. The catalyst component according to claim 4, further characterized in that R6 is a branched primary alkyl group or a cycloalkyl group having from 3 to 10 carbon atoms. 6. The catalyst component according to claim 1, further characterized in that the electron donor compound of formula (I) is selected from those in which at least two radicals of R3 to Re are different from hydrogen and are they select from linear or branched C- or C2o branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl groups optionally containing heteroatoms. 7. - The catalyst component according to claim 6, further characterized in that the two radicals other than hydrogen are bonded to the same carbon atom. 8. The catalyst component according to claim 6, further characterized in that the two radicals other than hydrogen are bonded to different carbon atoms. 9. The catalyst component according to claim 8, further characterized in that the succinate of formula (I) is selected from 2,3-diisopropylsuccinate diethyl, 2,3-diisopropylsuccinate diisobutyl, 2,3-diisopropylsuccinate of di-n-butyl, diethyl 2,3-dicyclohexyl-2-methylsuccinate, diisobutyl 2,3-dicyclohexyl-2-methylsuccinate, diisobutyl 2,2-dimethylsuccinate, diethyl 2,2-dimethylsuccinate, 2-ethyl -2-diethyl methylsuccinate, diisobutyl 2-ethyl-2-methylsuccinate, diethyl 2- (cyclohexylmethyl) -3-ethyl-3-methylsuccinate, diisobutyl 2- (cyclohexylmethyl) -3-ethyl-3-methylsuccinate. 10. The solid catalyst component according to any of the preceding claims, further characterized in that the succinates are used in the form of pure stereoisomers. 11. The solid catalyst component according to any of the preceding claims, further characterized in that the succinates are used in the form of mixtures of enantiomers, or mixtures of diastereomers and enantiomers. 12. - The solid catalyst component according to claim 11, further characterized in that diethyl 2,3-diisopropylsuccinate, diisobutyl 2,3-diisopropylsuccinate and di-n-butyl 2,3-diisopropylsuccinate are used as rae or meso forms pure, or mixtures thereof. 13. The solid catalyst component according to any of the preceding claims, further characterized in that it comprises a titanium compound having at least one titanium-halogen bond and the succinate of formula (I) supported on an Mg dichloride, in active form. 14. The solid catalyst component according to claim 10, further characterized in that the titanium compound is TiCl4 or TiCl3. 15. The solid catalyst component according to any of the preceding claims, further characterized in that it comprises another electron donor compound together with the succinate of formula (I). 16. The solid catalyst component according to claim 15, further characterized in that the additional electron donor compound is selected from ethers, esters of organic mono or bicarboxylic acids and amines. 17. The solid catalyst component according to claim 16, further characterized in that the donor compound of Additional electrons are selected from 1,3-propanedi ethers of formula (II) and esters of organic mono or bicarboxylic acids. 18. The solid catalyst component according to claim 17, further characterized in that the additional electron-donor compound is selected from phthalates or from 1,3-diethers in which Rv "and Rv?" are selected from C 1 -C 4 alkyl radicals, R 1"and Rlv form a condensed unsaturated cycle and R 1, R ", R and Rv? Are hydrogen 19.- A catalyst for the polymerization of olefins CH 2 = CHR, wherein R is hydrogen or a hydrocarbyl radical with 1-12 carbon atoms , which comprises the product of the reaction between: the solid catalyst component of any of claims 1-18, an alkylaluminum compound and, optionally, one or more electron-donor compounds (external donor). 