ES2371492T3 - METALOCENE COMPOUNDS. - Google Patents

Abstract

- Metallocene compound, bridged, of the formula (I) wherein, M, is an atom of a transition metal, selected from those belonging to group 3, 4 or to the lanthanide or actinide groups, of The periodic table; X, the same or different from each other, is a hydrogen atom, a halogen atom, a group R, OR, OSO2DF3, OCOR, SR, NR2, or PR2, where, R, is an alkyl radical C1-C40, C2-C40 alkenyl, C2-C40 alkynyl, C6-C40 aryl, C7-C40 alkylaryl, or C7-C40 arylalkyl, cyclic or acyclic, linear or branched; containing, optionally, heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; or two groups X, can be found together, to form an OR-O group, wherein, R-, is a C1-C20 alkylidene radical, C6-C20 arylidene, C7-C20 alkylarylidene, or C7-C20 arylalkylidene; L, is a divalent bridge group, selected from among the radicals C1-C20 alkylidene, C3-C20 cycloalkylidene, C6-C20 arylidene, C7-C20 alkylarylidene, or C7-C20 arylalkylidene, which optionally contains heteroatoms which belong to groups 13-17 of the Periodic Table of the Elements, or is a silidene radical, containing up to 5 silicon atoms; R 1, the same or different from each other, are a C1-C40 hydrocarbon radical, which optionally contains heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; R 2, the same or different from each other, are a group C (R 19) 2R 18; wherein, R 18 and R 19, the same or different from each other, are C1-C20 alkyl radicals; R 3, the same or different from each other, are hydrogen atoms, or C1-C40 hydrocarbon radicals, which belong to groups 13-17 of the Periodic Table of the Elements; W 1 and W 2, the same or different from each other, are aromatic rings of 5 or 6 members, which may contain heteroatoms belonging to groups 15-16 of the Periodic Table of the Elements; the valence of each atom of said ring is substituted with hydrogen, or it can be substituted, optionally, with R 5 groups, where R 5, equal or different from each other, are hydrocarbon radicals C1-C40, which optionally contain heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements.

Description

Metallocene compounds

The present invention relates to a new class of metallocene compounds that have a particular substitution pattern, suitable for polymerizing alpha olefins, at high productive yields, to provide a polymer having a high molecular weight. The present invention further relates to its catalyst system and the polymerization process therefrom.

10 Metallocene compounds are well known in the art of the art as catalyst components for the polymerization of olefins. International Patent Publication Document WO 04/106 351, refers to a class of bis-indolinmethalocene compounds, substituted in positions 2, 4 and 6. The compounds that are disclosed, have an IC symmetry, that is to say The two indenyls are substituted in a different way, in a particular way, the substituents in the 2-position of the indenyl ring are different. This

15 implies the fact that the synthesis of these compounds is quite complicated, due to the fact that two different indenyl halves must be prepared. US Patent 5,840,948, refers to some indenyl-based metallocene compounds, which contain a 2-methyl-4,6-diisopropyl portion and a 2,4,6-trimethylindenyl portion. European patent document EP 776 913, and Organometallics, volume 25, No. 5, 2006, refer to metallocene compounds, where, position 6 of the indenyl ring, is substituted

20 with an isopropyl radical and, position 4, is substituted with a phenyl radical. European patent document EP 576 970, refers to bis-indenyl metallocene compounds, generally substituted. However, the particular substitution pattern is not suggested for the compounds of the present invention.

Thus, in this way, there is still a need for the fact of finding a new class of compounds

25 of metallocene, suitable for polymerizing olefins in high degrees of productive yields, and for producing polymers having a very high molecular weight, especially when the process is carried out high temperature.

An object of the present invention is a bridged metallocene compound of the formula (I)

where,

M, is an atom of a transition metal, selected from those belonging to group 3, 4 or groups

35 of the lanthanides or actinides, from the Periodic Table of the Elements; preferably, M, is zirconium, titanium or hafnium; X, the same or different from each other, is a hydrogen atom, a halogen atom, a group R, OR, OSO2DF3, OCOR, SR, NR2, or PR2, where, R, is an alkyl radical C1-C40, C2-C40 alkenyl, C2-C40 alkynyl, C6-C40 aryl, C7-C40 alkylaryl, or C7-C40 arylalkyl, cyclic or acyclic, linear or branched; containing, optionally, heteroatoms belonging to groups 13-17 of the Periodic Table of the

40 items; or two groups X, can be found together, to form an OR'O group, where, R ', is a C1-C20 alkylidene radical, C6-C20 arylidene, C7-C20 alkylarylidene, or C7-C20 arylalkylidene, of a preferable form, X, is a hydrogen atom, or a halogen atoms, or an R group; more preferably, X, is chlorine or a methyl radical. L, is a divalent bridge group, selected from among the radicals C1-C20 alkylidene, C3-C20 cycloalkylidene,

C6-C20 arylidene, C7-C20 alkylarylidene, or C7-C20 arylalkylidene, which optionally contains heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements, or is a silidene radical, containing up to 5 silicon atoms .; preferably, L, is Si (R11) 2, wherein R11 is a C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C6-C40 aryl, C7-C40 alkylaryl, or C7 arylalkyl -C40, cyclic or acyclic, linear or branched; more preferably, L, is Si (CH3) 2 or SiPh2; R1, the same or different from each other, are a C1-C40 hydrocarbon radical, which optionally contains heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements, such with a

Methyl or ethyl radical; preferably, R1 is a linear C1-C20 alkyl radical, such as an ethyl or methyl radical. R2, the same or different from each other, are a group C (R19) 2R18; wherein, R18, is a C1-C20 alkyl radical; more preferably, R18 is a methyl or ethyl radical; R19, is a C1-C20 alkyl radical, linear or branched; more preferably, the two R2 groups are the same; R3, the same or different from each other, are hydrogen atoms, or C1-C40 hydrocarbon radicals,

10 belonging to groups 13-17 of the Periodic Table of the Elements; preferably, R3 is a hydrogen atom or C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C6-C40 aryl, C7-C40 alkylaryl, or C7-C40, cyclic or acyclic, linear alkyl or branched, belonging to groups 13-17 of the Periodic Table of the Elements; more preferably, R3, the same or different from each other, are hydrogen atoms or C1-C40 alkyl radicals, and even more preferably, R3, are atoms of

15 hydrogen W1 and W2, the same or different from each other, are aromatic rings of 5 or 6 members, which may contain heteroatoms belonging to groups 15-16 of the Periodic Table of the Elements; the valence of each atom of said ring is substituted with hydrogen, or it can be substituted, optionally, with R5 groups, where R5, equal or different from each other, are radical

C1-C40 hydrocarbon, optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; preferably, R5 are C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C6-C40 aryl, C7-C40 alkylaryl, or C7-C40 arylalkyl, cyclic or acyclic, linear or branched, containing , optionally, heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; Preferably, W1 and W2 are selected from the group comprising the following portions of the

25 formula (Wa), (Wb) and (Wc):

wherein, *, represent the point at which the portion is attached to the indenyl portion of the compound of the formula (I);

R6, R7, R8, R9 and R10, the same or different from each other, are hydrogen atoms or C1-C40 hydrocarbon radicals, which optionally contain heteroatoms belonging to groups 13-17 of The periodic table; R6, R7, R8, R9 and R10 are preferably hydrogen atoms or C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C6-C40 aryl, C7-C40 alkylaryl, or C7- arylalkyl C40, cyclic or acyclic, linear or branched, containing, optionally, heteroatoms belonging to groups 13-17

35 of the Periodic Table of the Elements; Z1, is a nitrogen atom, or a CR10 group; Z2, is a nitrogen atom, or a CR6 group; Z3, is a nitrogen atom, or a CR7 group; Z4, is a nitrogen atom or a CR8 group; Z5, is a nitrogen atom, or a CR9 group; with the proviso that, not more than two groups, from among the Z1, Z2, Z3, Z4 and Z5, are nitrogen atoms, preferably, not more than one group, from among the Z1, Z2, Z3 , Z4 and Z5, be a nitrogen atom;

