MXPA99011850A - Activating composition of metallocene complexes in the catalysis of (co)polymerization processes of olefins - Google Patents

Abstract

Organo-metallic composition without boron, comprising an extensively fluorinated organic compound, stable to the air, having a di-unsaturated cycle with five or six carbon atoms, and an alkyl derivative of magnesium or, preferably, of aluminum. Said composition can be used as activator of a metallocene complex of group 4 of the periodic table of elements to form a catalyst with a high activity and low metal content for the polymerization of a-olefins.

Description

ACTIVATING COMPOSITION OF METALOCENE COMPLEX IN THE CATALYSIS OF PROCESSES OF (CO) OLIMERIZATION OF OLEFINS DESCRIPTION OF THE INVENTION The present invention relates to a metallocene complex activating composition in the catalysis of processes for the (co) polymerization of α-olefins. More specifically, the present invention relates to an organometallic composition without boron and with a low content of other metals, particularly aluminum, capable of forming a catalyst with a high activity for the polymerization of α-olefins, combined with metallocene complexes of group IV of the periodic table of the elements. The present invention also relates to such a catalyst, as well as to a polymerization process of α-olefins which uses them. It is generally known in the art that ethylene, or α-olefins in general, can be polymerized or copolymerized by means of a low, medium or high pressure process with catalysts based on a transition metal. A particular group of catalysts active in the polymerization of olefins consists of the combination of an organic oxiderivative of aluminum (in particular polymeric methylaluminoxane or MAO) with a derivative of 5-cyclopentadienyl (metallocene) of a transition metal of group IV of the Periodic table of the elements (in the form approved by IUPAC and published by "CRC Press Inc." in 1989). For a known preparation technique of the above compounds, reference may be made to the description of H. Sinn,. Kamins and, in Adv. Organomet. Chem., Vol. 18 (1980), page 99 of the United States Patent 4,542,199. Despite the numerous advantages with respect to the prior art known, represented by traditional heterogeneous catalysts of the type called Ziegler-Natta, which have a multicentric nature, the metallocene-based catalysts have also been shown to have various disadvantages which have limited their industrial development. Among these, the production of polymer with an insufficient average molecular weight, especially with high temperature polymerization processes, an unsatisfactory activation speed of the catalytic system in processes characterized by reduced residence times in the reactor, the use of significant amounts of activator of MAO and the difficulty of preparing and preserving the latter on an industrial scale, can be mentioned. In an attempt to solve the problems in particular in relation to the use of MAO, metallocene-type catalysts capable of polymerizing olefins also have recently been developed without aluminum compounds, or in the presence of a more limited amount of this metal. However, these systems are based on the formation of catalytic species of a cationic nature, which is obtained by contacting a suitable metallocene with an activator consisting of a strong Lewis acid or, more advantageously, an organometallic salt whose Anion has a delocalised charge and is weakly coordinating, usually a fluorinated tetraarylborane. Various cationic systems of this type are described, for example, in the publications of R. R. Jordan in "Advances in Organometallic Chemistry" vol. 32 (1990), pages 325-387, and X. Yang et al., In "Journal of the American Chemical Society", vol. 116 (1994), page 10015, which provides, in addition to a broad description of the field, numerous patent references in this regard. However, the activity of cationic metallocene catalyst systems is generally lower than systems that use methylalumoxane, which is considerable. Furthermore, the known methods for the preparation of the above ionic activators based on fluoroarylboranes are complexes with not completely satisfactory yields, thus further limiting the industrial use of cationic catalysts. Another disadvantage is found in the sensitivity of these ionic activators to air and humidity, which makes their transfer and storage difficult.

Another aspect of the above catalysts, both ionic and those based on MAO, which is not completely satisfactory, is related to their behavior in the copolymerization of ethylene with α-olefins and / or dienes to produce a linear low density polyethylene or elastomers. olefinic, aging due to the difficulty of obtaining copolymers with sufficiently high molecular weights, suitable for their multiple industrial applications. In fact, it is known to operate with high amounts of comonomer to insert the desired amount into the copolymer, with a consequent increase in the rate of chain transfer reaction, which is competitive with the polymerization, and the production of weights unsatisfactory molecular This drawback becomes more critical when operating with high temperature polymerization process in which the chain transfer reaction is already significant without the comonomer. Other cationic systems based on metallocenes and fluoroaryl aluminates are described in the international patent application WO 98/0715, which claims superior catalytic activity. However, these catalysts are relatively complex in their preparation and are particularly unstable to air and moisture, similar to those which contain boronanions and which are not readily adaptable to nonalkylated metallocene complexes.

The Applicant has now found a new group of activators of metallocene complexes, suitable for forming catalysts of (co) polymerization of α-olefins with high activity and without the above disadvantages. These activators are based on certain fluorinated di-unsaturated cyclic compounds extensively and allow the preparation of high activity catalysts with a low aluminum content. In particular, they can be prepared at the time of use from precursors obtained with processes analogous to the known and relatively simple processes, which are stable to air and moisture, so they solve the problem of handling, transfer and storage. A first objective of the present invention therefore relates to an organometallic composition which can be used as an activator of a metallocene complex of a group IV metal to form a (co) polymerization catalyst of a-alefins, characterized in that comprises the reaction product between: (A) A fluorinated organic compound, comprising at least one diunsaturated cycle with 5 or 6 carbon atoms, having the following formula (I): wherein: each Rx group (i is an integer from 1 to 7) is a substituent of the diunsaturated cycle which is independently selected from hydrogen, fluorine and an aliphatic or aromatic hydrocarbyl group, fluorinated or non-fluorinated, having 1 to 20 carbon atoms, optionally linked to a hydrocarbyl group R? different to form an additional cycle, with the proviso that at least 2, and preferably 3 of the groups R1 R2, R3, R or R5 are independently selected from the group consisting of: fluorine, or a fluorinated alkyl group having the formula -CF (R9R10), in which each group R9 or R10 can have any of the above meanings of the Rx groups and at least one of them is fluorine, or fluorinated alkyl at least at position 1, or fluorinated aryl ArF as defined in the following, or a fluorinated vinyl group VF, as defined in the following, or a fluorinated aryl group ArF substituted on the aromatic ring with at least two groups selected from fluorine, a group -CF (R9R10 ) as defined in the above or a different ArF group, or a VF fluorinated vinyl group substituted in at least two positions of the double bond of groups selected from fluorine, a group -CF (R9R10) or an ArF group, such as it is defined before; the group Rs is hydrogen, -OH, -SH or, together with the group R5, forms a carbonyl oxygen; and "m" can have the values of 0 or 1; (B) an organometallic compound having the following formula (II): M '»X (p.n) n: wherein: M 'is a metal of group 2 or 13 of the periodic table of the elements, preferably Mg or Al, more preferably Al, each R is independently a hydrocarbyl, preferably an alkyl group having 1 to 10 carbon atoms, each X is a halogen atom, preferably chlorine or bromine, "p" is the valence of M 'and is equal to 2 for group 2 and 3 for group 13, "n" is a decimal number which varies from 1 ap, preferably p. A second objective of the present invention relates to an active catalyst composition in the (co) polymerization of α-olefins comprising the following components in contact with each other: the above organometallic composition a complex of a metallocene of a metal of group 4 of the periodic table, comprising at least one optionally substituted, penta-apt (5-) cyclopentadienyl anion coordinated with the metal. This complex preferably has the following formula (III): wherein: M represents a metal of group 4, specifically Ti, Zr or Hf; each RA independently represents a group of a binding of an anionic nature to the metal M, different from cyclopentadienyl or substituted cyclopentadienyl; "w" is an index which has integer values of 1 or 2, depending on whether the valence of M is 3 or 4; A represents an anionic ligand having from 5 to 30 carbon atoms, comprising a 5-cyclopentadienyl ring coordinated with the metal M; RB, regardless of the nature of the other substituents, can have any of the meanings previously specified for ligand A for the group RA, and can also be connected to group A by means of a divalent organic group having from 1 to 15 carbon atoms, to form what is called a metallocene complex "that forms a bridge".

Other possible objectives of the present invention will become apparent from the following description and examples. The term "(co) polymerization of α-olefins", as used in the following in the text and the claims, refers to both the homopolymerization and the copolymerization of α-olefins with each other or with another polymerizable ethylenically unsaturated compound.