21. The catalyst according to claim 20, further characterized in that the alkylaluminum compound (b) is a trialkylaluminum compound. The catalyst according to claim 20, further characterized in that the trialkylaluminum compound is selected from triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum 22. The catalyst according to claim 19, further characterized in that the external donor (c) is selected from 1,3-diethers of the general formula (I): where R1, R ", R1", RIV, RV and Rv? are they the same or different from each other, hydrogen or hydrocarbon radicals have 1 to 18 carbon atoms, and Rv "and Rv?", equal or different from each other, have the same meaning as R'-Rv? except that they can not be hydrogen; one or more of the groups R'-Rvl "can be joined to form a cycle 23. The catalyst according to claim 22, further characterized in that the 1,3-diethers are selected from those in which Rv" and Rv? "are selected from alkyl radicals of CrC, R1" and R? v form a condensed unsaturated ring, and R1, R ", Rv and R? are hydrogen, 24. The catalyst according to claim 23. , further characterized in that the diether of formula (II) is 9,9-bis (methoxymethyl) fluorene.- The catalyst according to claim 19, further characterized in that the external donor (c) is a silicon compound of formula Ra7Rb8Si (OR9) c, where a and b are integers from 0 to 2, c is an integer from 1 to 4 and the sum of (a + b + c) is 4, R7, R8 and R9 are C1-C18 hydrocarbon groups which optionally contain heteroatoms 26.- The catalyst according to claim 25, further characterized in that a is 1, b is 1 and c is 2. 27. - The catalyst according to claim 25 or 26, further characterized in that R7 and / or R8 are branched alkyl, cycloalkyl or aryl groups with 3-10 carbon atoms that optionally contain heteroatoms and R9 is a C1-C10 alkyl group, in particular methyl. 28. The catalyst according to claim 25, further characterized in that a is 0, c is 3 and R8 is a branched alkyl or cycloalkyl group and R9 is methyl. 29. A catalyst for the polymerization of olefins CH2 = CHR, wherein R is hydrogen or a hydrocarbyl radical with 1-12 carbon atoms, which comprises the product of the reaction between: (i) a solid catalyst component comprising Mg, Ti, halogen, and an electron donor (d); (I) an alkylaluminum compound and, (iii) a succinate of formula (I). 30. The catalyst according to claim 29, further characterized in that the succinate of formula (I) is selected from those in which at least two radicals of R3 to R6 are different from hydrogen and are selected from groups linear or branched C 1 -C 20 alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl optionally containing heteroatoms. 31. The catalyst component according to claim 30, further characterized in that the two radicals other than hydrogen are attached to different carbon atoms. 32. - The catalyst according to claim 29, further characterized in that the internal donor (d) is selected from ethers, esters of organic mono or bicarboxylic acids and amines. 33. The catalyst according to claim 32, further characterized in that the internal donor (d) is selected from 1,3-propanedi ethers of formula (II) and esters of organic mono or bicarboxylic acids. 34. The catalyst according to claim 33, further characterized in that the internal donor (d) is selected from phthalates or the 1,3-diethers in which Rv "and RVIN are selected from C-alkyl radicals. -? - C4, R1"and R? V form an unsaturated condensed cycle and R1, R ", Rv and Rv? Are hydrogen 35. A prepolymerized catalyst component for the polymerization of olefins CH2 = CHR, wherein R is hydrogen or an alkyl group of C? -C-? 2, further characterized in that it comprises a solid catalyst component according to claim 1-10 which has been prepolymerized with an olefin to such an extent that the amount of the olefin prepolymer is 0.2 to 500 grams per gram of the solid catalyst component. prepolymerized according to claim 35, further characterized in that the solid catalyst component has been prepolymerized with ethylene or propylene. 37. - A process for the (co) polymerization of olefins CH2 = CHR, wherein R is hydrogen or a hydrocarbyl radical with 1-12 carbon atoms, which is carried out in the presence of any of the catalysts of claims 19-36 . 38. The process according to claim 37, further characterized in that the olefin to be (co) polymerized is selected from ethene, propene, 1-butene, 4-methyl-1-pentene and 1-hexene. 39.- Propylene polymers characterized because they have a polydispersity index greater than 5, a content of isotactic units expressed in terms of pentanes greater than 97% and a flexural modulus of at least 2000 MPa. 40.- The propylene polymers according to claim 39, in which the polydispersity index is greater than 5.1, the flexural modulus is greater than 2100 and the percentage of propylene units in the form of pentads is greater than 97.5 %.