40 Z6, is an oxygen atom, a sulfur atom, an NR13 group, or a CR13 group; Z7, is an oxygen atom, a sulfur atom, an NR14 group, or a CR14 group; Z8, is an oxygen atom, a sulfur atom, an NR15 group or a CR15 group; Z9, is an oxygen atom, a sulfur atom, an NR16 group or a CR16 group; Z10, is a nitrogen atom or a carbon atom, which bonds the indenyl portion of the structure of the formula (I); with the proviso that, not more than 1 group, among the Z6, Z7, Z8, Z9 and Z10, is a sulfur atom, an atom

Oxygen, or a group containing nitrogen, selected from NR13, NR14, NR15, NR16, and a nitrogen atom; R13, R14, R15 and R16, the same or different from each other, are hydrogen atoms or C1-C40 hydrocarbon radicals, which optionally contain heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; preferably, R13, R14, R15 and R16 are hydrogen atoms or radicals

50 C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C6-C40 aryl, C7-C40 alkylaryl, or C7-C40 arylalkyl, cyclic or acyclic, linear or branched, optionally containing heteroatoms belonging to the groups 13-17 of the Periodic Table of the Elements; more preferably, R13, R14, R15 and R16 are hydrogen atoms, C1-C40 alkyl radicals or C6-C40 aryl; In the portion of the formula (Wa), in a preferred form of presentation, R7, is a C1-C40 alkyl radical, preferably, a branched C1-C40 alkyl radical, more preferably, R7, is a C1-C40 alkyl radical, branched, wherein the carbon atom in the alpha position, is a tertiary carbon atom, such as a tert.-butyl radical, and R6, R8, R9 and R10, are hydrogen atoms;

In an additionally preferred form of presentation, R10 and R8, are C1-C40 alkyl radicals, preferably, these are linear C1-C40 alkyl radicals, such as methyl radicals, and R7, R8 and R9, are hydrogen radicals ;

In an additionally preferred form of presentation, R6, R7 and R8, are C1-C40 alkyl radicals, linear or branched, such as methyl or tert.-butyl radicals, and R10 and R9 are hydrogen atoms;

In an additionally preferred form of presentation, R6, R7, R8, R9 and R9 are hydrogen atoms;

In the portion of the formula (Wb), in a preferred form of presentation, Z1, is a nitrogen atom, and Z2, Z3, Z4 and Z5 are, in a respective way CR6, CR7, CR8, and CR9, in where, the meaning of R6, R7, R8 and R9, is described above, above; in an additionally preferred form of presentation, Z3, is a nitrogen atom, and Z1, Z2, Z4 and Z5 are, respectively, CR10, CR6, CR8 and CR9, wherein, the meaning of R10, R6, R8 and R9, It is described above, above; in an additionally preferred form of presentation, Z2, is an atom of

20 nitrogen, and Z1, Z3, Z4 and Z5 are, respectively, CR10, CR7, CR8 and CR9, wherein, the meaning of R10, R7, R8 and R9, is described above, above;

In the portion of the formula (Wc), in a preferred form of presentation, Z6, is an oxygen atom, a sulfur atom, an NR16 group; preferably, this is a sulfur atom or an NR16 group; where, R16 is, of

A preferable form, a C1-C40 alkyl radical, more preferably, Z6, is a sulfur atom; and Z7, Z8, Z9 and Z10 are, respectively, CR14, CR15, CR16, and a carbon atom, wherein, R14, is a hydrogen atom or a C1-C40 alkyl radical, such as methyl or ethyl; and R15 and R16, are hydrogen atoms, or C1-C40 alkyl radicals.

In a preferred form of presentation of the present invention, in the compounds of the formula (I), T1 and T4,

The same or different from each other, are OR2, or SR2, where R2 is as described above, and T2 and T3, the same or different from each other, they are linear C1-C40 alkyl-alkyl radicals, such as methyl or ethyl radicals.

In a preferred form of presentation, T1 and T4, the same or different from each other, are a group OR2, SR2, or a group C (R18) 3; preferably, T1 and T4, are an OR2 group or an SR2 group; and T2 and T3, the same

or different from each other, are a group C (R19) 2R18, wherein, R18, described above, above, and, R19, is a C1-C40 hydrocarbon radical, optionally containing one or more heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; R19 is preferably a C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C6-C40 aryl, C7-C40 alkylaryl, or C7-C40 arylalkyl, cyclic or acyclic, linear or branched alkyl radical, containing, optionally, heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; or two radicals R19, can be joined together to form a ring provided with C4-C6 members, where, optionally, a carbon atom can be substituted with a nitrogen, sulfur or oxygen atom; more preferably, R19, is a C1-C20 alkyl radical, linear or branched; more preferably, R19, is a methyl or ethyl radical; Examples of groups C (R19) 2R18, are tert.-butyl radicals,

Isopropyl, cyclopentyl, cyclohexyl, 2-furanyl;

A preferred class of compounds of the formula (I), is represented by the formula (IIa) wherein, M, L, X, R1, R2, R3, R6, R7, R8 and R10, have the meanings given above, above. An additionally preferred class of compounds of the formula (I), has the formula (IIb)

where, M, L, X, R1, R2, R3, R14, R15 and R16, have the meanings given above, above.

Examples of compounds having the formula (I) are the following

5 Me2Si (racemic 2-methyl-4-phenyl-6-tert.-butylinden-1-yl) 2ZrCl2 Me2Si (2-methyl-4- (tert.-butylphenyl) -6-tert.-butylinden-1-yl) 2ZrCl2 racemic Racemic Me2Si (2-methyl-4- (thiophen-2-yl) -6-tert.-butylinden-1-yl) 2ZrCl2 Racemic Me2Si (2-methyl-4- (5-methylthiophe-2-yl) -6-tert.-butylinden-1-yl) 2ZrCl2 Racemic Me2Si (2-methyl-4- (benzothiophene-2-yl) -6-tert.-butylinden-1-yl) 2ZrCl2

10 Me2Si (2-methyl-4- (4-pyridyl) -6-tert.-butylinden-1-yl) 2ZrCl2 racemic Me2Si (2-methyl-4- (2,5-dimethylphenyl) -6-tert.-butylinden -1-yl) 2ZrCl2 racemic Me2Si (2-ethyl-4-phenyl-6-tert.-butylinden-1-yl) 2ZrCl2 racemic Me2Si (2-n-propyl-4-phenyl-6-tert.-butylinden-1 -il) racemic 2ZrCl2 anti-Me2Si (2-methyl-4-phenyl-6-tert.-butylinden-1-yl) (2-methyl-4- (5-methylthiophene-2-yl) -6-tert.- racemic butylinden-1-yl) ZrCl2

15 and their corresponding dimethyl derivative and, additionally, in addition, the corresponding titanium and hafnium compounds.

Preferably, the metallocene compounds object of the present invention are in their racemic (rac) or anti-racemic form.

For the purposes of the present invention, the term "racemic form (rac)" means the fact that the same substituents, in the two cyclopentadienyl portions, are on the opposite side, with respect to the plane containing the zirconium , and the center of said cyclopentadienyl portions. "Anti-racemic form" means the fact that the most massive substituents of the cyclopentadienyl portions, in the metallocene compounds, are

25 are located on the opposite side, with respect to the plane containing the zirconium and the center of said cyclopentadienyl portions, as shown in the following compound: A further object of the present invention is a catalyst system for the polymerization of olefins, which can be obtained by contacting:

5 a) a metallocene compound of the formula (I); b) at least one alumoxane or a compound capable of forming an alkylmethalocene cation; Y c) optionally, an organoaluminum compound.

Preferably, the metallocene compounds have the formulas selected from (Ia), (IIa) or (IIb).

The alumoxanes used as compound b), in catalyst system in accordance with the present invention, can be obtained by reacting water with an organo-aluminum compound of the formula HjAlU3-j or HjAl2U6-j, wherein the substituents U , the same or different, are hydrogen atoms, halogen atoms or radicals C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl, or C7-C20 aryl alkyl, which contain,

15 optionally, silicon or germanium atoms, with the proviso that, at least one of the U, is different from halogen and, j, is of a value corresponding to a range of 0 to 1, being , also, a non-integer number. In this reaction, the molar ratio factor of Al / water is, preferably, corresponding to a value within ranges ranging from 1: 1 to 100: 1

The alumoxanes used in the catalyst system in accordance with the present invention are considered to be linear, branched or cyclic compounds, which contain at least one group of the type

OR

I

25 Al - O

where, the substituents U, the same or different, have been defined above, above

30 In a particular way, the alumoxanes of the formula

U U U \ I ⁄ Al - O - (Al - O) n1— Al

35 ⁄ \ U U

40 may be used, in the case of linear compounds, where, n1, is 0 or an integer from 1 to 40, and the substituents U, are defined as defined above, above: or alumoxanes of the formula

OR

I

      (Al - O) n2

5 can be used, in the case of cyclic compounds, where, n2, is an integer from 2 to 40, and the substituents U, are defined in the manner defined above, above.