Organometallic Composition According to the present invention, the above fluorinated organic compound having the formula (I) is characterized by the presence in the molecule of a diunsaturated cycle having 5 or 6 carbon atoms, ie, a cyclopentadienyl ring or a ring 1 , 2, 4, ß-cyclohexadienyl, depending on whether the value of "m" in formula (I) is 0 or 1, respectively. Compounds having formula (I) with "m" = 0 are preferred, however, due to their higher activating capacity in polymerization processes of α-olefins. Each of the groups from Rx to R7 which form the substituents of this diunsaturated cycle can be, when taken alone, hydrogen, fluorine or an aliphatic or aromatic, monovalent, optionally fluorinated hydrocarbyl group. Typical but not limiting meanings of these R: -R7 groups are: hydrogen, fluoro, methyl, trifluoromethyl, ethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, 1,1-difluoroethyl, heptafluoroisopropyl, 1,1-difluorohexyl, perfluorocyclohexyl , pentafluorophenyl, ortho-, meta-, and para-nonafluorodiphenyl, 2,4,6-trifluorophenyl, 2, 3, 5-t-fluorophenol, 1,1-difluorobenzyl, heptafluorobenzyl, pentafluorophenylmethyl, 2,6-bis (trifluoromethyl) ) phenyl, 2,6-difluoro-4-trifluoromethylphenyl, etc. Fluoro, trifluoromethyl, pentafluorophenyl, ortho-meta- or para-bis (trifluoromethyl) phenyl are preferred as fluoro groups due to their high activating activity to the commercial availability of the precursors of compounds having the formula (I) substituted with these groups. When two or more groups Ri ~ R7 are joined together to form cyclic structures comprising two atoms of the diunsaturated cycle having the formula (I)These groups Rt (i = 1-7) are formally divalent and can be saturated or desaturate to form saturated, unsaturated condensed aromatic cycle with the first diunsaturated, preferably having 5 to 8 carbon atoms, more preferably aromatic rings with 6 atoms. In this way, compounds are formed having the formula (I) consisting of di- or poly-cyclic condensed structures. According to a preferred aspect of the present invention, the two groups R1 and R2, and optionally the two R groups, and R4 in the compound having the formula (I) with "m" equal to 0, consist of fluorinated vinyl groups as defined above, which are linked together in the second unsaturated carbon so as to form 1, or optionally 2 aromatic rings fused to the diunsaturated ring. In this manner the indenos or fluorenos (or the corresponding hydroxy-or thioderivados with R¿ equal to -OH or -SH, respectively) substituted on each aromatic ring with at least two groups that are selected from fluorine, fluorinated alkyl or fluorinated aryl , are formed respectively, according to the requirements of the compounds having the formula (I). Among these polycyclic compounds, particularly preferred are fluorenes, and especially fluorenes having 6 to 8 fluorine atoms, however placed on two aromatic rings, as well as the corresponding hydroxy- and thioderivatives. According to a particular embodiment, the component (A) of the organometallic composition of the present invention consists of a compound having the formula (I) wherein the two groups R5 and R8 together represent a carbonyl oxygen atom. Cyclopentadienones and cyclohexadienones substituted on the ring with fluorine or fluorinated groups according to that specified above, therefore are included in the scope of formula (I). The compound having the formula (I) preferably comprises from 5 to 50 carbon atoms, and from 5 to 25 fluorine atoms. More preferably, this compound is a cyclopentadiene compound ("m" = 0) having from 9 to 40 carbon atoms, and from 9 to 25 fluorine atoms. For example, compounds having the formula (I) with are perfluoro-3-hydroxycyclohexa-1,4-diene, 1,2,3,4,5,6,6-heptafluorocyclohexa-1,4-diene, 1, 2,4,5-tetra is (pentafluorophenyl) cyclohexa-1,4-diene, 1,2,4,5-tetrakis (tri fluoromethyl) cyclohexa-1,4-diene, 1,2,4,5-tetrakis ( pentafluorophenyl) -3-hidroxiciclohexa-l, 4-diene, 9, 10-dihidroperfluoroantraceno, 9-hydroxy-9, 10-dihidroperfluoroantraceno, 10, 10-H, H-perfluoro-9-phenyl-9, 10-dihydroanthracene, 10 , 10-H, H-9-hydroxyperfluoro-9-phenyl-9,10-dihydroanthracene. Typical examples of fluorinated compounds having formula (I) with "m" = 0 are fluorinated cyclopentadienes with at least 3 fluorine atoms in the ring, or cyclopentadiene substituted with trifluoromethyl groups. Also included in the scope of formula (I) are cyclopentadiene derivatives condensed with one or two extensively fluorinated aromatic rings such as hexafluoroindene or octafluoro-fluorene. Other examples of compounds having formula (I) are indenes and fluorenes hydrogenated on the aromatic rings such as 4, 4, 7, 7-tetrafluoro-4, 5, 6, 7-tetrahidroindenos substituted with at least two fluorine atoms or two pentafluorophenyl groups in the cyclopentadienyl ring and 1,1,4,4,5,5,8,8-octafluoro-l, 2,3,4,5,6,7,8-octahydrofluorenes and the corresponding compounds substituted with a pentafluorophenyl group in position 9. in addition to these fluorinated hydrocarbon compounds, hydroxy- and thio-derivatives substituted with a corresponding -OH or -SH group on the saturated position of the cyclopentadienyl ring, are typical examples of compounds included in formula ( I). According to a preferred embodiment of the present invention, in the compounds having formula (I), "m" = 0 and R5 is selected from fluorine, pentafluorophenyl, nonafluorodiphenyl, bis (trifluoromethyl) phenyl and tris- (trifluoromethyl) phenyl. According to another embodiment of the present invention, 1, 2, 3, 4, 5, 6, 7, 8-octafluorofluorenes wherein R6 is hydrogen or hydroxy and R5 is fluorine, trifluoromethyl, pentafluorophenyl or bis (trifluoromethyl) phenyl, they are preferred as compounds having formula (I). Additional specific and non-limiting examples of such compounds having formula (I) are: 1,2,4-tris- (pentaf 1 uoropheni 1) cic 1 op-entadiene, 1,2,3-tris- (pentafluorophenyl) cyclopentadiene, 1, 2, 3, 4-tetrakis- (pentafluorophenyl) cyclopentadiene, 1,2, 3, 4, 5, 6,7,8-octaf luorof luor ene, 1,2,3,4,5,6,7, 8-octaf luoro-9-hydroxy-9- (2,4- "bis-trifluoroethylphenyl) f luorene, 1,2,3,4,5,6,7, 8-octaf luoro-9- (2, 4 -bis-trif luoromethylphenyl) fluorene, 1,2,3,4,5,6,7,8-octaf luoro-9-hydroxy-9- (3, 5-bis-trif luoromethylphenyl) fluorene, 1, 2 , 3, 4, 5, 6, 7, 8-octafluoro-9- (pentafluorophenyl) fluorene, 1, 2, 3, 4, 5, 6, 7, 8 - octafluoro - 9 - hydroxy - 9 - (pentaf luorofenil ) fluorene, l, 2,3,4,5,6,7,8-octafluoro-9-hydroxy-9- (nonafluorodiphenyl) fluorene, 1,2,3,4,5,6,7, octafluorofluoren-9 The mixtures of these cyclic compounds having formula (I) are also suitable as component (A) of the organ compositions. omethalics of the present invention. Some of the compounds included in the formula (I) are known in the literature and their synthesis methods have been described. For example, pentafluorocyclopentadiene, octafluorofluorene, octafluoro-9-hydroxyfluorene, 9-pentafluorophenyl octafluorofluorene, 2, 3, 4, 5-tetrakis- (trifluoromethyl) -1-hydroxycyclopentadiene, 1,2,3,4, 5-pentakis- (trifluoromet il) cyclopentadiene, 1,4-bis (pentafluorophenyl) cyclopentadiene, 10, 10-H, H-perfluoro-9-phenyl-9,10-dihydroanthracene. As regards the knowledge of the applicants, the use of these compounds and others having the formula (I) which is not known, in the formation of an activating organometallic composition such as the objective of the present invention, has not been described or never suggested. In particular, the fluorinated cyclopentadiene compounds having formula (I) and having the following formula (IV) are new and form a further objective of the present invention: wherein: R5 and R8 have the same meaning defined for formula (I); (y) is an integer from 1 to 4; (Z) is an integer from 1 to 4; the groups Rn and R12 are independently substituents of hydrogen atoms of the respective aromatic ring in one or more of the four available positions, and are selected from fluorine or a fluorinated or non-fluorinated, aliphatic or aromatic hydrocarbyl group, having from 1 to 20 carbon atoms, optionally linked to a different hydrocarbyl group Ru or R12, respectively, to form another cycle, with the proviso that at least 3, preferably 4 of the groups R5, Rn and R12 are independently selected from the group consisting of : fluorine or a fluorinated alkyl group having the formula -CF (R9R10), wherein each group R9 or R10 can have any of the above meanings of the Rt groups and at least one of these is fluorine, or fluorinated alkyl less in position 1, or a fluorinated aryl ArF as defined in the following, or a fluorinated vinyl group VF as defined in the following, or a fluorinated aryl ArF substituted in the aromatic ring with n at least two groups selected from fluorine, a group -CF (R9R10) as defined above or a different ArF group, or a fluorinated vinyl group substituted on at least two positions of the double bond with groups that are selected of fluorine, a group -CF (R9R10) or an ArF group as defined above; and, in addition, R5 is different from H and, if R is H, R5 is different from pentafluorophenyl.

In a preferred embodiment, in the compounds having the formula (IV) all of the eight Rn and R12 are equal to each other and are trifluoromethyl or, even more preferably, fluorine. The above compounds having the formula (I), although they are new, generally can be obtained by adopting for the purpose of the usual synthetic methods of organic chemistry, using specific precursors and known reactions which an average expert in the field is capable of. to identify based on the structure of the desired compound. Examples of specific processes are described by R. Filler et al., In the publication "Journal of Organic Chemistry", vol. 45 (1980); page 1290; by Vlasov V.M. et al., in the revised publication in "Chemical Abstract" vol. 90 (1979), No. 90: 86522q; by Mark J.B. et al., in "Journal of the American Chemical Society", vol. 113 (1991), pages 2209-2222; by P.a. Deck et al., In "Órganometallics" vol. 15 (1996), pages 5287-5291; by V.M. Vlasov in "Journal of Flourine Chemistry" vol. 9 (1977), pages 321-325. According to a particular process established by the Applicant, octafluoren-9-hydroxyfluorenes substituted in the 9-position with a fluorinated alkyl or aryl group can be obtained from the perfluorofluorenone by reaction with an equivalent amount (about 1/1 in moles) of a lithium derivative having the formula R5Li (with alkyl R or fluorinated aryl having from 1 to 20 carbon atoms, preferably trifluoromethyl, pentaf luoroethyl, pentafluorophenyl and bis (trifluoromethylphenyl), in a solution of a hydrocarbon solvent , preferably at temperatures ranging from -50 to + 20 ° C, followed by hydrolysis.

The corresponding octafluorofluorenes can be obtained from the hydroxy derivatives by the bromination reaction of the hydroxyl group with a suitable brominating agent such as PBr3, optionally followed by reduction by means of Zinc or another reducing agent of the bromide group, to provide the hydrocarbon corresponding fluoride. In the specific case in which "y" and "z" are both 4, RX1 and R12 are F and R5 in the formula (IV) is 3, 5-bis (trifluoromethylphenyl), it is not necessary to perform any reduction step of according to this preparation process. The component (B) of the activating organometallic composition of the present invention consists, in its most general sense, of an alkyl compound of a metal of groups 2 or 13 of the periodic table, preferably Mg or Al, more preferably Al This compound may also contain halogen atoms, especially chlorine, as well as the alkyl part. Non-limiting examples of these compounds are: Grignard reagents, such as methylmagnesium chloride, ethylmagnesium chloride, octylmagnesium chloride and phenylmagnesium chloride; magnesium dialkyl such as diethylmagnesium, dibutylmagnesium, etc; aluminum alkyls and aluminum alkyl halides such as aluminum triethyl, aluminum triisobutyl, aluminum tri-hexyl, aluminum tri-octyl, aluminum isoprenyl, aluminum diethylchloride, aluminum dibutylchloride, aluminiomethyl sesquichloride, diisobutyl chloride of aluminum, and aluminum di-n-octylchloride, aluminum triisoprenyl or mixtures thereof. Many of these organometallic compounds are known in the art and some are commercially available. The aluminum alkyls which are particularly suitable as components (B) are aluminum trialkyl in which "n" in the formula (II) is 3 and the three alkyl group are equal to each other and have from 2 to 6 carbon atoms , such as aluminum triethyl, aluminum tributyl, aluminum tri-n-hexyl, aluminum triisobutyl, or mixtures thereof. These aluminum alkyls are commercial products or can be obtained in any case by means of preparative methods recognized in organometallic chemistry. In the activating organometallic composition of the present invention, the two compounds (A) and (B) are preferably present in molar proportions (B) / (A) ranging from 0.1 to 100. It has been found that the use of molar proportions of (B) / (A) greater than 100 does not provide any particular advantage to the catalyst system but is inconvenient as the amount of aluminum which remains in the olefin polymer at the end of the polymerization increases. Particularly preferred molar ratios of (B) / (A) vary from 0.1 to 10.

With reference to the amount of component (B) effectively used for the preparation of the catalyst systems of the present invention, it should be noted that these can vary considerably in relation to the various parameters associated with the subsequent use of the activating composition of the present invention. In particular, as can be seen in the following, the aluminum and magnesium alkyl having the formula (II), especially aluminum trialkyl, can be used to a variable degree also to favor the activation of the metallocene complex having the formula (III), when the RA groups are different from alkyl or aryl, or according to what is already known in the art (for example in "Journal of Polymer Science, part A", vol 32 (1994), pages 2387-2393), as "eliminators" to ensure the removal or deactivation of poisonous impurities from the catalytic system possibly present in the reactor or in the polymerization solvent and in the monomers themselves. The portions of the component (B) used in the different phases of preparation of the catalyst and the polymerization processes contribute to determine the total amount of metal of group 2 or 13, especially aluminum or magnesium, contained in the olefinic polymer that is obtained in the end. of the polymerization, and represent a critical parameter, which as a rule should be as low as possible to provide the polymer itself with the desired dielectric properties for insulation applications and to avoid contamination of food. In addition, as will be described in more detail in the following, in the catalytic formation of the present invention (activating organometallic composition + metallocene complex), it is possible to preactivate a chlorinated metallocene complex, for example with an aluminum alkyl, before contact with a real activating composition itself, and simultaneously placing the three compounds having the formulas (I), (II) and (III), respectively, in contact with each other in the appropriate proportions. In this case, the component (B) having the formula (II) can be conveniently metered in greater quantity if the metallocene complex is chlorinated, in a smaller amount if the metallocene complex is alkylated. With reference to the present invention, the amounts of the component (B) with respect to a proportion of the component (A), specified in the present description and claims, does not comprise the metal alkyl having the formula (II), usually a trialkyl of aluminum, optionally used as a "scavenger", which is normally introduced in the final preparation phase of the polymerization reactor, with concentrations ranging from 0.5 to 1 mmol / 1 with respect to the volume of the polymerization mixture. The activating organometallic composition according to the present invention is preferably prepared in a suitable hydrocarbon solvent, in an inert atmosphere, usually nitrogen or argon, by contact with components (A) and (B) in the desired proportions. The reaction between the two components occurs rapidly within a wide temperature range. The two components (A) and (B) can also be brought into contact with each other in the presence of a metallocene complex having the formula (III) in order to obtain the formation of a catalytic composition according to the present invention, in a single stage.

