Title of Invention

BRIDGED METALLOCENE COMPOUNDS

Abstract METALLOCENE COMPOUNDS A bridged metallocene compound of formula (I) wherein: M is an atom of a transition metal; X, is a hydrogen atom, a halogen atom, or a hydrocarbon-based group; Rl is a C1-C40 hydrocarbon radical; R2 and R3, form together a condensed 3-7 membered ring; R4, is a hydrogen atom or a C1-C40 hydrocarbon radical; W is an aromatic 5 or 6 membered ring.
Full Text

Title:
Metallocene compounds
The present invention relates to a class of bridged bis indenyl metallocene compounds having C2 symmetry, wherein the indenyl moieties are in particular substituted in position 4 by a phenyl moiety and in positions 5 and 6 by a condensed ring, the present invention further relates to the catalyst system thereof and the polymerization process therefrom. Metallocene compounds are well known in the art as catalyst components for the polymerization of olefins. WO 03/050131 relates to a class of bis indenyl metallocene compounds wherein the indenyl moieties are at least substituted in position 4 and 5. However WO 03/050131 does not report that the substituents on positions 5 and 6 can form a condensed ring. PCT/EP03/12236 relates to a bis indenyl metallocene compound substituted at least in positions 2 5 and 6, wherein the substituents in positions 5 and 6 form a condensed ring. However the substituent in position 4 is defined only in a generic way and in the compounds exemplified in the examples it is always a hydrogen atom. In PCT/EP2004/013827 a class of bis indenyl metallocene compounds wherein the indenyl moieties are substituted in position 5 and 6 by a condensed ring is disclosed. PCT/EP2004/013827 is mainly focused on Ci symmetric structures and there are no explicit disclosures of C2 symmetric compounds. In other words this document is focused on metallocene compounds comprising two cyclopentadienyl moieties having different substitution pattern.
All the compounds disclosed in these documents are able to polymerize alpha-olefins, in particular propylene. However there still is the need to find a new class of metallocene compounds able to polymerize olefin in higher yields and to produce polymers having very high molecular weight. An object of the present invention is a bridged metallocene compound of 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 in the Periodic Table of the Elements; preferably M is
zirconium, titanium or hafnium;
X, equal to or different from each other, is a hydrogen atom, a halogen atom, a R, OR,
OR'O, OS02CF3,.OCOR, SR, NR2 or PR2 group wherein R is a linear or branched, cyclic
or acyclic, Ci-Qo-alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C6-C40-aryl, C7-C4o-alkylaryl or
C7-C4o-aiylalkyl radical; optionally containing heteroatoms belonging to groups 13-17 of the
Periodic Table of the Elements; and R' is a CrC^o-alkylidene, C6-C2o-arylidene5
C7-C2o-alkylarylidene, or C7-C2o-arylalkylidene radical; preferably X is a hydrogen atom, a
halogen atom, a OR'O or R group; more preferably X is chlorine or a methyl radical;
L is a divalent bridging group selected from C1-C20 alkylidene, C3-C20 cycloalkylidene, C6-
C20 arylidene, C7-C20 alkylarylidene, or a C7-C20 arylalkylidene radicals, optionally
containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements, or
it is a silylidene radical containing up to 5 silicon atoms; preferably L is Si(Ru)2 wherein R11
is a linear or branched, cyclic or acyclic, G-C4o-alkyl, C2-C4o alkenyl, C2-C40 alkynyl,
C6-C4o-aryl, C7-C4o-alkylaryl or C7-C4o-arylalkyl radical; more preferably L is Si(CH3)2 or
SiPh2;
R1 is a linear C1-C40 hydrocarbon radical optionally containing heteroatoms belonging to
groups 13-17 of the Periodic Table of the Elements such as methyl or ethyl radical or an