Examples of suitable alumoxanes for use in accordance with the present invention are those consisting of methylalumoxane (MAO), tetra- (isobutyl) alumoxane (TIBAO), tetra- (2,4,4-trimethyl-pentyl) alumoxane (TIOAO ), tetra- (2,3-dimethylbutyl) alumoxane (TDMBAO) and tetra- (2,3,3-trimethylbutyl) alumoxane (TTMBAO).

Particularly interesting catalysts are those described in international patent documents WO 99/21 899 and WO 01/21 674, in which the alkyl and aryl groups have a standard model

15 specific branches.

Non-limiting examples of aluminum compounds that can be reacted with water, to provide appropriate alumoxanes (b), which are described in the patent documents tris (2,3,3-trimethyl-butyl) aluminum, tris (2,3- dimethyl-hexyl) aluminum, tris (2,3-dimethylbutyl) aluminum, tris (2,3-dimethylpentyl) aluminum, tris (2,3-dimethyl-heptyl) aluminum, tris (2-methyl-3-ethyl-pentyl) aluminum, tris (2-methyl-3-ethyl-hexyl) aluminum, tris (2methyl-3-ethyl-heptyl) aluminum, tris (2-methyl-3-propyl-hexyl) aluminum, tris (2-ethyl-3- methyl butyl) aluminum, tris (2-ethyl-3-methylpentyl) aluminum, tris (2,3-diethyl-pentyl) aluminum, tris (2-propyl-3-methylbutyl) aluminum, tris (2-isopropyl-3- methyl butyl) aluminum, tris (2-isobutyl-3-methylpentyl) aluminum, tris (2,3,3-trimethyl-pentyl) aluminum, tris (2,3,3-trimethyl-hexyl) aluminum, tris (2- ethyl-3,3-dimethyl-butyl) aluminum, tris (2-ethyl-3,3-dimethyl-pentyl) aluminum, tris (2-isopropyl-3,3-dimethyl-butyl) aluminum, tris (2

Trimethylsilylpropyl) aluminum, tris (2-methyl-3-phenyl-butyl) aluminum, tris (2-ethyl-3-phenyl-butyl) aluminum, tris (2,3-dimethyl-3-phenylbutyl) aluminum, tris (2-phenyl -propyl) aluminum, tris [2- (4-fluoro-phenyl) -propyl] aluminum, tris [2- (4-chlorophenyl) -propyl] aluminum, tris [2- (3-isopropyl-phenyl) -propyl] aluminum , tris (2-phenylbutyl) aluminum, tris (3-methyl-2-phenyl-butyl) aluminum, tris (2-phenyl-pentyl) aluminum, tris [2- (pentafluorophenyl) -propyl] aluminum, tris [2,2 -diphenyl-ethyl] aluminum and tris [2-phenyl-2-methylpropyl] aluminum, as well as the corresponding compounds, wherein one of the hydrocarbyl groups is replaced with an isobutyl atom.

Among the aforementioned aluminum compounds, trimethylaluminum (TMA), triisobutylaluminum (TIBA), tris (2,4,4-trimethyl-pentyl) aluminum (TIOA), tris (2,3-dimethylbutyl) are preferred aluminum (TDMBA) and tris (2,3,3-trimethylbutyl) aluminum.

35 Non-limiting examples of the compounds suitable for forming an alkylmethalocene cation are compounds of the formula D + E-, wherein, D +, is n Broensted acid suitable for donating a proton, and for reacting, in an irreversible way , with an X metallocene substituent of the formula (I) and E -, is a compatible anion, which is capable of stabilizing the active catalytic species that originate from the reaction of two compounds, and which is sufficiently labile as to be removed, by an olefinic monomer. Preferably, the anion E - comprises one or more boron atoms. More preferably, the E - anion is an anion of the formula BAr4 (-), wherein the Ar substituents, which may be identical or different, are aryl radicals, such as phenyl, pentafluorophenyl or bis (trifluoromethyl) )phenyl. Tetrakis-pentafluorophenyl is preferred, in a particular way, as described in the publication of the international patent document WO 91/02 012. Additionally, in addition,

45 compounds of the formula BAr3, can be used, in a convenient way. Compounds of this type are described, for example, in the international patent application WO 92/00 333. Other examples of compounds suitable for forming an alkylmethalocene cation are compounds of the formula BAr3P, where P is a pirrolo radical, substituted or unsubstituted. These compounds are described in international patent document WO 01/62 764. Compounds containing boron atoms can be conveniently provided in accordance with the description of German patent applications DE-A-19 962 814 and DE-A-19 962 910. All these compounds containing boron atoms can be used in a molar ratio factor, between boron and metallocene metal, corresponding to a value within a range between approximately 1 : 1 and about 10: 1; preferably, within a range between

1: 1 and 2: 1; more preferably, in a ratio factor corresponding to a value of approximately

55 1: 1.

 Non-limiting examples of the compounds of the formula D + E are the following: Tetrakis (pentafluorophenyl) tributylammonium borate, Tetrakis (pentafluorophenyl) tributylammonium aluminate, Tetrakis (trifluoromethylphenyl) tributylammonium borate, Tetrakis (4-fluorophenyl) tributylammonium borate, Tetrakis (pentafluorophenyl) dimethylbenzylammonium borate, Tetrakis (pentafluorophenyl) dimethylhexylammonium borate, Tetrakis (pentafluorophenyl) N, N-dimethylanilinium borate,

65 Tetrakis (pentafluorophenyl) N, N-dimethylanilinium aluminate, Tetrakis (pentafluorophenyl) dimethylbenzylammonium borate, 8

Tetrakis (pentafluorophenyl) dimethylhexylammonium borate, Tetrakis (pentafluorophenyl) di (propyl) ammonium borate, Tetrakis (pentafluorophenyl) di (cyclohexyl) ammonium borate, Tetrakis (pentafluorophenyl) triphenylcarbenium borate,

5 Tetrakis (pentafluorophenyl) triphenylcarbenium aluminate, Tetrakis (pentafluorophenyl) ferrocene borate, Tetrakis (pentafluorophenyl) ferrocene aluminate.

The organic compounds used as compound c) are those of the formula HjAlU3-j or HjAl2U6-j in the manner described above, above.

The catalysts of the present invention can also be supported as an inert support. This is achieved by depositing the metallocene compound a) or the product of its reaction with component b),

or component b) and then the metallocene compound a), on an inert support. The support can be

A porous solid, such as talc, laminar silicate, an inorganic oxide, or a powder polymer, finally divided (such as, for example, polyolefin). Appropriate inorganic oxides can be found among the oxides of the elements of groups 2, 3, 4, 5, 13, 14, 15 and 16 of the Periodic Table of the Elements. Examples of preferred oxides, as supports, include silicon dioxide, aluminum oxide, and also, mixed oxides of the elements consisting of calcium, aluminum, silicon, magnesium or titanium, and aluminum, and also, the

20 corresponding mixtures of oxides, magnesium halides, styrene / divinylbenzene copolymers, polyethylene or polypropylene. Other inorganic oxides that can be used alone or in combination with the preferred oxide supports mentioned above are, for example, MgO, ZrO2, TiO2 or B2O3.

An appropriate class of supports that can be used is that consisting of porous organic supports,

25 functioning with groups that have active hydrogen atoms. Particularly suitable are those, in which, the organic support, is a partially crosslinked styrene polymer. Supports of this type are described in European patent application EP-633 272.

Another class of inert supports particularly suitable for use in accordance with the present invention is that consisting of porous polyolefin prepolymers, in a particular form, polyethylene.

Another class of inert supports particularly suitable for use in accordance with the present invention are those consisting of porous magnesium halides, such as those described in international patent application WO 95/32 995.