The catalytic composition The metallocene complex having the formula (III) which forms the component (ii) of the catalytic composition of the present invention can comprise both a cyclopentadienyl ligand A and two pentacyclodienyl ligands when R8 has this meaning. In any case, the groups RA and Rs other than cyclopentadienyl are preferably selected from hydride, halide, more preferably chloride or bromide, a hydrocarbyl or halogenated hydrocarbyl radical having from 1 to 30, preferably from 1 to 10 carbon atoms, different from a cyclopentadienyl group, a phosphonate, sulfonate or carbonate, an alkoxy, carboxy or aryloxy group having from 1 to 20, preferably from 1 to 10 carbon atoms and an amide group, an organic group having from 1 to 20, preferably from 1 to carbon atoms, bonded to metal M with an amide nitrogen atom, an organic group having from 1 to 20, • preferably from 1 to 10 carbon atoms, attached to the metal M with a silicon atom. Complexes having formula (III) wherein RB is different from cyclopentadiene are known in the art as monocyclopentadienyl complexes. A particular group of these complexes is what is termed "restricted metallocenes", in which the RB group, preferably an alkyl, alkylsilyl or alkylamide group is bridged by a single cyclopentadienyl group of the complex. These complexes are described, for example, in published patent applications EP-A 420,436, EP-A 418,044, EP-A 416,815. Metal complexes of group 4 comprising two cyclopentadienyl ligands which are suitable as component (ii) according to the present invention, are for example those represented by the following formula (V): wherein: M represents a metal that is selected from titanium, zirconium or hafnium; each A 'or A "independently represents an organic group containing a 5-cyclopentadienyl ring of an anionic nature, coordinated with the metal M, each R' or R" independently represents a group of an anionic nature with bond s to the metal M, which is preferably selected from hydride, halide, an alkyl Cx-C alkylaryl group, a C3-C20 alkylsilyl group, a C5-C20 cycloalkyl group, a C6-C20 aryl group or arylalkyl, a C-alkoxy group ^ C ^ oo thioalkoxyl, a carboxylate group of C¿-C20 or carbamate, a dialkylamide group of C2-C20 and an alkylsilylamide group of C, -C20.

According to the present invention, in particular, the R 'and R "groups having the formula (V) each independently represent a group of an anionic nature with bond s to the metal M. Typical examples of R' and R" are hydride, halide, preferably chloride or bromide, a linear or branched alkyl group such as methyl, ethyl, butyl, isopropyl, isoamyl, octyl, decyl, benzyl, an alkylsilyl group such as, for example, trimethylsilyl, triethylsilyl or tributylsilyl, an cycloalkyl group such as cyclopentyl, cyclohexyl, 4-methylcyclohexyl, an aryl group such as phenyl or toluyl, an alkoxy or thioalkoxy group such as methoxy, ethoxy, iso- or sec-butoxy, ethyl sulfide, a carboxylate group such as acetate, trifluoroacetate, propionate, butyrate, divalate, stearate, benzoate or again, a dialkylamide group such as diethylamide, dibutylamide or an alkylsilyl amide group such as bis (trimethylsilyl) amide or ethyltrimethylsilylamide. The two groups R 'and R "can also be chemically bonded together and form a cycle having from 4 to 7 different hydrogen atoms, which also comprises the metal M. Typical examples of this aspect are divalent anionic groups such as Trimethylene or tetramethylene group, or the ethylendioxy group The groups R 'and R "which are particularly preferred for their accessibility and the easy preparation of the complexes comprising them, are chloride, methyl and ethyl. According to the present invention, each group of an anionic nature A in the formula (III) and A 'or A "in the formula (V) contains a? 5-cyclopentadienyl ring coordinated with the metal M which is formally derived from a molecule of cyclopentadiene, substituted or unsubstituted, by the extraction of an H + ion The molecular structure and the typical electronic and coordinated configuration of the metallocene complexes of titanium, zirconium and hafnium generally comprise two? 5-cyclopentadienyl groups, which are They are widely described in the literature and are known to those skilled in the art In the most general form of the present invention, a divalent organic group, preferably containing from 1 to 20 carbon atoms, and optionally also one or more heteroatoms which are selected from silicon, germanium and halogens, can be attached to any of the carbon atoms of the cyclopentadienyl ring of groups A 'and A "having the respective formula (V) mind (with the condition that a union valence is available). Preferred groups A 'and A "are the known cyclopentadienyl groups, indenyl or fluorenyl, and their homologous products, wherein one or more carbon atoms of the molecular backbone (including or not included in the cyclopentadienyl ring), are substituted with a radical selected from the group consisting of halogen, preferably chlorine or bromine, a linear or branched alkyl group having from 1 to 10 carbon atoms, optionally halogenated, such as methyl, trifluoromethyl, ethyl, butyl, isopropyl, isoanyl, octyl, decyl, benzyl, an alkylsilyl group such as for example , tthylsilyl, triethylsilyl, or tributylsilyl, a cycloalkyl group such as cyclopentyl, cyclohexyl, 4-methylcyclohexyl, an aryl group having from 6 to 10 carbon atoms, optionally halogenated such as phenyl, pentafluorophenyl or toluyl, an alkoxy or thioalkoxy group such such as methoxy, ethoxy, iso- or sec-butoxy, ethyl sulfide or again, a dialkylamide group such as a diethylamide, dibutylamide or alkylsilylamide group l as bis (tthylsilyl) amide or ethyltthylsilylamide. These groups A 'or A "can also comprise several fused aromatic rings, as in the case, for example, of 4,5-benzoindenyl, Particularly preferred groups A' or A" are cyclopentadienyl, indenyl, 4, 5, 6, 7-tetrahydroindenyl, fluorenyl, azulenyl and the corresponding methyl-substituted groups. Typical examples of complexes having formulas (III) and / or (V) suitable for the purposes of the present invention are the compounds listed below, which however do not in any way limit the full scope of the present invention. (? 5-C5H5) 2TiCl2; [Me2Si (? 5C5Me4) (Nbu)] TiCl2 (? 5-C5H5) 2TiClMe; [1,2-en (? 5-Ind),] TiMe2; (? 5-C5H5) 2TiCl3; (? 5-C5Me5) 2TiCl2; (? 5-C5Me5) 3TiCl; [1, 2-en (? 5-Ind) 2] TiCl2; (? 5-C5H5) Ti (OCOMe) 3; (? 5-C5H5) 2Ti (OCOPh) 2 [(? 5- (3,5-CF3), Bz) 2C5H 2T1C12; (? 5-Ind) Ti (OCOMe) 3; (? 5-C5Me5) Ti (OCOMe) 3; [o-Xen- (? 5- (THInd) 2] TiCl2; (? 5-Ind) Ti (OCOCF3) 2; [? 5- (4-CF3Bz) C5H4] 2TiCl2; [? 5-l, 3- ( CF3) 2C5H3] Ti (OCOMe),; (? 5-C5H5) Ti (OCOCF3) 2; [l, 2-en (? -l- (CF3Bz) Ind),] TiMe2; (? 5-C5H5) Ti ( OCOPh) 3; [Pr1 (? 5-C5H3) (rr-Flu)] TiCl2; o-Bzn [l- (3-Me-? 5-Ind)] 2TiCl2; o-Bzn- [l- (4.7 -Me2) -? 5-Ind], TiBz2; [1.2-en (? 5-Ind) 2] ZrCl2; o-Bzn- [1- (? 5-THInd) 2] TiCl2; [Ph2Si (? 5-Ind ) 2] ZrCl2; (? 5-THInd) 2ZrCl2; (? 5-C5H5) 2ZrCl2; o-Bzn- [l- (4,7-Me) -? 5-Ind] 2] TiBr2; (? 5-Ind Zr (NMe2) 3; [Pri (? 5-C5H5) (? 5-Flu)] ZrCl2; (? 5-C5H5) 2ZrCl (NMe2); (? 5-C? Me5) 2ZrMe2; [1, 2- in (? 5-THInd),] ZrCl ,; (? 5-Ind) 2Zr (NMe2) 2; [Pri (? 5-C5H3) (? 5-Flu)] ZrCl2; (? 5-C5H5) 2ZrCl (NMe2); [Me2Si (? 5-Ind) 2] HfCl2; (? 5-C5Me5) 2ZrCl3; o-Bzn- [1- (4, 7- (Me) 2Ind)] 2ZrCl >; [o-Xen (? 5-Ind) 2] ZrCl2; (? 5-C5Me5) Zr (OCOPh) 3; (? 5-C5Me5) 2ZrBz2; [1, 2-en (? 5-l- (2,4- (CF3), Bz) Ind),] ZrCl2; [? 5- (2, 4- (CF3) 2Bz) C5H4] 2ZrCl; [Me2Si (CH2-? 5-C5H4) 2] ZrCl2; [o-Xen- (? 5-C5H5) 2] ZrCl2; (? 5-THInd) 2Zr (OCOCF3),; [o-Xen- (? E-THInd) 2] ZrCl?; [o-Xen- (? 5-THInd) 2] ZrBz ,; [? 5- (2,4- (CF3) 2Bz) C5H4] 2ZrCl (NMe2); [o-Xen- (? 5-C5H5) 2] ZrMe2; [o-Xen- (? 5-C5H5) (? 5-Flu)] ZrCl2; [? 5- (4-F-Ph) C5H4], ZrCl2; (? 5-C5Me5), ZrCl2; [Me2Si (CH2) 2- (? 5-Ph-C5H3) 2] ZrCl2; o-Bzn [1- (5, 6- (Me) 2Ind)] 2ZrCl2; [1, 2-en (? 5-THInd) 2] ZrMe2; o-Bzn [1- (4,7-di-phenyl) -? 5-Ind] 2ZrMe2; o-Bzn- (Flu) 2HfCl; o-Bzn [l- (-? 5-THInd) 2] ZrCl 2; o-Bzn- [? 5-C5Me4] 2ZrCl2; o-Bzn [l- (3-Me) -? 5-Ind] 2 HfCl 2; [Me2Si (? 5-C5H4) 2] HfCl2; o-Bzn [l-? 5-Ind) 2Zr (OCO-n-C3H7) 2; [Me2Si (? 5- (1-Ind) 2] HfCl2; [Me2Si (? 5-THInd),] HfCl2; o-Bzn [1-? 5- (3-Me) Ind] 2HFCl2; The following abbreviations are used in the above formulas: Me = methyl, Et = ethyl, But = tertbutyl, Bz = benzyl, Prx = 2, 2-isopropylidene, Ind = indenyl, THInd = 4, 5, 6, 7-tetrahydro-indenyl, Flu = fluorenyl , 1,2-en = 1,2-ethylidene, Ph2Si = diphenylsilylene, Me2Si = dimethylsilylene, o-Xen = ortho-xylylene, o-Bzn = ortho-benzylidene The catalytic composition according to the present invention comprises, and obtains, by contact of the previous components (i) and (ii). (ii) Metallocene can be performed each time by experts in the field based on optimization and industrial design criteria, with reference to the specific characteristics of the metallocene complexes in relation to the various parameters of the polymerization process that are they will get. Also included within the scope of the present invention are those catalytic compositions comprising two or more complexes having the formula (III) or (V) mixed together. The catalyst compositions of the present invention based on the metallocene complex mixtures having a different catalytic behavior can be advantageously used, for example, in the polymerization when a wider molecular weight distribution of the polyolefins being produced is desired. When the metallocene complex having the formula (III) does not comprise sufficient reactive RA groups, such as for example alkyl or aryl, it is preferable, in accordance with the present invention, to add to the objective catalyst composition of the present, a sufficient amount of organometallic compound having the formula (II) also capable of acting as an alkylating agent of the complex having the formula (III). The compound having the formula (II), more preferably an aluminum alkyl, can be added as a prepared portion to the metallocene complex to form the component (ii) of the catalyst composition, in a proportion M '/ M which it varies from 1 to 10, preferably from 3 to 10, using a different portion for the formation of the activating organometallic composition (i) according to what has been described above. Alternatively the complete compound having the formula (II), which also comprises the alkylating portion of the metallocene complex, can be contacted with the fluorinated compound having the formula (I) or with the metallocene complex having the formula (II) and the product thus obtained subsequently it is reacted with the component that is lost to form the catalytic composition of the present invention. According to another aspect of the present invention, in order to produce solid components for the formation of olefin polymerization catalysts, for example for use in gas phase polymerization, the above complexes can also be supported on inert solids, which they preferably consist of Si and / or Al oxide such as, for example, silica, alumina or silicoaluminates, but if necessary also of a polymeric nature, such as certain known polystyrenes functionalized for the purpose. The known support techniques for the support of these catalysts, which normally comprise contacting, in a suitable inert liquid medium, between the carrier, optionally activated by heat at temperatures above 200 ° C, and one or two components can be used. (i) and (ii) of the catalyst of the present invention. For the purposes of the present invention, it is not necessary that both components be supported, since only the complex having the formula (III), or the activating composition which forms the component (i) can be present on the surface of the carrier. In the latter case, the component which is lost on the surface is subsequently brought into contact with the supported component, at the time at which the active catalyst for polymerization is to be formed. Also included within the scope of the present invention are the complexes, and the catalyst compositions based thereon, which have been supported on a solid by functionalization of the latter and the formation of a covalent bond between the solid and a solid. metallocene complex included in the previous formula (III). As well as the two components (i) and (ii), one or more additives or components can optionally be added to the catalytic composition of the present invention, according to what is known in the normal practice of the polymerization of olefins to obtain an adequate catalytic system to meet the specific requirements in the field. The catalyst systems obtained in this way should be considered as included in the scope of the present invention. The additives or components which may be included in the preparation and / or formulation of the catalytic composition of the present invention are inert solvents such as, for example, aliphatic and / or aromatic hydrocarbons, weakly coordinated additives which are selected, for example, of non-polymerizable olefins or particular fluorinated ethers, halogenating agents such as silicon halide, halogenated hydrocarbons, preferably chlorinated, etc., and again all other possible components normally used in the art for the preparation of traditional homogeneous metallocene-type catalysts for the (co) polymerization of α-olefins. The components (i) and (ii) of the catalyst composition of the present invention by contacting each other, preferably in an inert diluent at a temperature ranging from room temperature to the temperature selected for the polymerization which may also be certain processes, 150 ° C or higher, and for times ranging from 10 seconds to 1 hour, more preferably from 1 to 30 minutes. Inert diluents suitable for the purpose are, for example, aliphatic and aromatic hydrocarbons liquid at room temperature. The relative amounts between the two components of the present catalyst composition is selected such that the molar ratio (A) / (M), wherein (M) are the moles of metallocene complex having the formula (III) and (A) ) the moles of fluorinated compound having the formula (I), varies from 0.5 to 50, preferably from 1 to 10. For values of proportions greater than 50 there are no significant variations in the results obtained in the polymerization process. It has been systematically observed that the catalyst composition according to the present invention has a characteristic shape of the ultraviolet spectrum with a peak at much higher wavelengths, usually at least 50 nm, with respect to the characteristic peak observed in the ultraviolet spectra of typical ionic metallocene catalysts obtained using known activators based on tetrakis (pentafluorophenyl) borans combined with the same metallocene complex. Figures 1 and 2 of the present patent application indicate, for illustrative purposes, the ultraviolet spectra (absorbance A of various catalytic compositions obtained by contact and reaction at room temperature, in toluene as a solvent, of the following components: Figure 1 (a) 1, 2-ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium-dimethyl / MAO (itco provider) (Al / Zr = 2000); (b) 1,2-ethylenebis (4, 5, 6, 7-tetrahydroindenyl) zirconium-dimethyl / B (C6F5) 4CPh3 (B / Zr = 1/1); (c) 1,2-ethylenebis (4, 5, 6, 7-tetrahydroindenyl) zirconium-dimethyl / 1, 2, 3, 4, 5, 6, 7, 8-octafluoro-9- (pentafluorophenyl) -fluoren / TIBAL (Zr / fluoren / Al = 1/1 / 0.33); (d) 1,2-ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium-dimethyl / 1, 2,3,4,5,6,7,8-octafluorofluoren / TIBAL (Zr / fluoren / Al = 1 /1/0.33); Fissure 2 (e) (pentamethyl) cyclopentadienyl titanium trichloride / TIBAL / B (C6F5) 4CPH3 (Al / B / Zr = 50/1/1); f) (pentamethyl) cyclopentadienyl titanium / MAO / (Al / Zr = 250) trichloride; (e) (pentamethyl) cyclopentadienyl titanium trichloride / TIBAL / -l, 2,3,4,5,6,7,8-octafluoro-9- (pentafluoro-phenyl) fluorene (Zr / flurene / Al = 1 / 1/50).