alpha branched aryl or arylalkyl radical containing from 2 to 20 carbon atoms optionally containing O, N, S, P and Se atoms, in particular O, N and S atoms such as 2(5 -Me-thiophenyl) or 2(5-Me-furanyl) radicals; preferably R1 is a linear Ci-C2o-alkyl, C2-C4o alkenyl, C2-C40 alkynyl radical, optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; preferably R1 is a linear d-Cio-alkyl radical; more preferably R1 is a methyl, or ethyl radical;
R2 and R3, are part of 4-7 membered ring condensed to the benzene ring of the indenyl moiety; preferably a 5 or 6 membered ring; said ring optionally containing heteroatoms belonging to groups 13-16 of the Periodic Table of the Elements preferably groups 15-16 of the Periodic Table of the Elements; the valence of each atom forming said ring being substituted with R18 radicals; that means that is filled with R18 groups, wherein R18, equal to or different from each other, are hydrogen atoms or a C1-C40 hydrocarbon radical; preferably R18 is a hydrogen atom or a linear or branched, cyclic or acyclic, Ci-Qo-alkyl, C2-C40 al kenyl, C2-C40 alkynyl, Q-C^-aiyl, C7-C4o-alkylaiyl or C7-C4o-arylalkyl radical, optionally containing one or more heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; more preferably R is a hydrogen atom or a linear or branched, Ci-C2o-alkyl radical; more preferably R18 is a hydrogen atom or a methyl or ethyl radical; said ring can be saturated or it can contain double bonds; preferably R2 and R3, form together a condensed saturated 3-7 membered ring;
R4 is a hydrogen atom or a C1-C40 hydrocarbon radical optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; preferably R4 is a hydrogen atom or a linear or branched, cyclic or acyclic, Ci-C4o-alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C6-C4o-aryl, C7-C4o-alkylaiyl or C7-C4o-arylalkyl radical optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; preferably R4 is a hydrogen atom a Ci-Cio-alkyl or a C6-C4o-aryl radical;
W is an aromatic 5 or 6 membered ring that can 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 atom or it can optionally be substituted with R5 groups, wherein R5, equal to or different from each other, are C1-C40 hydrocarbon radicals optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; preferably R5, are linear or branched, cyclic or acyclic, Ci-C4o-alkyl, C2-C40 alkenyl,

C2-C4o alkynyl, Q-Qo-aiyl, C7-C4o-alkylaryl or C7-C4o-arylalkyl radicals optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements;
Preferably W is selected from the group comprising the following moieties of formula (Wa), (Wb) and (Wc):

wherein the * represents the point in which the moiety bounds the indenyl moiety of the compound of formula (I);
R6, R7, R8, R9 and R10, equal to or different from each other, are hydrogen atoms or Ci-C40 hydrocarbon radicals optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; preferably R , R , R , R and R , are hydrogen atoms or linear or branched, cyclic or acyclic, Ci-C4o-alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C6-C4o-aryl, C7-C4o-alkylaryl or C7-C4o-arylalkyl radicals optionally containing heteroatoms belonging to groups 13-17 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; provided that not more that 2 groups among Z], Z2, Z3, Z4 and Z5 are nitrogen atoms, preferably not more that one group among Z , Z , Z , Z and Z is a nitrogen atom; Z6 is an oxygen atom, a sulfur atom, a NR13 group or a CR13 group; Z7is an oxygen atom, a sulfur atom, a NR14 group or a CR14 group; Z8is an oxygen atom, a sulfur atom, a NR15 group oraCR15group; Z9 is an oxygen atom, a sulfur atom, aNR16 group or aCR16group; Z10 is a nitrogen atom or a carbon atom that bonds the indenyl moiety of the structure of formula (I); with the proviso that not more than 1 group among Z6, Z7, Z8, Z9 or Z10 is a sulfur atom, an oxygen atom or a nitrogen-containing group atom selected from NR13, NR14, NR15, NR16, and a nitrogen atom;

R13, R14, R15 and R16, equal to or different from each other, are hydrogen atoms or C1-C40 hydrocarbon radicals optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; preferably R6, R7, R8, R9 and R10, are hydrogen atoms or linear or branched, cyclic or acyclic, G-C4o-alkyl, C2-C40 alkenyl, C2-C40 alkynyl , C6-C4o-aryl, C7-C4o-alkylaryl or C7-C4o-arylalkyl radicals optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; more preferably R , R , R8, R9 andR10are hydrogen atoms, G-C4o-alkyl or C6-C4o-aryl radicals; In the moiety of formula (Wa), in a preferred embodiment, R is a Ci-C4o-alkyl radical, preferably a branched C]-C4o-alkyl radical such as a tertbutyl radical, more preferably R7 is a branched Ci-C4o-alkyl radical wherein the carbon atom in position alpha is a tertiary carbon atom and R6, R8, R9 and R10 are hydrogen atoms;
In a further preferred embodiment R and R are CrQo-alkyl radicals, preferably they are linear G-Gtoalkyl radicals such as methyl radicals and R7, R8 and R9 are hydrogen radicals:
(\ *7 ft
In a further preferred embodiment R , R and R are linear or branched Ci-C4o-alkyl
radicals such as methyl or tertbutyl radicals and R10 and R9 are hydrogen atoms.
In a further preferred embodiment R6, R7, R8, R9 and R10 are hydrogen atoms;
In the moiety of formula (Wb), in a preferred embodiment, Z is a nitrogen atom and Z",
Z3, Z4 and Z5 are respectively CR6, CR7, CR8 and CR9 wherein the meaning of R6, R7, R8,
and R is described above; in a further preferred embodiment Z3 is a nitrogen atom and
Z\ Z2, Z4 and Z5 are respectively CR10, CR6, CR8 and CR9 wherein the meaning of R10,
f\ ft 0 i
R , R , and R is described above; in a further preferred embodiment Z" is a nitrogen
atom and Z\ Z3, Z4 and Z5 are respectively CR10, CR7, CR8 and CR9 wherein the
1 ft *7 R 0
meaning of R , R , R , and R is described above;
In the moiety of formula (Wc) in a preferred embodiment Z6 is an oxygen atom, a sulfur
atom, a NR16 group; preferably it is a sulfur atom or a NR16; wherein R16 is preferably a
CrC4(ralkyl radical; more preferably Z6 is a sulfur atom; and Z7, Z8, Z9 and Z10 are
respectively a CR14, CR15, CR16 and a carbon atom, wherein R14 is a hydrogen atom or a
Crdo-alkyl radical such as methyl or ethyl; and R15 and R16 are hydrogen atoms or
Ci-Gnralkyl radicals.
Examples of compounds having formula (I) are as follows