35 The support materials used preferably have a specific surface area corresponding to a value ranging from 10 to 1,000 m2 / g, a pore volume, corresponding to a value within margins ranging from 0.1 to 5 ml / g, and an average particle size, corresponding to a value within margins ranging from 1

40 to 500 μm. A preference is given, to the supports that have a specific surface area, corresponding to a value comprised within ranges ranging from 50, up to 500 m2 / g, a pore volume, corresponding to a value comprised within ranges that They range from 0.5 to 3.5 ml / g, and an average particle size, corresponding to a value within ranges ranging from 5 to 350 μm. A particular preference is given to supports that have a specific surface area, corresponding to

45 a value within margins ranging from 200, to 400 m2 / g, a pore volume, corresponding to a value within margins ranging from 0.8 to 3.0 ml / g, and a size particle medium, corresponding to a value within ranges ranging from 10 to 300 μm.

50 The inorganic support can be subjected to a heat treatment, for example, to remove the absorbed water. Such type of treatment is carried out, in a general way, at a temperature corresponding to a value comprised within ranges ranging from 80 to 300 ° C, preferably from 100 to 200 ° C, being carried out , drying a temperature within a range from 100 to 200 ° C, preferably, by the action of reduced pressure and / or a blanket of inert gas

55 (such as nitrogen), or the inorganic support, can be calcined at a temperature within ranges from 200 to 1,000 ° C, to produce the desired solid structure / or deposit the desired OH concentration , Over the surface. The support can also be chemically treated, using custom desiccants, such as those consisting of metal alkyls, preferably, aluminum alkyls, chlorosilanes or SiCl 4, or also, methylaluminoxane. Appropriate treatment procedures are

60 described, for example, in WO 00/31 090.

The inorganic support material can also be chemically modified. Thus, for example, a treatment of silica gel with (NH4) 2SiF6, leads to the fluorination of the surface of the silica gel, or treatments with silica gels with silanes containing groups containing nitrogen, fluorine, or sulfur, lead to silica gel surfaces

65 correspondingly modified.

Organic support materials, such as finely divided polyolefins powder (such as, for example, polyethylene, polypropylene or polystyrene), can also be used and, preferably, they are released in the same way, from adhered moisture, solvent residues or other impurities, by means of appropriate purification and drying operations, before use. It is also possible to proceed to use media

5 functionalized polymers, such as polystyrene-based supports, by means of whose functional groups, such as, for example, ammonium groups or hydroxy groups, at least one of the catalyst components can be immobilized. The solid compound obtained by the support of the catalyst system object of the present invention, on a support, in combination with the additional addition of alkylaluminum compound, either purified, or previously reacted with water, if necessary , can be used in a successful way, in the gas or suspension phase polymerization.

The catalyst system of the present invention can be used in a suspension polymerization process.

For the purposes of the present invention, the term solution polymerization means, in a preferable way, the fact that the polymer is completely soluble in the polymerization medium, at the polymerization temperature used, and in the range of concentration, corresponding to a percentage of at least 5%, by weight; more preferably, in a concentration range within ranges ranging from 5% to 50%, by weight.

In order to have the polymer completely soluble in the polymerization medium, a mixture of monomers for copolymers, or only a monomer for homopolymers, can be used in the presence of an inert solvent. This solvent may be an aliphatic or cycloaliphatic hydrocarbon, such as hexane, heptane, isooctane, cyclohexane and methylcyclohexane. It is also possible to proceed to use a mineral alcohol, or a fraction of

25 diesel diesel, hydrogenated. Also, aromatic hydrocarbons, such as toluene, can also be used. Preferred solvents for use are cyclohexane and methylcyclohexane. In the case where propylene is used as a monomer, to obtain propylene copolymers in solution polymerization processes, the content of propylene, in the liquid phase of the polymerization medium is, preferably, corresponding to a value within ranges ranging from 5% to 60%, by weight; preferably, within ranges ranging from 20% to 50%, by weight.

The catalyst system comprising the metallocene compound of the formula (I), can be used for the preparation of polyolefins, in a particular way, for the preparation of alpha-olefins, in high productive yields, to provide polymers having a high molecular weight. Thus, therefore, an additional objective

35 of the present invention, is a process for preparing an alpha-olefin polymer, comprising contacting, under polymerization conditions, one or more alpha-olefins of the formula CH2-CHA, wherein, A, is hydrogen or a C1-C20 alkyl radical, in the presence of a catalyst system, as described above, above.

Non-limiting examples of alpha-olefins of the formula CH2 = CHA are the following: ethylene, propylene, 1-butene, 1hexene, 1-octene and 4-methyl-1-pentene, and the preferred alpha-olefins, are ethylene, propylene and 1-butene.

The metallocene compounds of the formula (I) object of the present invention are particularly suitable

45 for homo- and copolymerization of propylene. In fact, the metallocene-based catalyst system of the present invention, when used for homo- or copolymerization of propylene, is suitable for providing polymers having a high molecular weight, at high productive yields, also, at high temperatures. , thereby making it possible to use them in industrial plants that use polymerization temperatures greater than 50 ° C, and which can be found within a range between 60 ° C and 200 ° C, preferably , within a range between 80 ° C and 120 ° C.

As mentioned above, above, the metallocene compounds of formula II), are suitable, in a particular way, for the copolymerization of propylene, and thus, therefore, a further object of the present invention, it is a process for the preparation of propylene copolymers, which comprises

The step of bringing into contact, under polymerization conditions, propylene, with ethylene or one or more alpha olefins of the formula CH2 = CHA1, wherein, A1, is a C2-C20 alkyl radical, in the presence of a catalyst system described above, above. This procedure is preferably carried out, in solution, in the manner described above, above.

Examples of alpha-olefins of the formula CH2 = CHA1 are ethylene, 1-butene, 1-hexene, 1-octene and 4-methyl-1pentene and, preferably, the alpha-olefins are ethylene and 1- butene; alpha-olefin being mostly preferred, ethylene.

The content of alpha-olefin units, in the propylene copolymer object of the present invention, is the

65 corresponding to a percentage within ranges ranging from 0.1% to 90%, per mole; preferably, this is the one corresponding to a percentage comprised within ranges ranging from 5%, per mole, to 70%, per mole; in a mostly preferable way, this is the one corresponding to a percentage within ranges ranging from 10%, per mole, to 60%, per mole.

The metallocene compounds of the present invention are also particularly suitable for the

Preparation of copolymers of ethylene and higher alpha-olefins, such as propylene, 1-butene, 1-hexene, 1-octene. The copolymers have a comonomer content, corresponding to a percentage within ranges ranging from 5%, per mole, to 50%, per mole. Particularly preferred are ethylene / 1-butene copolymers, which have a content of units derived from 1-butene, corresponding to a percentage within ranges ranging from 5%, per mole, to 50%, per mol.

As explained above, the process for the polymerization of olefins in accordance with the present invention can be carried out in the liquid phase, in the presence or absence of an inert hydrocarbon solvent, such as in a suspension, or in the gas phase. The hydrocarbon solvent may be either aromatic, such as toluene, or aliphatic, such as hexane, heptane, isobutane or

15 cyclohexane

As a general rule, the polymerization temperature is generally within a range between -100 ° C and +200 ° C, this being, preferably, corresponding to a value within a range between 60 ° C and 200 ° C, and more preferably, the

20 corresponding to a value within a range between 80 ° C and 120 ° C. The polymerization pressure is, in a general way, within a range between 0.5 and 100 bar.

The lower the polymerization temperature, the higher the molecular weights resulting from the 25 polymers obtained.

The productive yields of the polymerization depend on the purity of the metallocene compound of the catalyst. The metallocene compounds obtained by the process of the invention can therefore be used as such, or they can be subjected to purification treatments.

A further objective of the present invention is a ligand of the formula (III)

or its double bond isomers 35 where, L, R1, R2, R3, W1 and W2, have the meanings reported above, above.

Preferred ligands have the formulas (IIIa) or (IIIb):

or its double bond isomers where, L; R1 - R16, have the meanings reported above, above.