In the ultraviolet spectra indicated in the figures 1 and 2 above, the absorption peaks at 630, 640 and 920 nm of the curves (c), (d) and (f), respectively, relate to catalytic compositions according to the present invention, which can be distinguished clearly. These peaks fall at much higher wavelengths than the peaks obtained with traditional compositions based on the corresponding metallocenes activated with MAO or with B (C6F5) 4CPh3. The catalytic composition of the present invention can be used basically with excellent results in all known processes of (co) polymerization of α-olefins, continuously as in batches, in one or more stages, such as, for example, a low pressure (0.1-1.0 MPa), medium (1.0-10 MPa) or high (10-150 MPa), at temperatures ranging from 20 to 240 ° C, optionally in the presence of an inert diluent. Hydrogen can be conveniently used as a molecular weight regulator. Typical α-olefins which can be (co) polymerized with the catalysts according to the present invention are aliphatic unsaturated hydrocarbons having from 2 to 30 carbon atoms, linear or branched, optionally substituted with one or more halogen atoms, such as fluoro or chloro, whose molecule contains at least one primary unsaturated group (-CH = CH2). These unsaturated hydrocarbons also comprise cyclic groups and / or one or more additional terminal or internal C = C unsaturations, conjugated or unconjugated with the primary unsaturated group. Examples of these α-olefins include ethylene, propylene, 1-butene, 4-methylpent-1-ene, 1-hexene, 1-octene, 1-decene, 1-octadecene, 1,4-hexadiene, 1, 3- butadiene, ethylidene norbornene. Ethylene is particularly preferred both in the processes of homopolymerization to obtain a high-density, highly crystalline polyethylene, as well as in the processes of copolymerization with one or more different α-olefins or with non-conjugated dienes, to obtain a low density polyethylene ( also referred to as LLDPE or VLDPE) or olefinic saturated (for example EPR) or unsaturated (for example EPDM) rubbers. These processes can be carried out in solution or suspension in a liquid diluent which usually consists of a saturated aliphatic or cycloaliphatic hydrocarbon having from 3 to 8 carbon atoms, but which can also consist of a monomer such as, for example, the known copolymerization process of ethylene and propylene in liquid propylene. The amount of catalyst introduced into the polymerization mixture is preferably selected such that the concentration of metal M ranges from 10"5 to 10" 8 moles / liter. Alternatively, the polymerization can be carried out in the gas phase, for example in a fluid bed reactor normally at pressures ranging from 0.5 to 5 MPa and temperatures ranging from 50 to 150 ° C. According to a particular aspect of this invention, the catalytic composition for the (co) polymerization of α-olefins is prepared separately (preformed) by contacting components (i) and (ii), and subsequently it is introduced into the polymerization environment. The catalyst composition can first be introduced into the polymerization reactor followed by the reagent mixture containing the olefin or the mixture of olefins to be polymerized, or the catalyst composition can be introduced into the reactor which already contains the reagent mixture. , or finally the reagent mixture and the catalyst composition can be fed into the reactor at the same time in a typical process continuously. Alternatively, the three components corresponding to the compounds having the formulas (I), (II) and (III) can be brought into contact with each other, and they are reacted at the same time, in appropriate proportions, and the catalytic composition that is obtained in this way is introduced into the polymerization environment. According to another aspect of the present invention, the catalyst is formed in itself, for example by introducing the preformed components (i) and (ii), separately into the polymerization reactor containing the preselected olefinic monomers. According to a different technique, which however is included within the scope of the present invention, the compound (A) fluorinated cyclopentadienyl, the complex (ii) of metallocene in a suitable amount of aluminum alkyl (B) (sufficient to carry out the activator formation and, if necessary, the alkylation of the metallocene complex), can be introduced into the polymerization environment, in order to form the polymerization catalyst from the components previous initials. The catalysts according to the present invention can be used with excellent results in the polymerization of ethylene to provide linear polyethylene and in the copolymerization of ethylene with propylene of higher α-olefins, preferably having from 4 to 10 carbon atoms, to provide copolymers having various characteristics in relation to the specific polymerization conditions and the amount and structure of the α-olefin itself.

For example, linear polyethylenes with densities ranging from 0.880 and 0.940 with molecular weights ranging from 10,000 to 2,000,000 can be obtained. The α-olefins preferably used as ethylene comonomers in the production of linear polyethylene of low or medium density (known by the abbreviations ULDPE, VLDPE, and LLDPE according to the density) are propylene, 1-butene, 1-hexene and 1 -octeno The catalyst composition of the present invention can also be conveniently used in copolymerization processes of ethylene and propylene to provide saturated elastomeric copolymers which can be vulcanized, for example, by means of peroxides, and which are extremely resistant to aging and degradation , or in the terpolymerization of ethylene, propylene and a non-conjugated diene having from 5 to 20 carbon atoms, to obtain vulcanizable rubbers of the EPDM type. In the case of the latter process, it has been found that the catalyst of the present invention allows polymers having a particularly high diene and an average molecular weight under the polymerization conditions to be obtained. Preferred non-conjugated dienes for this purpose are, for example: 1,4-hexadiene and 1,6-octadiene; 5-methyl-1,4-hexadiene; 3, 7-dimethyl-l, 6-octadiene; 1,4-cyclohexadiene; 1,5-cyclooctadiene; 5-methylene-2-norbornene, 5-ethylidene-2-norbornene (ENB) and mixtures thereof.

In the case of the EPDM terpolymers, the amount of diene monomer conveniently does not exceed 15% by weight, and preferably ranges from 2 to 10% by weight. On the other hand, the propylene content ranges from 20 to 50% by weight. The catalyst composition of the present invention can also be used in homo- and copolymerization processes of α-olefins other than ethylene, under the conditions commonly adopted in the art for the corresponding polymerization processes with known metallocene-based catalysts to provide with yields excellent, atactic, isotactic and syndiotactic polymers, depending on the structure and geometry of the activated metallocene complex. The a-olefins suitable for the purpose are those having from 3 to 20, preferably from 3 to 10 carbon atoms, optionally substituted with halogen atoms or aromatic nuclei such as, for example, propylene, 1-butene, 1-hexene , 4-methyl-1-pentene, 1-decene and styrene. The present invention is further illustrated by the following practical examples which are illustrative only and in no way limit the scope of the invention itself.

EXAMPLES The following analytical and characterization techniques are used in the embodiment of the illustrative examples of the invention. Spectroscopy-NMR and 19FRMN, for the characterization of molecular structures and activators, complexes and olefinic polymers, by means of the nuclear magnetic resonance spectrometer model MSL-300, using CDC13 as a solvent, unless otherwise specified. UV spectroscopy, for the characterization of the catalytic compositions in a toluene solution, in a Perkin-Elmer spectrometer model LAMBDA-20. Gel Permeation Chromatography (GPC) for the determination of the average molecular weights of the olefinic polymers Mn and Mw and the relative MWD distribution, by means of a Waters 150-CV chromatograph with a differential refractometer Waters as detector, eluting with 1, 2, 4-trichlorobenzene (stabilized with Santonox) at 135 ° C. A set of μ-Styragel HT columns (Waters) of which 3 have pore dimensions of 103, 104, 105 A, respectively and 2 with pore dimensions of 106 A, establishing a flow rate of the eluent of 1 ml / min. The data is obtained and processed by means of the programming element (software) Maximum 820 version 3.30 (Millipore); the calculation of the number (Mn) and weight (Mw) average of molecular weights is carried out by means of universal calibration, selecting polyethylene standards with molecular weights within the range of 6,500,000-2,000 for calibration. DSC calorimetry for the determination of the melting point Tf and the point of crystallization Tc of the olefinic polymers and the respective enthalpies? H £ and? HC, in a Perkin-Elmer differential calorimeter. The calorimetric curve is obtained by heating or cooling the polymer sample at a constant speed of 10 ° C / min. The melting point or crystallization is determined in the curve obtained in the second scan, using heating or cooling, respectively, after subjecting the sample to a first heating or cooling cycle at 10 ° C / min. The reagents and solvents used in the embodiment of the following examples are pure commercial products, unless otherwise indicated. Before use, the solvents are subjected to drying or distillation by drying according to conventional methods. Unless otherwise indicated, all synthesis reactions and preliminary operations of the polymerization processes as well as the conservation and handling of the organometallic compounds are carried out in an inert atmosphere of nitrogen or argon depending on the needs.

EXAMPLE 1: Preparation of 1, 2, 4-tris- (pentafluorophenyl; cyclopentadiene (VI) 2.6 g (0.039 mole) of cyclopentadiene is added for about 30 minutes to 100 ml of anhydrous THF containing 1.61 g (0.035 mole) of a 50% paraffin metal sodium dispersion, which is maintained at a temperature of 20-25. ° C, the mixture is kept under stirring and in an inert atmosphere. When the production of hydrogen is finished, 3.05 g (0.070 mole) of NaH is introduced as a 55% paraffin dispersion, together with 65 g (0.35 mole) of C6F6 and the mixture is refluxed for 70 hours. At the end of the heating, the solvent is distilled under vacuum at 30-40 ° C and the residue is washed three times with 100 ml of petroleum ether, stirring the mass vigorously. The residue is then dissolved in 50 ml of ethyl ether, 50 ml of water are added followed by 250 ml of petroleum ether. The ether phase is separated, filtered on a 5 cm layer of silica gel and then dried. 50 ml of petroleum ether are added to the semi-solid residue; a solid product is separated which is filtered. The solid obtained is crystallized from hot heptane and decolorized with carbon. After filtration and drying, 1.2 g of the desired product is obtained as a white crystalline solid. ^ NMR: 4.13 ppm (s, 2H); 7.31 ppm (s, 1H); 19FRMN: -140.3 ppm (m, 4F); -140.7 ppm (m, 2F); -153.3 ppm (t, 1F); -153.8 ppm (t, 1F); -154.4 ppm (t, 1F); -160.9 ppm (quintet 4F); -162.0 ppm (t, 2F).

EXAMPLE 2: Preparation of 1,2,3-tris- (pentafluorophenyl) -cyclopentadiene (VII). 0.2 g of the isomer of 1,2,3-tris- (pentafluorophenyl) cyclopentadiene, in the form of a white crystalline solid, is obtained from the crystallization of the mother liquors of the compound 1, 2, 4-tris - (pentafluorophenyl) cyclopentadiene, which is obtained at the end of the method of example 1 above, after concentration and separation on a column of silica gel (eluent, petroleum ether). XH NMR: 3.84 ppm (d, 2H); 6.98 ppm (t, 1H); 19FRMN: -140.38 ppm (m, 4F); -140.8 ppm (m, 2F); -151.8 ppm (t, 1F); -152.9 ppm (t, 1F); -153 ppm (t, 1F); -160 ppm (m, 6F).

EXAMPLE 3: Preparation of 1, 2, 3,, 5, 6, 7, 8-octafluoro-9-hydroxy-9- (2,4-bis-trifluoromethylphenyl) fluorene (VIII). 7 ml of butyllithium (2.5 M) are added dropwise to a 100 ml solution of anhydrous ethyl ether having 5 g (0.017 mol) of 2,4-bis (trifluoromethyl) bromobenzene, cooled to -75 ° C.

After 1 hour, 3 g (0.009 mole) of 1, 2, 3, 4, 5, 6, 7, 8-octafluorofluorenone prepared in accordance with the prescription indicated in the publication "Journal of the Chemical Society, part (C) ", pages 2394 (1968) The mixture is stirred for 1 hour, then hydrolysed in water, the ether phase is separated, dried over Na 2 SO 4 and dried, a small amount of ether is added from cold oil to the solid which is obtained which is then filtered and dried to obtain 2.55 g of the desired pure product (yield, 52.64% with respect to octafluorofluorenone). ^ NMR: 8.8 ppm (d, 1H), 8.0 ppm (d, 1H), 7.9 ppm (s, 1H), 3.0 ppm (s, 1H), 19FRMN: -58.2 ppm (s, 3F); -63.2 ppm (s, 3F); -133.3 ppm (s, 2F); -143.2 ppm (d, 2F); -150.2 ppm (s, 2F); -152.0 ppm (t, 2F).

EXAMPLE 4: Preparation of 1, 2, 3, 4, 5, 6, 7, 8-octafluoro-9- (2,4-bis-trifluoromethylphenyl) fluorene (IX). 0.95 g (0.0017 mole) of the product obtained according to the preparation of example 3 above are heated with 10 ml (0.105 mole) of PBr3 at 110-120 ° C for 40 minutes. The reaction mass is hydrolysed on ice, extracted with ethyl ether, the extract is washed with an aqueous solution of NaHCO 3 (10%), dried over Na 2 SO 4, filtered and the ether solution is dried. The residue is purified by chromatography on a column of silica gel (eluent, petroleum ether), which is obtained, after evaporation of the purified fractions, 0.61 g of a white crystalline product. THRMN: 8.05 ppm (s, 1H); 7.6 ppm (d, 1H); 6.7 ppm (d, 1H); 5.86 ppm (s, 1H). 19FRMN: -58.3 ppm (s, 3F); -63.2 ppm (s, 3F); -133.9 ppm (d, 2F); -140.9 ppm (d.2F); -152.3 ppm (t, 4F).

EXAMPLE 5: Preparation of 1, 2, 3, 4, 5, 6, 7, 8-octafluoro-9-hydroxy-9- (3,5-bistrifluoromethylphenyl) fluorene (X). 4.2 ml of butyllithium (1.6 M), in an inert atmosphere, are added to an ethereal solution (100 ml of anhydrous solvent) of 2 g (0.0068 mol) of 3,5-bis (trifluoromethyl) -bromobenzene cooled to -75 °. C. At the end of the addition, the mixture is heated for 1 h and then 1 g (0.003 mole) of 1, 2, 3, 4, 5, 6, 7, 8-octafluorofluorenone is added, which is prepared according to the prescription specified in Literature (RD Chambers and DJ Spring, J. Chem. Soc. (C), 2394 (1968) .The mixture is stirred for 1 h, and then hydrolysed in water, the ether phase is separated, dried over Na 2 SO 4, it is filtered and the ether solution is dried, obtaining 2.1 g of a yellow product, 1.6 g of pure product are obtained (yield, 99%) by separation on a column of silica gel (eluent, petroleum ether / acetone (90/10). )). XHRMN (solvent CDC13): 7.87 ppm (s, 1H), 7.84 ppm (s, 2H); 3.2 ppm (s, 1H). 19FRMN (solvent CDC13): -62.9 ppm (s, 6F); 132.6 ppm (s, 2F); -142.1 ppm (s, 2F); -149.3 ppm (s.2F); -150.5 ppm (t, 2F).

EXAMPLE 6: Preparation of 1, 2, 3, 4, 5, 6, 7, 8-octafluoro-9- (3,5-bis-trifluoromethylphenyl) fluorene (XI).

Warm g (0.002 mole) of the product (X), which is obtained according to the preparation reported in the example , with 10 ml (0.105 mole) of PBr3 at 110 ° C for 40 minutes. The reaction mass is hydrolysed on ice, extracted with ethyl ether, the ether extract is washed with an aqueous solution of NaHCO 3 (10%), dried over Na 2 SO 4, filtered and the ether solution is dried. The residue is dissolved in 20 ml of acetic acid and 1 g of Zn in pulverized form are added. The mixture is stirred for 1 h at room temperature, hydrolyzed in water and then extracted with ethyl ether. The ether extract is neutralized with an aqueous solution of NaHCO 3 (10%), dried over Na 2 SO 4, filtered and then dried. The residue is purified on a column of silica gel (eluent, petroleum ether) which, after evaporation of the pure fractions, is obtained 0.8 g of the pure product (yield, 76.6%. NMR: 7.84 ppm (s, 1H). 7.53 ppm (s, 2H), 5.57 ppm (s, 1H) 19FRMN: -63 ppm (s, 6F), -133.5 ppm (s, 2F), -141.2 ppm (d, 2F), -151.9 ppm d, 2F); -152.2 ppm (t, 2F).

EXAMPLE 7: Preparation of 1, 2, 3, 4, 5, 6, 7, 8-octafluoro-9-hydroxy-9- (pentafluorophenyl) fluorene (XII). 3 ml of butyllithium (1.6 M) are added dropwise over 15 minutes to an ethereal solution of 5 g (0.02 mole) of bromopentafluorobenzene (120 ml of anhydrous solvent), cooled to -75 ° C. The solution is stirred for 30 minutes and then 3.2 g (0.0097 mole) of 1,2,3,4,5,6,7,8-octafluorofluorenone, which is prepared according to the prescription specified in RD literature Chambers and D.J. Spring, J. Chem. Soc. (C), 2394 (1968). After 30 minutes under stirring, the solution is poured into water and extracted with ethyl ether. The ether solution, after drying over Na 2 SO 4, is filtered and dried. 20 ml of cold oil are added to the solid obtained, which is then filtered. It is washed with a small amount of cold petroleum ether and then dried under vacuum. 4.6 g of the white crystalline product are obtained, with a yield of 93%. XHRMN: 3.75 ppm (t, 1H). 19FRMN: -133 ppm (d, 2F); -141 ppm (m, 2F); -143.8 ppm (d, 2F); -149.7 ppm (s.2F); -151.4 ppm (t, 2F); -151.7 ppm (t, 1F); -159.8 ppm (m, 2F).

EXAMPLE 8: Preparation of 1, 2, 3, 4, 5, 6, 7, 8-octafluoro-9- (pentafluorophenyl) fluorene (XIII). 4.5 g (0.009 mole) of 1,2,3,4,5,6,7,8-octafluoro-9-hydroxy-9- (pentafluorodiphenyl) fluorene (XII), prepared as described in example 7 above, are added. , to 25 ml (0.26 moles) of PBr3 and heated at 110 ° C for 30 minutes in an inert atmosphere. The reaction mass is hydrolysed on ice, extracted with ethyl ether, the extract is washed with an aqueous solution (10%) of NaHCO 3, dried over sodium sulfate, filtered and dried. The residue is purified by chromatography on a column of silica gel (eluent: petroleum ether / methylene chloride, 98/2), obtaining after evaporation of the pure fractions, 3.61 g of a white crystalline product (yield, 84%). %). XH NMR: 5.87 ppm (s, 1H). 19FRMN: -133.8 ppm (s, 2F); -141.6 ppm (d, 1F); -142.6 ppm (d, 1F); -143.1 ppm (d, 2F); -152.1 ppm (m, 2F); -152.4 ppm (t, 1F); -152.7 ppm (t, 2F); -160.1 ppm (m, 1F); -160.7 ppm (m, 1F).