The metallocene compounds of the formula (I) can be obtained by a process comprising the

5 steps of reacting the di-anion, with an appropriate transition metal, such as a metal tetrahalide, such as, for example, zirconium tetrachloride. The di-anion can be obtained, for example, by deprotonation of the ligand of the formula (III), for example, by using an organolithium compound, such as butyl or methyl lithium. The above-mentioned procedures, above, are carried out, preferably, in an aprotic solvent, either polar or non-polar. Said aprotic solvent

10 is, preferably, an aromatic hydrocarbon or an aromatic hydrocarbon, optionally halogenated, or an ether; more preferably, it is selected from benzene, toluene, pentane, hexane, heptane, cyclohexane, dichloromethane, diethyl ether, tetrahydrofuran, or mixtures thereof. The above-mentioned procedure is carried out at a temperature corresponding to a value within a range from -100 ° C to + 80 ° C, preferably at a

15 temperature corresponding to a value within a range from 20 ° C to + 70 ° C.

The examples given below are provided to illustrate the invention, but not intended to limit it.

20 Examples

The examples given below are provided to illustrate the invention, and not to limit it.

General characterization

25 Intrinsic viscosity (I.V.) in tetrahydronaphthalene

Intrinsic viscosity (I.V.), was measured in tetrahydronaphthalene (THN), at a temperature of 135 ° C.

30 Melting temperature (Tm)

The calorimetric measurements were made using a DSC differential scanning calorimeter of the Mettler brand. The instrument is calibrated with indium and tin patterns. The sample, heavy (6-8 mg), was sealed in aluminum trays, heated at a temperature of 200 ° C, at a rate of 20 ° C / minute, and kept at

35 this temperature, over a period of 5 minutes. Subsequently, after proceeding to cool to a temperature of 5 ° C, and to maintain for a period of 5 minutes, at this temperature of 5 ° C, the sample was heated, at a temperature of 200 ° C, at a rate of 20 ° C / minute. In this second heating pass, the peak temperature was assumed to be the melting temperature (Tm), and the area, as the global enthalpy of fusion (L H).

40 Gel Permeation Chromatography (CPC)

Gel permeation chromatography was carried out at a temperature of 135 ° C, in 1,2,4-trichlorobenzene, using a gel permeation chromatography apparatus, of the type "Waters 150C GPC apparatus"

45 Measurement using 13C-NMR

The microstructure of the polymer was investigated, by an analysis of 13C-NMR. The samples were dissolved with a concentration of 8%, weight / volume, in 1,1,2,2-tetrachloroethane-d2, at a temperature of 120 ° C. The

50 13C-NMR spectra were obtained at a temperature of 120 ° C, on a Bruker DPX400 type spectrometer, operating at 100.61 MHz. Each spectrum was obtained with a 90 ° C pulse, 12 seconds between pulses , and CPD (WALTZ 16), to eliminate the coupling of 1H-13C. Approximately 1500 transient data were stored, at 32 K data points, using a 6000 Hz spectral window.

55 In the case of isotactic polypropylene, the mmmm peak, at 12.8 ppm, is the one used as an internal reference, and the distribution of the pentadas, and the amounts of the regioerrors, were determined as described by Resconi , L .; Cavallo, L .; Fait, A .; Piemontesi, F. Chem. Rev. 2000, 100, 1253.

In the case of ethylene-propylene copolymers, the assignments of the peaks were made in accordance with Randall 60

[one]

 and Tritto [2], and the distribution of triads and polymer compositions, was determined in accordance with Kakugo. [3].

[one]

 J. C. Randall, Macromol. Chem Fys. 1989, C29, 201.

The SMM peak, at 29.9 ppm (nomenclature in accordance with reference 4), was used as internal reference. The product of the reactivity factors r1 x r2, was calculated from the triads, in accordance with Carman. [4].

[2] I. Tritto, Z. Fan, P. Locatelli, M. Sacchi, I. Carmurati, M. Galimberti, Macromolecules 1995, 28, 3342.

[3] M. Kakugo, Y. Naito, K. Mizunuma, T. Miyatake, Macromolecules 1982, 15, 1150.

[4] C. J. Cannan, R. A. Harrington, C. E. Wilkes, Macromolecules 1977, 10, 535.

5 Chemical compounds and characterization

All chemical compounds were manipulated using standard Schlenk techniques.

10 Methylalumoxane (MAO) was received from Albemarle, as a 30% weight / weight toluene solution, and was used as is.

Racemic dimethylsilylbis (2-methyl-4-phenyl-inden-1-yl) dichlorocirconium (C1) was prepared in accordance with the teachings of European patent EP 576970;

The racemic dimethylsilylbis (2-methyl-4- (4-tert.-butylphenyl) -inden-1-yl) dichlorocirconium (C2) was prepared in accordance with the teachings of international patent document WO 98/40 331 (example 65).

Synthesis of rac-dimethylsilyl (2-methyl-4 (4-tert.-butylphenyl) -6-tert.-butylinden-1-yl) dichlorocirconium (A1) 20

3- (2-Bromo-4-tert.-butylphenyl) -2-methylpropanoic acid

N-Bromosuccinimide (98 g, 0.55 mol) and 0.5 g of benzoyl peroxide were added to a solution of 2-bromo-4-tert.-butyl-1-methylbenzene (113.5 g, 0 , 5 mol) in CCl4 (500 ml). The resulting mixture was refluxed, over a period of 6 hours, cooled to a temperature of 20 ° C and filtered. The resulting filtrate was evaporated and this was used without further purification. A solution of sodium diethylmethylmalonate, prepared from 104.5 g (0.6 mol) of diethyl malonate and 40.8 g of sodium ethylate, in 500 ml of ethanol was treated.

Absolute, by drip process, with 2-bromo-1- (bromomethyl) -4-tert.-butylbenzene (0.5 mol). The resulting mixture was refluxed, over a period of 4 hours, it was treated with a solution of NaOH (50 g, 1.25 mol) in water (60 ml), and refluxed, during a After 2 hours, it was then poured into water (11), and finally washed with toluene (2 x 100 ml). The aqueous solution was treated with 130 ml of 35% HCl. The resulting mixture was extracted with chloroform (4 x 250 ml), the organic phase was dried

35 over MgSO4 and evaporated. The residue was heated, at a temperature of 160-170 ° C, for a period of 15 minutes, providing the product (92 g, yield from 1-tert.-butyl-4-methylbenzene 60%).

4-Bromo-6-tert.-butyl-2-methyl-1-indanone

A mixture of 3- (2-bromo-4-tert.-butylphenyl) -2-methylpropanoic acid (46 g, 150 mmol) and SOCl2 (18 ml, 220 mmol) was stirred for a period of time of 1 hour, at a temperature of 40 ° C. The excess of SOCl2, was removed, by the action of vacuum. The residue was dissolved in CH2Cl2 (50 ml) and this was added at a temperature of 0 ° C, to a suspension of 20 g of AlCl3 in CH2Cl2Cl2 (200 ml). The reaction mixture was stirred, overnight, and poured into water / ice (500g), containing 50 ml of concentrated HCl. The phase

Organic, collected, washed with water, dried over MgSO4, and evaporated. The residue was distilled, under conditions of temperature / pressure of 125-130 ° C / 0.5 tor, to provide 32 g (76%) of product. 1 H NMR (CDCl 3, 20 ° C) M: 7.83 (d, 1 H); 7.75 (d, 1 H); 3.32 (q, 1 H); 2.77 (m, 1 H); 2.64 (dd, 1 H); 1.36 (s, 9H); 1.35 (d, 3H). 13C NMR (CDCl3, 20 ° C) M: 208.78; 153.29; 150.33; 138.00; 135.06; 121.68; 119.37; 42.26; 35.34; 34.89; 31.14; 16.18

50 6-tert.-Butyl-4- (4-tert.-butylphenyl) -2-methyl-1-indanone

Pd (OAc) 2 (0.3 g, 3 mol%) and PPh3 (0.7 g, 3 mol%) were added to a well-stirred mixture of 4-bromo-6tert.-butyl-2 -methyl-1-indanone (12.65 g, 45 mmol), tert.-butylphenylbonic acid (11.2 g, 63 mmol) and Na2CO3 (13.4 g, 126 mmol) in DME (170 ml) - H2O ( 56 ml) The resulting mixture was refluxed, under stirring, during a

After 6 hours, it was poured into water, CHCl3 (300 ml) was added, the organic phase was separated, washed with water, dried over MgSO4, evaporated, purified, by column chromatography gradient (hexane / chloroform, from 4: 1 to 1: 1). The productive yield was 10.84 g (72%). 1 H NMR (CDCl 3, 20 ° C) M: 7.83 (d, 1 H); 7.71 (d, 1 H); 7.55 (d, 2H); 7.46 (d, 2H); 3.43 (q, 1 H); 2.79 (m, 2 H); 1.43 (s, 9H); 1.42 (s, 9H); 1.35 (d, 3H).