EXAMPLE 9: Preparation of 1, 2, 3, 4, 5, 6, 7, 8-octafluoro-9-hydroxy-9- (nonafluorodiphenyl) fluorene (XIV). 1.6 ml of butyllithium (1.6 M) are added dropwise to an ethereal solution (50 ml of anhydrous solvent) of 1.1 g (0.0028 mol) of 2-bromononafluorodiphenyl, prepared according to the procedure described in the literature (SC Cohen et al. ., Organomet, Chem., 11, 385, (1968)), cooled to -70 ° C. The solution is stirred for 1 night and then 0.6 g (0.0018 mol) of 1,2,3,4,5,6,7,8-octafluorofluorenone, prepared according to the prescription provided in the literature, are added in one go. (RD Chambers and DJ Spring, J. Chem. Soc. (C), 2394 (1968)). After 1 h, under stirring, the solution is hydrolyzed in water and extracted with ethyl ether. The ether solution, after drying over Na 2 SO 4, is filtered and dried. The residue is purified on a column of silica gel (eluent of petroleum ether / acetone, 90/10) obtaining, after evaporation of the pure fractions, 1.1 g of the white product with a yield of 96%. NMR: 3.35 ppm (s, 1H). 19FRMN: -133 ppm (m, 2F); -133.6 ppm (m, 1F); -136.3 ppm (m, 1F); -137.9 ppm (m, 1F); -138.3 ppm (d, 1F); -141.6 ppm (m, 1F); -141.8 ppm (m, 1F); -149.9 ppm (m, 2F); -151.39 ppm (m, 3F); -152.6 ppm (t, 1F); -153.9 ppm (t, 2F); -163.3 ppm (m, 2F).

EXAMPLE 10: Preparation of 1, 2, 3, 4-tetrakis (pentafluoro-phenyl) cyclopentadiene (XV).

G (4.1 mmol) of sodium hydride and 10 g of hexafluorobenzene are added to a solution of 1 g (1.77 mmol) of 1,2,3-tris- (pentafluorophenyl) cyclopentadienyl, which is prepared as described in Example 1. Example 1 above, in 50 ml of anhydrous THF. The reaction mixture is refluxed for 50 h. It is then hydrolyzed in approximately 200 g of ice containing 5 ml of 10% HCl and extracted with ethyl ether.The extract is dried over Na 2 SO 4 and filtered through a 5 cm layer of granular silica. The residue is separated on a column of silica gel (eluent: petroleum ether / acetone = 95/5) After evaporation of the pure fractions, 150 mg of the desired product is obtained as a white crystalline solid .: HRMN: 4.3 ppm (s, 2H).

EXAMPLE 11: Preparation of 9, 9'-bis (9H-f luoren-1,1 ', 2, 2', 3, 3 ', 4, 4', 5, 5 ', 6, 6', 7, 7 ', 8, 8' -exadecaf luoro) (XVI) i) Reduction of 8F-fluorenone, 12 g of octafluorofluorenone are suspended in 20 ml of acetic acid (CH 3 COOH) and are added with 1 g of powdered zinc. The mixture is stirred for 1 hour at room temperature, and the complete disappearance of the initial octafluorofluorenone is detected (by CCD, eluent, petroleum ether: acetone, 8: 2). The reaction mixture is diluted with 150 ml of water and extracted with ethyl ether. After evaporating the solvent from the extract, 2 g of essentially pure 9-OH, 9-H-octafluorofluorenone (99% yield) are obtained. XHRMN (CDC13) 6.16 ppm (d, 1H); 2.62 ppm (d, 1H.OH). 19FRMN (CDCl 3) -134.3 ppm (s, 2F); -142.5 ppm (d, 2F); -151.3 ppm (s, 2F); -152.8 ppm (t, 2F). ii) Bromination of 9H, 9-hydroxyoctafluorofluorene 2 g of 9H, 9-hydroxyoctafluorofluorene obtained as described above in step (i) are mixed with 10 ml of phosphorus tribromide and heated at 80 ° C for 1 hour. The reaction mixture is poured onto ice and extracted with ethyl ether. The ether extract is washed with water several times until neutralized and dried over Na 2 SO 4. After evaporating the solvent, 2 g of pure 9H, 9Br-octafluorofluorene are obtained. X H NMR (CDCl 3): 6.14 ppm (s) 19 FRMN: -133.8 ppm (s, 2 F), -137.2 ppm (t, 2 F); -150.5 ppm (d, 2F); -152.5 ppm (t, 2F). iii) Dimerization To a solution of 2 g of 9H, 9Br-octafluorofluorene in 50 ml of anhydrous ethyl ether is added 10 ml of a 1 M ethereal solution of sec-butylmagnesium chloride. After stirring for 2 hours at room temperature, the reaction mixture is hydrolyzed with ice and extracted with about 500 ml of CH, C12. After drying the extract with Na 2 SO 4, the solvent is evaporated and the solid residue is dissolved with hot toluene. The solution is filtered over active carbon and Celite, and cooled. Solid crystals are formed which, after filtering and drying, provide 1 g of the desired 9,9 'bis (9H-hexadecafluorofluorene) as a pure product. XHRMN (CDC13): 5.4 ppm (s). 19FRMN: -133.2 ppm (s, 4F); -138 to -142 ppm (m, 4F); -151.6 ppm (s, 4F); -152.7 ppm (d, 4F).

EXAMPLES 12-33: POLYMERIZATION Polymerization tests were carried out under different conditions using different combinations of compounds having the formula (I) for the formation of reactive catalytic compositions.

General Method Preparation of the activating organometallic composition An exactly measured amount of 0.03 moles of the selected fluorinated compound having the formula (I) (component A), it is dissolved in approximately 9 ml of toluene.

An amount of triisobutylaluminum (TIBAL) is added to the solution obtained in this manner in order to obtain the desired molar ratio with respect to the compound having the formula (I). The mixture is kept under stirring for a few minutes and then brought to the exact volume of 10 ml before being used in the preparation of the catalyst composition.

Preparation of the catalytic composition Dissolve 0.03 mmoles of the selected metallocene complex in 20 ml of toluene. 0.09 moles of TIBAL (Al / Zr = 3) are added, and the whole mixture is left under stirring for a few minutes. The metallocene complex solution obtained in this way is added to the solution of the activating composition prepared as described above, in such an amount that the selected molar ratio (component A) / (metallocene) is obtained each time, and the mixture obtained is left under agitation for a few minutes before it is used as a catalytic component.

EXAMPLE 12 98.5 ml of toluene containing 0.3 mmoles / 1 of TIBAL that acts as impurity remover are charged in a 250 ml glass reactor equipped with a magnetic stirrer and regulated by thermostat at 30 ° C. The catalyst composition is prepared as described above in the general methods, and contains 1.5 x 10"3 mmoles of 1,2-Et (Ind) 2ZrCl 2 and 1.5 x 10" 3 mmoles of 1,2,3-tris (pentafluorophenyl) cyclopentadiene, which is prepared as described in Example 2 above with a molar ratio (component A) / Zr = 1 and then a molar ratio is introduced (Al total / (component A) = 3.5 The reactor is pressurized to 50 Kpa (re.) with ethylene and the mixture is kept low stirring for 60 minutes, ethylene is fed continuously to keep the pressure constantly at the initial value.At the end, the reactor is depressurized and 5 ml of methanol is introduced to complete the polymerization and deactivate the catalyst.The polymer is recovered by precipitation in 400 ml of methanol acidified with hydrochloric acid, filtration and drying under vacuum at 40 ° C for about 8 hours 0.5 g of polyethylene are obtained.

EXAMPLE 13 The same procedure is adopted as in the previous example 12, but using 1.5 x 10 ~ 3 mmoles 1,2,4-tris- (pentafluorophenyl) cyclopentadiene (prepared according to previous example 1) instead of 1, 2, 3 -tris- (pentafluorophenyl) -cyclopentadiene, 0.4 g of polyethylene are obtained.

EXAMPLE 14 The same procedure as in Example 12 above is adopted, but using 3.0 x 10 ~ 3 mmoles of 1, 2, 4, 5-tetrakis- (pentafluorophenyl) cyclopentadiene (prepared according to example 10 above) instead of 1.5 x 10 ~ 3 mmoles of 1,2,3-tris (pentafluorophenyl) cyclopentadiene with a molar ratio of Al / (component A) = 3.5 and a molar ratio of Zr / activator = 0.5. 0.8 g of polyethylene are obtained.

EXAMPLE 15 The same procedure is adopted as in Example 12 above, but using 1.5 x 10 ~ 3 mmoles of 1,2,3,4,5,6,7,8-octafluoro-9- (3,5-bis-trifluoromethylphenyl) fluorene (prepared according to example 6 above) instead of 1,2,3-tris (pentafluorophenyl) cyclopentadiene with a molar ratio of Al / (component A) = 5. 1.15 g of polyethylene are obtained.

EXAMPLE 16 The same procedure as in Example 12 above is adopted, but using 1.9 x 10 ~ 3 mmoles of 1,2,3,4,5,6,7,8-octafluoro-9- (pentafluorophenyl) fluorene (prepared in accordance with Example 8 above) Instead of 1.5 x 10 ~ 3 mmoles of 1,2,3-tris (pentafluorophenyl) cyclopentadiene, with a molar ratio of Al / (component A) = 3.3 and a molar ratio of Zr / (component A ) = 0.8. 1.2 g of polyethylene are obtained.

EXAMPLE 17 (comparative) The same equipment and the same conditions as in Example 12 above are adopted, but using a traditional ionic type catalytic system. Consequently, 1.5 x 103 mmoles of 1,2-Et (Ind) 2 ZrCl 2 are dissolved in 1 ml of toluene and 0.15 mmoles of triisobutylaluminum are added to this solution as the alkylating agent, the mixture is left under stirring for 15 minutes. This mixture is added to a solution of 1.5 x 10 ~ 3 mmoles of B (C6F5) 4PhNHMe, in 1 ml of toluene and the whole mixture is left under stirring for a few minutes. The resulting (comparative) catalyst composition is charged in a 250 ml glass reactor, which is pressurized to 50 Kpa (re.) With ethylene and the same procedure as in example 12 is adopted. In the end, 1.1 g is obtained. of polyethylene.

EXAMPLE 18 98.5 ml of toluene containing 1 mmol / 1 of TIBAL, which acts as an impurities remover, are charged in a 250 ml glass reactor equipped with a magnetic stirrer and regulated with a thermostat at 80 ° C. The catalytic composition, prepared separately as described above in the general methods, is then introduced, containing 1.5 x 10"3 mmoles of 1,2-Et (Ind) 2ZrCl¿ and 3.0 x 10" 3 mmoles of 1, 2, 3, 4, 5, 6, 7, 8-octafluoro-9-hydroxy-9- (pentafluorophenyl) fluorene (as component A), prepared as described in example 7 above, with a molar ratio (component A) / Zr = 2 and a molar ratio (To total / (component A) = 2.7 The reactor is pressurized to 50 Kpa (re.) With ethylene and the mixture is kept under agitation for 60 minutes at 80 ° C, continuously feeding ethylene to maintain At the end, the reactor is depressurized and 5 ml of methanol are introduced to complete the polymerization and deactivate the catalyst The polymer is recovered by precipitation in 400 ml of methanol acidified with hydrochloric acid, filtration, and dry under vacuum at 40 ° C for about 8 hours, 10 g of polyethylene, which has Mw = 114000, Mn = 47200, MWD = 4.2; Tf = 132.98 ° C,? Hf = -194.34 J / g, Tc = 144.22 ° C,? HC = -197.52 J / g.

EXAMPLE 19 The same procedure as in Example 18 is adopted, using the same molar amount of 1,2,3,4,5,6,7,8-octafluoro-9- (pentafluorophenyl) fluorene, prepared as described in Example 8 previous, instead of 1,2,3,4,5,6,7,8-octafluoro-9- (hydroxypentafluorophenyl) fluorene. 10.5 g of polyethylene are obtained with Mw = 88250, Mn = 42270, MWD = 2.08; Tf = 132.6 ° C,? H £ = 203.7 J / g, Tc = 113.54 ° C,? HC = -205.33 J / g.