10 13C NMR (CDCl3, 20 ° C) M: 209.75; 151.35; 150.38; 148.34; 139.44; 136.63; 132.59; 128.05; 125.37; 119.03; 42.41; 34.77; 34.48; 34.43; 31.27; 31.23; 16.15

5-tert.-Butyl-2-methyl-7-tert.-butylphenyl-1H-indene

15 5-tert.-butyl-7- (4-tert.-butylphenyl) -2-methyl-1-indanone (10.37 g, 31 mmol) in Et2O (150 ml) was added, by dropping procedure and at a temperature of 0 ° C, to LiAlH4 (0.6 g, 16 mmol) in Et2O (100 ml). After a period of 1 hour, under stirring, 5% HCl (50 ml) was added, the organic phase was separated, and the water was extracted, in Et2O (2x50 ml). The combined organic phase was washed with aqueous Na2CO3, dried over MgSO4, and evaporated. The residue was dissolved in benzene (500 ml), p-TSA (1 g) was added and the

The resulting mixture was refluxed, over a period of 10 minutes, cooled, washed with water, dried over MgSO4, evaporated, and dried, under the action of vacuum. empty. The productive yield was 9.9 g (approximately quantitative); viscous oil of yellow hue. 1H NMR (CDCl3, 20 ° C) M: 7.61 (m, 4H); 7.43 (d, 1 H); 7.32 (d, 1 H); 7.64 (q, 1 H); 3.48 (s, 2 H); 2.24 (d, 3 H); 1.51 (s, 18H).

13C NMR (CDCl3, 20 ° C) M: 150.02; 149.59; 146.34; 146.19; 138.80; 137.89; 136.49; 128.00; 127.24; 125.15; 121.47; 115.84; 42.37; 34.64; 34.44; 31.61; 31.33; 16.67

Bis (6-tert.-butyl-2-methyl-4-tert.-butylphenyl-1H-inden-1-yl) (dimethyl) silane

A solution of 5-tert.-butyl-2-methyl-7-tert.-butylphenyl-1H-indene (5.0 g, 15.7 mmol) in Et2O (70 ml) was cooled to a temperature from -40 ° C, and n-BuLi in hexane (1.6M, 9.81 ml, 15.7 mmol) was added. The resulting mixture was allowed to warm to room temperature, stirred for a period of 3 hours, and cooled, to a temperature of -60 ° C. CuCN (42 mg, 0.47 mmol) and SiMe2Cl2 (0.95 ml, 7.85 mmol) in Et2O (20 ml) were added. The resulting mixture was allowed to warm to room temperature, and stirred for a

35 time course of 16 hours. H2O (20 ml) and benzene (150 ml) were added and the organic phase was separated, dried over MgSO4, passed through silica gel, and evaporated. The residue was dried, under the action of vacuum (solid pale yellow hue) and used in the next step, without any further purification. 1H NMR (CDCl3, 20 ° C) M: 7.62-7.40 (group of m, 12H, CAr-H); 6.91 (bs); 6.88 (bs) {2H, -CH =}; 3.86 (s); 3.82 (s) {2H,> CH-}; 2.31 (bs); 2.25 (bs) {6H, -C-CH3}; 1.49 (s); 1.47 (s); 1.46 (s); 1.45 (s) {36H, -C (CH3) 3}; -0.06 (bs); -0.10 (bs);

40 0.11 (bs) {6H, Si-CH3}.

Synthesis of rac-dimethylsilyl (2-methyl-4 (4-tert.-butylphenyl) -6-tert.-butylinden-1-yl) dichlorocirconium

The bis (6-tert.-butyl-2-methyl-4-tert.-butylphenyl-1H-inden-1-yl) (dimethyl) silane (7.85 mmol) obtained was dissolved

45 above, in Et2O (80 ml) above, it was cooled to a temperature of -40 ° C, and n-BuLi (1.6 M in hexane, 10.4 ml, 16.7 mmol) was added. The reaction mixture was allowed to warm to room temperature, it was stirred for a period of 3 hours, and evaporated. The resulting yellow-brown solid was suspended in pentane (200 ml), cooled to a temperature of -60 ° C, and ZrCl4 (1.94 g, 8.33 mmol) was added. After a period of 5 minutes, Et2O (1 ml) was added. The resulting mixture was allowed to

50 was heated to room temperature, stirred for an additional 16 hours, and filtered. The residue was extracted by evaporation, by pentane / CH2Cl2 (2: 1), to provide a mixture of isomers (1.12 g, 16.7%). This mixture was recrystallized from pentane / CH2Cl2 (5: 1) to give the pure rac form (0.11 g, 3.3%). 1H NMR (CDCl3, 20 ° C) M: 7.57 (bs, 2H); 7.56 (" d ",4H); 7.47 (" d ",4H); 7.46 (bs, 2H) {CAr-H}; 6.87 (s, 2H, H of

55 C5 ring); 2.25 (s, 6H, C-CH3); 1.35 (s, 6H, Si-CH3); 1.33 (s, 18H, -C (CH3) 3); 1.32 (s, 18H, -C (CH3) 3);

Preparation of catalyst systems.

S1A1 catalyst system

60 A solution of 9.9 ml of TIBA / cyclohexane (113 g / l), with 2.4 ml of an MAO / toluene solution, was added to obtain a MAO / TIBA molar ratio factor of 2: 1. The solution was stirred, for a period of 1 hour, at room temperature, and it was transferred to a 50 ml capacity Schlenk flask, containing 20.8 mg of Al. This solution, it was diluted with 23.5 ml of cyclohexane, to reach a concentration of 50 gTOT / l and 0.582 gmetalocene / l.

S2C1 catalyst system

5 A solution of 39.1 ml of TIBA / isododecane (90 g / l) was mixed with 7.4 ml of MAO / toluene to obtain a MAO / TIBA molar ratio factor of 2: 1. The solution was stirred, for a period of 1 hour, at room temperature, and transferred to a 50 ml capacity Schlenk flask, containing 55.8 mg of C1. The resulting mixture was diluted with 9.8 ml of isododecane, to provide a solution of 100 gTOT / l and

10 0.99 gmetalocene / l.

S3C1 catalyst system

39.1 ml of a solution of TIBA / cyclohexane (113 g / l) was mixed with a solution of 2.8 ml of MAO

15 / toluene, to obtain a MAO / TIBA molar ratio factor of 2: 1. The solution was stirred, for a period of 1 hour, at room temperature, and a Schlenk flask of 50 was transferred ml of capacity, containing 21.1 mg of Cl. This solution was diluted with 6.78 ml of cyclohexane, to provide a solution of orange hue, of a concentration of 100gTOT / l and 0.99 gmetalocene / l.

20 S4C2 catalyst system

8.1 ml of a TIBA / isododecane solution (110 g / l) was mixed with 1.9 ml of a MAO / toluene solution to obtain a MAO / TIBA molar ratio factor of 2: 1 The solution was stirred, for a period of 30 minutes, at room temperature. Then, 25 mg of C2 was added,

25 to provide a clear solution, which was diluted 4.4 ml of toluene, to obtain a concentration of 100gTOT / l and 1.74 gmetalocene / l.

Examples of propylene polymerization

The polymerization procedure and the conditions for each test test are described in detail, below, below, and these data are also collected in Table 1.

The results of the analysis performed on the polymer samples are compiled in Table 2.

35 Example 1

As a previous step, an autoclave of 4.4 l of useful capacity, equipped with a double blanket and equipped with a mechanical drive agitator and a stainless steel vial, of 35 ml of useful capacity, was connected and connected to a thermostat for temperature control, for whose previous purification process, we proceeded to

A wash with a solution of Al (i-Bu) 3 in hexane and dried, at a temperature of 50 ° C in a stream of nitrogen. Then, at room temperature, 6 mmol of Al (i-Bu) 3 (as a 100 g / l hexane solution), 629 g of cyclohexane and 732 g of propylene were charged and the autoclave was adjusted by the thermostat, at a temperature of 100 ° C (the polymerization temperature). Under these conditions, the liquid composition, at a temperature of

45 100248C, is calculated as being the one corresponding to a ratio value of 50% / 50%, by weight, of propylene / cyclohexane. 4 ml of S1A1 catalyst system was injected into the autoclave, through 4 ml of cyclohexane, through the stainless steel vial. Propylene was introduced, continuously, for a period of 30 minutes, to maintain a pressure corresponding to a value of 35 bar-g; 53 g of

50 propylene Then, the autoclave discharge valve was opened and the polymer was discharged into a heated steel tank containing water at a temperature of 70 ° C. The heating system was switched off and, a nitrogen flow of 0.5 bar-g was introduced. After stirring at room temperature, the steel tank was opened and the wet polymer was collected. The wet polymer was dried, under the action of reduced pressure,

55 at a temperature of 70 ° C. The polymerization data, are compiled in Table 1, and the characterization of the polymer obtained, is compiled in Table 2:

Comparative Example 2

60 The procedure of example 1 was repeated, except as regards the fact that, 5 ml of the catalyst system S2C1, which contained a catalyst / cocatalyst mixture (solution of 0, was injected into the autoclave) 99 mg metallocene / ml solution), through 4 ml of cyclohexane, through a stainless steel vial. Propylene was introduced, in a continuous regime, over a period of 30 minutes, at a pressure of 31.5 bar-g, for a total consumption of 43.7 g of propylene.

The polymer was discharged, in accordance with the procedure described in Example 1. The polymerization data is collected in Table 1 and, the characterization of the polymer obtained, is collected in Table 2.

Table 1

Example

Catalyst system Metallocene (mg) P (bar - g) T (minutes Absorbed propylene KgPOL / gcat activity

one

S1A1 2.33 32 30 53 24.3

2*

 S2C2 4.95 31.5 40 43.7 6.8

Activity in kg of the polymer, per gram of metallocene, averaged over a period of 30 minutes. 10 * Comparative example

Table 2

Example

I.V. dl / g Tm ° C MMM (%) mrrm (%) 2.1 (%) 3.1 (%) Mn (10-3) MW (10-3) MW / Mn

one

2.1 150.1 96.1 0.14 0.5 0.17 n. d. n. d. n. d.

2*

1.5 154.6 96.6 0.30 0.30 0.11 109 246 2.3

n. d. = not available

Examples of propylene / ethylene copolymerization.

20 Example 3

The procedure of example 1 was repeated, introducing 720 g of cyclohexane, 35 g of ethylene and 654 g of propylene. 4 ml of S1A1 catalyst system solution was injected into the autoclave, through 4 ml of cyclohexane, through the stainless steel vial.

25 An ethylene / propylene mixture was introduced, in a mixing ratio, in percentage, of 10% / 90%, on a continuous basis, over a period of 30 minutes, to maintain the pressure of 35 bar-g: they consumed 103.4 g of propylene and 11.6 g of ethylene. The copolymer was discharged, in accordance with the procedure described in Example 1. The polymerization data, are collected in Table 3

30 Example 4

The procedure of example 1 was repeated, introducing 716 g of cyclohexane, 61 g of ethylene and 631 g of propylene. 3 ml of S1A1 catalyst system solution was injected into the autoclave, through mediation

35 of 4 ml of cyclohexane, through the stainless steel vial. An ethylene / propylene mixture was introduced in a percentage ratio of 17/83%, in a continuous regime, over a period of 30 minutes, to maintain the pressure of 37 bar-g: 17.9 g of propylene were consumed and 17.9 g of ethylene. The copolymer was discharged, in accordance with the procedure described in Example 1. The data of

40 polymerization, are compiled in Table 3.

Example 5

The procedure of example 1 was repeated, introducing 776 g of cyclohexane, 72 g of ethylene and 647 g of

45 propylene. 2 ml of S1A1 catalyst system solution was injected into the autoclave, through 4 ml of cyclohexane, through the stainless steel vial. An ethylene / propylene mixture was introduced in a percentage mixing ratio of 21/79%, continuously, over a period of 30 minutes, to maintain the pressure of 39 bar-g: 30.5 g of propylene and 8 g of ethylene.

The copolymer was discharged, in accordance with the procedure described in Example 1. The polymerization data, are collected in Table 3.

Comparative Example 6

The procedure of example 1 was repeated, introducing 720 g of cyclohexane, 35 g of ethylene and 654 g of propylene. 3 ml of S3C1 catalyst system solution was injected into the autoclave, through 4 ml of cyclohexane, through the stainless steel vial.

An ethylene / propylene mixture was introduced in a percentage mixing ratio of 10/90%, in a continuous regime, over a period of 30 minutes, to maintain the pressure of 34 bar-g: 40 g of propylene were consumed and 4.4 g of ethylene. The copolymer was discharged, in accordance with the procedure described in Example 1. The data of

5 polymerization, are compiled in Table 3.

Comparative Example 7

The procedure of example 1 was repeated, introducing 716 g of cyclohexane, 61 g of ethylene and 631 g of propylene. 4 ml of the S3C1 catalyst system solution was injected into the autoclave, through 4 ml of cyclohexane, through the stainless steel vial. An ethylene / propylene mixture was introduced in a percentage mixing ratio of 17/83%, on a continuous basis, over a period of 20 minutes, to maintain the pressure of 37 bar-g: 103.7 g of propylene and 21.2 g of ethylene.

The copolymer was discharged, in accordance with the procedure described in Example 1. The polymerization data, is collected in Table 3.

Comparative Example 8

The procedure of example 1 was repeated, introducing 676 g of cyclohexane, 72 g of ethylene and 647 g of propylene. 2.5 ml of the S3C1 catalyst system solution was injected into the autoclave, through 4 ml of cyclohexane, through the stainless steel vial. An ethylene / propylene mixture was introduced in a percentage mixing ratio of 21/79%, continuously, over a period of 30 minutes, to maintain the pressure of 38 bar-g: they were consumed

25 78.4 g of propylene and 21 g of ethylene. The copolymer was discharged, in accordance with the procedure described in Example 1. The polymerization data is collected in Table 3.

Comparative Example 9

The procedure of example 1 was repeated, introducing 958 g of cyclohexane, 31 g of ethylene and 500 g of propylene, in order to obtain a liquid composition, at a temperature of 90 ° C, and 21 bar-g, corresponding to a a liquid composition a mixture of 5% / 95%, by weight, of ethylene / propylene. 4 ml of the S4C2 catalyst system solution was injected into the autoclave, through 4 ml of

35 cyclohexane, through the stainless steel vial. An ethylene / propylene mixture was introduced in a percentage mixing ratio of 11% / 89%, on a continuous basis, over a period of 30 minutes, to maintain the pressure of 21 bar-g: 33.7 g were consumed of propylene and 4.1 g of ethylene. The copolymer was discharged, in accordance with the procedure described in Example 1. The polymerization data is collected in Table 3.

Comparative Example 10

The procedure of example 1 was repeated, introducing 958 g of cyclohexane, 50 g of ethylene and 484 g of

45 propylene, in order to obtain a liquid composition, at a temperature of 90 ° C, and 24 bar-g, corresponding to a liquid composition a mixture of 8% / 92%, by weight, of ethylene / propylene. 4 ml of S4C2 catalyst system solution was injected into the autoclave, through 4 ml of cyclohexane, through the stainless steel vial. An ethylene / propylene mixture was introduced in a percentage mixing ratio of 16% / 31.2%, continuously, over a period of 30 minutes, to maintain the pressure of 24 bar-g: 31 were consumed, 2 g of propylene and 5.9 g of ethylene. The copolymer was discharged, in accordance with the procedure described in Example 1. The polymerization data is collected in Table 3.

55 Comparative Example 11

The procedure of example 1 was repeated, introducing 958 g of cyclohexane, 64 g of ethylene and 473 g of propylene, in order to obtain a liquid composition, at a temperature of 90 ° C, and 26 bar-g, corresponding to a a liquid composition a mixture of 10% / 90%, by weight, of ethylene / propylene. 4 ml of S4C2 catalyst system solution was injected into the autoclave, through 4 ml of cyclohexane, through the stainless steel vial. An ethylene / propylene mixture was introduced in a 20% / 80% percentage mixing ratio, continuously, over a period of 30 minutes, to maintain the pressure of 26 bar-g: 86.5 g were consumed of propylene and 21.6 g of ethylene.