EXAMPLE 20 The same procedure is followed as in Example 18, using, however, 7.5 x 10"3 mmoles of 1,2,3,4,5,6,7,8-octafluoro-9- (2,4-bis- trifluoromethylphenyl) fluorene, prepared as described in Example 4 above, instead of 3.0 x 10"3 mmoles of 1, 2, 3, 4, 5, 6, 7, 8 -oct af luoro- 9-hydroxy- 9- (pentafluorophenyl) fluorene, with a molar ratio of component A / Zr = 5.0 and a molar ratio of Altotal / (aspnent A) = 1.6. At the end, 7.5 g of polyethylene are obtained.

EXAMPLE 21 The same procedure as in Example 18 is adopted, but using the same molar amount of 1,2,3,4,5,6,7,8-octafluoro-9-hydroxy-9- (3,5-bis-trifluoromethylphenyl) ) fluorene instead of 1, 2, 3, 4, 5, 6, 7, 8 - octaf luo ro - 9 -hi dr oxy-9 - (pentafluorophenyl) fluorene. 6 g of polyethylene are obtained.

EXAMPLE 22 (comparative: The same equipment and the same conditions as in example 18 above are adopted, but using a traditional ionic type catalytic system. Consequently, 1.5 x 10 ~ 3 mmoles of 1,2-Et (Ind) 2ZrCl2 are dissolved in 1 ml of toluene and 0.015 mmoles of triisobutylaluminum are added to this solution as the alkylating agent, the mixture is left under stirring for 15 minutes. This mixture is added to a solution of 1.5 x 10 ~ 3 mmoles of B (C6F5) 4Ph3C in 1 ml of toluene and the whole mixture is left under stirring for a few minutes. The resulting (comparative) catalyst composition is charged to the 250 ml glass reactor preheated to 80 ° C and pressurized to 50 Kpa (re.) With ethylene and the same procedure as in example 17 is adopted. they obtain 9.6 g of polyethylene, with Mw = 56000, Mn = 23100, MWD = 2.4; Tf = 130.05 ° C,? H £ = 214.09 J / g, Tc = 112.95 ° C,? HC = -218.7 J / g.

EXAMPLE 23 500 ml of toluene containing 0.72 mmoles / 1 of TIBAL that acts as impurities remover are charged in a 1 liter AISI steel reactor equipped with a mechanical stirrer. The reactor is regulated by thermostat at 80 ° C and the catalytic composition, prepared separately as described above in the general methods, containing 1.5 x 10"3 mmoles of 1,2-Et (Ind) 2ZrCl2 and 1.5 x 10" 3 mmoles of 1,2,3,4,5,6,7,8-octafluoro-9-hydroxy-9- (pentafluorophenyl) fluorene (as component A), prepared as described in example 8 above, with a proportion molar (component A) / Zr = 1 and a molar ratio (To total / (component A) = 4, is introduced later.The reactor is pressurized to 0.80 MPa (re.) with ethylene and the mixture is kept under stirring for 60 minutes. minutes at 80 ° C. Ethylene is continuously supplied to keep the pressure constantly at the initial value.At the end the reactor is depressurized and 5 ml of methanol is introduced to complete the polymerization and deactivate the catalyst.The polymer is recovered by precipitation in 1000 ml of methanol acidified with hydrochloric acid, filtration and drying under vacuum at 40 ° C for a approximately 8 hours. 78 g of the polyethylene having Mn = 47800, Mw = 88500, MWD = 1.85 is obtained.

EXAMPLE 24 The same procedure as in Example 23 is adopted, but using the same molar amount of 1,2,3,4,5,6,7,8-octafluoro-9-hydroxy-9- (pentafluorophenyl) fluorene, prepared in accordance with example 7 instead of 1, 2, 3, 4, 5, 6, 7, 8-octafluoro-9- (pentafluorophenyl) fluorene. You get 79.2 g of polyethylene that has Mn = 47350, Mw = 110560, MWD = 2.3 EXAMPLE 25 The same procedure as in Example 23 is adopted, but using 1, 2, 3, 4, 5, 6, 7, 8-octafluoro-9- (3,5-bis-trifluoromethylphenyl) fluorene, prepared according to the example 6 instead of 1, 2, 3, 4, 5, 6, 7, 8-octafluoro-9- (pentafluorophenyl) fluorene. 74 g of polyethylene are obtained, with Mw = 46000, Mn = 80000, MWD = 1.73; Tf = 137 ° C,? H £ = 216.3 J / g, Tc = 110.5 ° C,? HC = -206.45 J / g.

EXAMPLE 26 The same procedure as in Example 23 is adopted, but using as fluoro compound 4.5 x 10"3 mmoles of 1, 2, 3, 4, 5, 6, 7, 8-octafluorofluorene, prepared according to the method described in the publication "Journal of Organic Chemistry", vol. 45 (1980), page 1290, instead of 1.5 x 10"3 mmoles of 1, 2, 3, 4, 5, 6, 7, 8-octaf luoro-9- (pentafluorophenyl) fluorene, with a molar ratio of (component A) / Zr = 3 and a molar ratio of Al / (component A) = 4. 66.8 g of polyethylene having Mn = 50600 are obtained, Mw = 11200, MWD = 2.19 EXAMPLE 27 The same procedure and the same proportions are adopted between the catalytic components as in the example , but using 1, 2, 3, 4, 5, 6, 7, 8-octafluoro-9-hydroxy-9- (nonafluorophenyl) fluorene, prepared according to the example 9 previous, instead of 1, 2, 3, 4, 5, 6, 7, 8-octafluorofluorene. 66.8 g of polyethylene are obtained, which has Mn = 45100, Mw = 85800, MWD = 1.9.

EXAMPLE 28 (comparative) The same equipment and the same conditions as in the previous example 23 are adopted, but using the same traditional ionic type catalyst system as in the previous example 22 (comparative). 76.6 g of polyethylene are obtained.

EXAMPLE 29 ml of toluene are charged to a 100 ml glass reactor equipped with a magnetic stirrer. The reactor is regulated with a thermostat at 30 ° C. Dissolve 1.5 x 10"3 mmoles of 1,2-ethylenebis (4,5,6,7-tetrahydroindenyl) zirconiodimethyl- (Et (THInd) ¿ZrMe¿) in 10 ml of toluene, and this solution is added to a solution of toluene with a volume of 10 ml containing 1.5 x 10"3 mmoles of 1, 2, 3, 4, 5, 6, 7, 8-octafluoro-9- (pentafluorophenyl) fluorene and 1.5 x 10" 3 mmoles of TIBAL The entire mixture is left under stirring for a few minutes (molar ratio of Zr / (component A) / TIBAL = 1/1/1 /.) The resulting catalytic mixture is charged to the reactor which is pressurized to 50 Kpa (laugh) with ethylene and the mixture is kept under stirring for 60 minutes at 30 ° C, continuously feeding ethylene to keep the pressure constantly at the initial value.At the end, the reactor is depressurized and 5 ml of methanol are introduced to finish the polymerization and deactivate the catalyst.The polymer is recovered by precipitation in 200 ml of methanol acidified with hydrochloric acid, filtration and dried. at low vacuum at 40 ° C for approximately 8 hours. 0.65 g of polyethylene are obtained.

EXAMPLE 30 (comparative) The same procedure is adopted as in the previous example 29, but using as catalytic composition a traditional ionic catalyst prepared by the reaction of 1.5 x 10"3 mmole of Et (THInd) 2ZrMe2 with 1.5 x 10" min. Of CPH3B (C6F5) 4 in toluene (molar ratio of Zr / B = 1). 0.7 g of polyethylene are obtained.

EXAMPLE 31 98.5 ml of toluene containing 1.1 mmoles / 1 of TIBAL, as impurities remover, and 2.5 g of 1-hexene, are charged in a 250 ml glass reactor. The reactor is regulated by thermostat at 50 ° C and 1.5 ml of the catalytic solution prepared according to the general procedure described above, which contains 1.5 x 10"3 mmoles of 1,2-Et (Ind), ZrCl 2 and, as a component A, 1.5 x 10"3 mmoles of 1, 2, 3, 4, 5, 6, 7, 8-octafluoro-9- (pentafluorophenyl) fluorene, with a molar ratio of Zr / (component A) = 1, and with a molar ratio of (Alt tal) / (component A) = 1. The reactor is pressurized to 50 Kpa (re.) with ethylene and the same procedure is adopted as in the previous examples.In the end, 7 g of copolymer is obtained ethylene / hexene (hexene content in the polymer = 16 mole%).

EXAMPLE 32 (comparative) The same procedure is adopted as in the previous example 31, but using as catalyst composition a traditional ionic catalyst prepared by the reaction of 1.5 x 10"3 mmole of Et (THInd) 2ZrMe2 with 1.5 x 10" 3 mmole of Cph3B (C6F5) 4 in toluene (molar ratio of Zr / B = 1). At the end of the polymerization, 8.5 g of ethylene / hexene copolymer are obtained (content of hexene in the polymer = 17 mole%).

EXAMPLE 33 The following products are charged in order, in a glass vial of 25 ml, equipped with a magnetic stirrer: 6.7 ml of toluene, 0.03 mmoles of (pentamethylcyclopentadienyl) titanium trichloride (Cp * TiCl3), 3 ml of TIBAL and 0.03 mmoles of 1, 2, 3, 4, 5, 6, 7, 8 -oc taf luo ro- 9 - (pentafluorophenyl) fluorene (molar ratio of Ti / Al / (component A) = 1: 1: 1). The mixture is heated at 65 ° C for 15 minutes, and 6.9 ml (60 mmol) of styrene, previously purified by distillation under reduced pressure in NaH, is subsequently added (molar ratio of styrene / Ti = 2000). After 60 minutes, the polymerization is stopped by the addition of 30 ml of methanol acidified with 10% HCl. The polymer is recovered by filtration and dried under vacuum at 80 ° C for about 48 hours. 3.5 g of polystyrene are obtained.

EXAMPLE 34 (high temperature polymerization) A polymerization test is carried out in a 1 liter adiabatic steel reactor, capable of operating up to 100 MPa and at temperatures ranging from 160 to 220 ° C. Two streams are fed into the reactor, which contains the monomers and the catalyst solution, respectively, at flow rates that are kept at a value such that they allow a residence time of about 45 seconds. The conversion per passage, and consequently the temperature, is controlled and regulated by means of the flow rate of the catalyst solution, in order to maintain a production of the polymer within the range of 3-4 kg / h. The catalyst solution is prepared by dissolving 550 mg (1.14 mmol) of the o-benzylidene-bis- (5-indenyl) zirconium dichloride complex, prepared according to Example 1 of the patent application number MI98-A00479, in 211 ml of toluene and by adding 552.2 mg (1.16 mmoles) of 1, 2,3,4,5,6,7,8-octafluoro-9- (pentafluorophenyl) fluorene (molar ratio of (component A) / Zr = approximately 1) and 116 mmoles equal to 29 ml of TIBAL (which also comprises the amount of TIBAL necessary as a remover). This solution is kept under stirring at room temperature, for about 30 minutes and then diluted by adding 1800 ml of Isopar-L before introduction into the reactor. The concentration of Zr in the feed solution is 0.57 mM. The stream containing the monomers consists of 64% ethylene in volume 1-butene 46%. The polymerization temperature is kept constant at about 160 ° C and the pressure is set at 80 MPa. Under these conditions, an ethylene-butene copolymer (LLDPE) having the following characteristics is obtained: Mn = 38000, Mw = 102000, MWD = 2.6 MFI = 0.5 g / 10 min, density = 0.9280 g / cm3 Short chain branches = 8.3 / (1000 C) Melting point = 118.4 ° C The catalytic activity proves to be 9200 kg / g of Zr.