65 The copolymer was discharged, in accordance with the procedure described in Example 1. The polymerization data is collected in Table 3. 18

E07712441 11-11-2011

Table 3

Example

Catalyst system mg zirconium compound P (bar - g) KgPOL / Gcat activity Ethylene content I.V. (dl / g)

3

S1A1 2.3 34 -35 95.1 7.9 1.82

4

S1A1 1.8 37 99.4 13.9 1.68

5

S1A1 1.5 39 48.2 15.8 1.76

6 *

 S3C1 3.0 3. 4 30, .0 8.7 1.13

7 *

 S3C1 40 37 68.0 14.0 1.09

8 *

 S3C1 2.5 38 58.5 16.2 1.10

9 *

 S4C2 7.0 twenty-one 12.9 8.1 1.29

10 *

 S4C2 7.0 24 18.0 13.8 1.16

eleven*

 S4C2 7.0 25.6 37.1 17.2 1.26

Activity in kg of the polymer, per gram of metallocene, averaged over a period of 30 minutes. * Comparative example

Claims (13)

1.- Bridged metallocene compound of the formula (I) 5 where, M, is an atom of a transition metal, selected from those belonging to group 3, 4 or to the lanthanide or actinide groups, from the Periodic Table of the Elements; 10 X, the same or different from each other, is a hydrogen atom, a halogen atom, a group R, OR, OSO2DF3, OCOR, SR, NR2, or PR2, where, R, is a radical C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C6-C40 aryl, C7-C40 alkylaryl, or C7-C40 arylalkyl, cyclic or acyclic, linear or branched; containing, optionally, heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; or two X groups, can be found together, to form an OR’O group, where, R ’, is an alkylidene radical C1-C20, C6-C20 arylidene, C7-C20 alkylarylidene, or C7-C20 arylalkylidene; L, is a divalent bridging group, selected from the radicals C1-C20 alkylidene, C3-C20 cycloalkylidene, C6-C20 arylidene, C7-C20 alkylarylidene, or C7-C20 arylalkylidene, which optionally contains heteroatoms which belong to groups 13-17 of the Periodic Table of the Elements, or is a silidene radical, containing up to 5 silicon atoms; R1, the same or different from each other, are a C1-C40 hydrocarbon radical, which optionally contains heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; R2, the same or different from each other, are a group C (R19) 2R18; wherein, R18 and R19, the same or different from each other, are C1-C20 alkyl radicals; R3, the same or different from each other, are hydrogen atoms, or C1-C40 hydrocarbon radicals, 25 belonging to groups 13-17 of the Periodic Table of the Elements; W1 and W2, the same or different from each other, are aromatic rings of 5 or 6 members, which may contain heteroatoms belonging to groups 15-16 of the Periodic Table of the Elements; the valence of each atom of said ring is substituted with hydrogen, or it can be substituted, optionally, with R5 groups, where R5, equal or different from each other, are radical C1-C40 hydrocarbon, optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements. 2. The bridged metallocene compound according to claim 1, wherein M is zirconium, titanium or hafnium; X, is a hydrogen atom, a halogen atom, an OR'O group or an R, L group, is Si (R11) 2 where, R11, is a C1-C40 alkyl radical, C2-C40 alkenyl, C2-C40 alkynyl, C6-C40 aryl, C7-C40 alkylaryl, or C7-C40 arylalkyl, cyclic or acyclic, linear or branched. 3. The bridged metallocene bridged compound according to claim 1 or 2, wherein R2, the same or different from each other, is a group C (R19) 2R18; wherein, R18, the same or different from each other with respect to each other, are hydrogen atoms or a C1-C40 hydrocarbon radical, which optionally contains one or more heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements;  4. The bridged metallocene compound according to any one of claims 1-3, wherein W1 and W2 are selected from the group comprising the following portions of the formula (Wa), (Wb) and ( Wc): where * represent the point at which the portion is attached to the indenyl portion of the compound of the formula (I); R6, R7, R8, R9 and R10, the same or different from each other, are hydrogen atoms or C1-C40 hydrocarbon radicals, which optionally contain heteroatoms belonging to groups 13-17 of The periodic table; Z1, is a nitrogen atom, or a CR10 group; Z2, is a nitrogen atom, or a CR6 group; Z3, is a nitrogen atom, or a CR7 group; Z4, is a nitrogen atom or a CR8 group; Z5, is a nitrogen atom, or a group 10 CR9; with the proviso that, no more than two groups, among the Z1, Z2, Z3, Z4 and Z5, are nitrogen atoms; Z6, is an oxygen atom, a sulfur atom, an NR13 group, or a CR13 group; Z7, is an oxygen atom, a sulfur atom, an NR14 group, or a CR14 group; Z8, is an oxygen atom, a sulfur atom, an NR15 group or a CR15 group; Z9, is an oxygen atom, a sulfur atom, an NR16 group or a CR16 group; Z10, is a nitrogen atom or a carbon atom, which bonds the indenyl portion of the formula structure 15 (I); with the proviso that, not more than 1 group, from among the Z6, Z7, Z8, Z9 and Z10, is a sulfur atom, an oxygen atom, or a nitrogen-containing group, selected from among NR13, NR14, NR15, NR16, and a nitrogen atom; R13, R14, R15 and R16, the same or different from each other, are hydrogen atoms or C1-C40 hydrocarbon radicals, which optionally contain heteroatoms belonging to groups 13-17 of the 20 Periodic Table of the Elements;  5. The bridged metallocene compound according to claim 5, wherein, in the portion of the formula (Wa), R7, is a C1-C40 alkyl radical, and R6, R8, R9 and R10 are atoms of hydrogen; The bridged metallocene compound according to claim 5, wherein, in the portion of the formula (Wa), R10 and R8, are C1-C40 alkyl radicals, and R7, R8 and R9, are hydrogen radicals .  7. The bridged metallocene compound according to claim 5, wherein, in the portion of the formula (Wa), R6, R7 and R8, are C1-C40 alkyl radicals, linear or branched, and R10 and R9, They are hydrogen atoms. 8. The bridged metallocene compound according to claim 5, wherein, in the portion of the formula (Wa), R6, R7, R8, R9 and R9 are hydrogen atoms; 9. The bridged metallocene compound according to claim 5, wherein, in the portion of the formula (Wb), Z1 is a nitrogen atom, and Z2, Z3, Z4 and Z5 are, in one form respectively, CR6, CR7, CR8, and CR9, wherein the meaning of R6, R7, R8 and R9 is described in claim 4. 10. The bridged metallocene compound according to claim 5, wherein, in the portion of the formula (Wb), Z3, is a nitrogen atom, and Z1, Z2, Z4 and Z5 are, respectively, CR10, CR6, CR8 and CR9, wherein the meaning 40 of R10, R6, R8 and R9 is described in claim 4. 11. The bridged metallocene compound according to claim 5, wherein, in the portion of the formula (Wb), Z2, is a nitrogen atom, and Z1, Z3, Z4 and Z5 are, respectively, CR10, CR7, CR8 and CR9, wherein the meaning of R10, R7, R8 and R9 is described in claim 4. 12. The bridged metallocene compound according to claim 5, wherein, in the portion of the formula (Wb), Z6, is an oxygen atom, a sulfur atom, an NR16 group. 13. The bridged metallocene compound according to any one of claims 1-11, having the formula (IIa) where, M, L, X, R1, R2, R3, R6, R7, R8 and R10, have the meanings described in claim 1. 14. The bridged metallocene compound according to any one of claims 1-11, having the formula (IIb) 10 where, M, L, X, R1, R2, R3, R14, R15 and R16, have the meanings described in Table 1.  15. A system for the polymerization of olefins, which can be obtained by contacting: a) a metallocene compound of the formula (I), as described in claims 1-13; B) at least one alumoxane or a compound suitable to form an alkylmethalocene cation; and c) optionally, an organoaluminum compound. 16. A process for preparing an alpha-olefin polymer, which comprises contacting, under polymerization conditions, one or more alpha-olefins of the formula CH2-CHA, wherein, A, is hydrogen or an alkyl radical C1-C20, in the presence of a catalyst system of claim 14.