Claims (28)

KE5IVINDICATIONS

1. An organometallic composition, suitable as an activator of a metallocene complex of a group 4 metal to form a (co) polymerization catalyst of α-olefins, characterized in that it comprises the reaction product between: (A) a fluorinated organic compound, comprising at least one diunsaturated cycle with 5 or 6 carbon atoms, having the following formula (I): wherein: each Rx group (i is an integer from 1 to 7) is a substituent of the diunsaturated cycle which is independently selected from hydrogen, fluorine and an aliphatic or aromatic hydrocarbyl group, fluorinated or non-fluorinated, having from 1 to 20 carbon atoms, optionally linked to a different hydrocarbyl group R 'to form an additional cycle, with the proviso that at least 2, and preferably 3 of the groups R1 R2, R3, R4 or R5 are independently selected from the group which consists of: fluorine, or a fluorinated alkyl group having the formula -CF (R9R10), in which each group R9 or R10 can have any of the above meanings of the R groups and at least one of them is fluorine, or fluorinated alkyl at least in the 1-position, or a fluorinated aryl ArF as defined in the following, or a fluorinated vinyl group VF, as defined in the following, or a fluorinated aryl group ArF substituted in the aromatic ring with at least two groups that are fluorine, a group -CF (R9R10) as defined above or a different ArF group, or a fluorinated vinyl group substituted in at least two positions of the double bond of groups selected from fluorine, a group - CF (R9R10) or an ArF group, as defined above; the group R8 is hydrogen, -OH, -SH or, together with the group R5, forms a carbonyl oxygen; and "m" can have the values of 0 or 1; (B) an organometallic compound having the following formula (II): M 'RnX (p-n) (II) wherein: M 'is a metal of group 2 or 13 of the periodic table of the elements; each R is independently a hydrocarbyl group, having from 1 to 10 carbon atoms; each X is a halogen atom; "p" is the valence of M 'and is equal to 2 for group 2 and 3 for group 13, "n" is a decimal number that varies from 1 to p.

2. The organometallic composition, as described in claim 1, wherein M 'in the formula (II) is Mg or Al and X is chlorine or bromine.

3. The organometallic composition, as described in any of claims 1 or 2, wherein, in the formula (II), M 'is Al, "p" = "n" = 3 and R is alkyl.

4. The organometallic composition, as described in any of the previous claims, wherein "m" in the formula (I) is equal to zero.

5. The organometallic composition, as described in any of the previous claims, wherein R5 in the formula (I) is selected from fluorine or fluorinated aryl.

6. The organometallic composition, as described in any of the previous claims, wherein R8 in the formula (I) is hydrogen.

7. The organometallic composition, as described in any of the previous claims from 1 to 5, wherein R3 in the formula (I) is from the -OH hydroxy group.

8. The organometallic composition, as described in any of the previous claims, wherein the fluorinated diunsaturated compound has the following formula (IV): wherein: - R5 and R8 have the same meaning defined for formula (I); - "y" and "z" independently have integer values ranging from 1 to 4, including the ends - the groups Rn and R12 are independently substituents of hydrogen atoms of the respective aromatic ring in one or more of the four positions available in each one, and are selected from fluorine or a fluorinated or non-fluorinated aliphatic or aromatic hydrocarbyl group, having 1 to 20 carbon atoms, optionally linked to a different hydrocarbyl group R11 or R12, respectively, to form another cycle, with the proviso that at least 3, preferably at least 4 of the groups R5, R1X and R12 are independently selected from the group consisting of: - fluorine, or - a fluorinated alkyl group having the formula -CF (R9R10), wherein each group R9 or R10 can having any of the above meanings of the Rx groups and at least one of these is fluorine, or fluorinated alkyl, at least in the 1-position, or a fluorinated aryl ArF as defined in the following, or a fluorinated vinyl group VF as defined in the following, or - a fluorinated aryl ArF substituted on the aromatic ring with at least two groups selected from fluorine, a group -CF (R9R10) as defined above or a different ArF group, or - a VF fluorinated vinyl group substituted in at least two positions of the double bond with groups that are selected from fluorine, a -CF (R9R10) group or an ArF group as defined above.

9. The composition as described in claim 8, wherein, in the formula (IV), all of the 8 Ru and R12 are equal to each other and are trifluoromethyl or, preferably, fluorine.

10. The composition as described in any of the previous claims, wherein the components (A) and (B) are in an amount such that the ratio between M 'in the organometallic compound having the formula (II) and the compound cyclic diunsaturated having the formula (I) or (IV) varies from Q1 to 100, preferably from 1 to 10.

11. An active catalyst composition in the (co) polymerization of α-olefins comprising the following components in contact with each other: the organometallic composition according to any of the previous claims from 1 to 10, - a metallocene complex of a metal M of group 4 of the periodic table, comprising at least one cyclopentadienyl group, optionally substituted, penta-apt (? 5-) coordinated with the metal.

12. The catalyst composition as described in claim 11, wherein the components (i) and (ii) are in an amount such that the molar ratio (A) / (M), wherein (M) are the moles of metal in component (ii) and (A) the moles of diunsaturated compound in the organometallic composition (i), ranges from 0.5 to 50, preferably from 1 to 10.

13. The catalyst composition as described in any of the previous claims 11 or 12, wherein the metallocene complex (ii) has the following formula (III): A \ M - (RA) / w (III) R B wherein: - M represents a metal that is selected from Ti, Zr or Hf; - each RA independently represents a group of an anionic nature bound to the metal M, different from cyclopentadienyl or substituted cyclopentadienyl; - "w" is an index which can have integer values of 1 or 2, depending on whether the valence of M is 3 or 4; - A represents an anionic ligand having from 5 to 30 carbon atoms, RB, regardless of the nature of the other substituents, can have any of the meanings specified previously for ligand A and for group RA, and can also be connected with group A by means of a divalent organic group having from 1 to 15 carbon atoms, to form what is termed a metallocene complex "which forms a bridge".

14. The catalyst composition as described in any of the previous claims, from 1 to 13, wherein, in the metallocene complex having the formula (III), the RA and RB groups are independently selected from hydride, chloride, bromide, a hydrocarbyl or halogenated hydrocarbyl radical, other than cyclopentadienyl, having from 1 to 30, preferably from 1 to 10 carbon atoms, a phosphonate, sulfonate or carbonate group, an alkoxy, carboxy or aryloxy group having from 1 to 20, preferably from 1 to 10 carbon atoms, an amide group, an organic group having from 1 to 20, preferably from 1 to 10 carbon atoms, attached to the metal M with an amide nitrogen atom, an organic group having 1 to 10 carbon atoms; to 20, preferably 1 to 10 carbon atoms, attached to the metal M with a silicon atom.

15. The catalyst composition as described in any of the previous claims, from 11 to 13, wherein the metallocene complex having the formula (III) is a bis-cyclopentadienyl complex having the following formula (V): wherein: - M represents a metal that is selected from titanium, zirconium or hafnium; - each A 'or A "independently represents an organic group containing a 5-cyclopentadienyl ring of an anionic nature, coordinated with the metal M; - each R' or R" independently represents a group of an anionic nature with a binding s to the metal M, which is selected from hydride, chloride, bromide, a C1-C20 alkyl group or an alkylaryl group, a C3-C20 alkylsilyl group, a C5-C20 cycloalkyl group, a C6-C20 aryl group or arylalkyl, a C1-C20 alkoxy or thioalkoxy group, a C-C20 carboxylate or carbamate group, a C2-C20 dialkylamide group and a C4-C20 alkylsilylamide group.

16. The catalyst composition as described in any of the previous claims, wherein, in the metallocene complex having the formula (V), the groups A 'and A "are cyclopentadienyl, indenyl or fluorenyl, and their homologous products , wherein one or more carbon atoms of the molecular backbone are substituted with an alkyl, aryl or straight or branched alkylsilyl radical having from 1 to 10 carbon atoms, preferably methyl.

17. A method for the preparation of a catalyst composition as described in any one of claims 1 to 16, comprising placing the components (i) and (ii) as previously defined in claim 11, in contact with each other, so that the ratio of (A) / (M) where (M) are the moles of the metallocene complex having the formula (III) and (A) in the moles of the fluorinated compound having the formula (I), it varies from 0.5 to 50, preferably from 1 to 10.

18. The method as described in claim 17, wherein the components (i) and (ii) are placed in contact and reacted with each other in an inert diluent and at temperatures ranging from room temperature to 150 ° C during Times that vary from 1 to 30 minutes.

19. The method as described in any of the previous claims 17 or 18, wherein the metallocene complex in component (ii) consists of a complex having the formula (III) in which RA and RB are both different from alkyl , or a complex having the formula (V), wherein R 'and R "are both different from alkyl, which comprises the step of reacting the metallocene complex with an amount of organometallic compound having the formula (II) enough to carry out the alkylation of the metallocene complex.

20. The method as described in the claim 19, wherein the metal M 'in the compound having the formula (II) is Mg or, preferably, Al, and the atomic ratio of M' / M varies from 3 to 10.

21. A process for the (co) polymerization of one or more α-olefins, either continuously or in batches, in one or more stages, the appropriate reactors, at a low pressure (0.1-1.0 MPa), medium (1.0-10 MPa) or high (10-150 MPa), at temperatures ranging from 20 to 240 ° C, optionally in the presence of an inert diluent, characterized in that one or more α-olefins are (co) polymerized, under one of the above conditions , in the presence of a catalytic composition according to any of the previous claims from 11 to 16.

22. The process as described in the claim 21, wherein the ethylene is copolymerized with at least one α-olefin having from 3 to 10 carbon atoms.

23. The process as described in claim 22, wherein, in addition to at least one α-olefin, an aliphatic or alicyclic non-conjugated diene having from 5 to 20 carbon atoms, is copolymerized with ethylene.

24. The process as described in any of the previous claims from 21 to 23, wherein it is carried out in a suspension solution in a suitable inert liquid medium consisting of an aliphatic or cycloaliphatic hydrocarbon having from 3 to 15 carbon atoms, or a mixture of these.

25. The process as described in any of the previous claims from 21 to 24, wherein the catalyst composition is prepared by placing separately and subsequently in contact with one or more α-olefins.

26. The process as described in any of the previous claims from 21 to 24, wherein the catalytic composition is prepared by placing the fluorinated organic compound having the formula (I), the organometallic compound having the formula (II) and the metallocene complex having the formula (III) in contact with each other, in suitable proportions, directly in the polymerization environment.

27. A fluorinated organic compound, having the following formula (IV): wherein: - R5 and R8 have the same meaning defined for formula (I); - ?? and "y" z "independently have integer values ranging from 1 to 4, including the extremes, the Ru and R 12 groups are independently substituents of hydrogen atoms of the respective aromatic ring in one or more of the four available positions, and each, and are selected from fluorine or a fluorinated or non-fluorinated hydrocarbyl group, aliphatic or aromatic, having 1 to 20 carbon atoms, linked to a different hydrocarbyl group Rn or R12, respectively, to form another cycle, with the condition that at least 3, preferably 4 of the groups R5, Rn and Ri2 are independently selected from the group consisting of: - fluorine or - a fluorinated alkyl group having the formula -CF (R9R10), in each group R9 or R10 may have any of the above meanings of the RL groups and at least one of these is fluorine, or fluorinated alkyl at least at the 1-position, or fluorinated aryl ArF as defined below, or a vinyl group fluorine VF as defined in the following, or - a fluorinated aryl ArF substituted on the aromatic ring with at least two groups selected from fluorine, a group -CF (R9R10) as defined above or a different ArF group, or - a VF fluorinated vinyl group substituted on at least two positions of the double bond with groups selected from fluorine, a group -CF (R9R10) or an ArF group as defined above; and, in addition, R3 is different from H and, if R3 is H, R5 is different from pentafluorophenyl.

28. The composition as described in claim 27, in which, in formula (IV), all of the eight Rn and R12 are equal to each other and are trifluoromethyl or, preferably, fluorine.