Me2Si(6-Me-4-Ph-1,2,3,5-tetrahydro-^-mdacen-7-yl)2ZrCl2j
Me2Si(6,8-Me2-4-Ph-ls2,3,5-tetrahydro-5-indacen-7-yl)2ZrCl2,
Me2Si[6-Me-4«(4-r-BuPh)-l,2)3,5-tetrahydro-5-mdacen-7-yl]2ZrCl2,
Me2Si(6,8-Me2-4 Me2Si[6«Me-4-(2-MePh)-l,233,54etrahydro-5'-indacen--7-yl]2ZrCl2,
Me2Si(6,8-Me2-4 Me2Si(l,l53,3,6-Me5-4 Me2Si[6-Me-4-(2s5-Me2Ph)»l?2,3,5-tetrahydro-5-indacen-7»yl]2ZrCl2,
Me2Si[6-Me-4-(4-biphenyl)-l,2,3,5-tetrahydro-5-indacen-7"yl]2ZrC]2,
Me2Si(l,l;3,3,6-Me5-4-Ph-l,2,3,5-tetrahydro-j-indacen-7-yl)2ZrCl2,
Me2Si[lJ,33,6-Me5-4-(44BuPh)-l,2,3,54etrahydro^-indacen-7-yl]2ZTCl2,
Me2Si(2,2,6-Me3-4-Ph-l,2,3,5-tetrahydro-5-indacen-7-y1)2ZrCl2,
Me2Si(2-Me-4-Ph- 777-cyclopenta[2>]naphthalen-1 -yl)2ZrCl2,
Me2Si(2,5J8»Me3-4-Ph-;^-cyclopenta[6]naphthalen-1 -yl)2ZrCl2,
Me2Si(2-Me-4-Ph-5,6,7,84etrahydro-7//-^
Me2Si(2,6-Me2-4-Ph-5//-l-thia-5-indacen-7-yl)2ZrCl2,
Me2Si(2,3,6-Me3-4-Ph-5/7-1 -thia-5-indacen-7-y])2ZrCl2,
Me2Si(2,6-Me2-4-(4-r-BuPh)-5/7-l-thia^«inciacen-7-yl)2ZrCl2,
Me2Si(2,3,6-Me3-4-(4^-BuPh)-5//-l-thia-5-indacen-7-yl)2ZrCl2,
Me2Si(2-Me-4-Ph-1,5,6,7,8,9-hexahydrocyclohepta^inden-1 -yl)2ZrCl2,
Me2Si(6-Me-4-(2-benzothiophenyl)-l,233,5-tetrahydro-5,-indacen-7-yl)2ZrCl2,
Me2Si(6-Me-4-(2 Me2Si(6-Me-4-(2-(5-methylfuryl))-l,23,54etrahydro-5-indacen-7-yl)2ZrCl2,
Me2Si(6-Me-4-(4-pyridyl)-l,2J3,5-tetrahydro-5'-indacen-7-y])2ZrCl2,
and they correspondent dimethyl derivatives.
A preferred class of the compounds of formula (I) is represented by formula (II):


Wherein M, L, X, R1, R4, R6, R7, R8, R9 and R10have the meaning reported above and R11 and R12> equal to or different from each other, are hydrogen atoms or C1-C40 hydrocarbon radicals optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; preferably R and R are hydrogen atoms or linear or branched, cyclic or acyclic, Q-C^-alkyl, C2-C40 alkenyl, C2-C40 alkynyl radicals, optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; more preferably R11 and R12 are hydrogen atoms or Ci-Cio-alkylradicals such as methyl or ethyl radicals. A further preferred class of compounds of formula (I) has formula (Ila)


Wherein M, L, X, R1, R4, R1 ], R12, R14, R15 and R16 have the meaning reported above.
In the metallocene compounds object of the present invention the two cyclopentadienyl
moieties have the same substitution patterns That means that the two indenyl moieties
bounded on the central metal atom are substituted in the same way, or in other words, the
substituents R , R", R , R and W are the same on each indenyl moiety. Preferably the
metallocene compounds of formula (I) have C2 symmetry. Metallocene symmetry classes
can be found on Resconi et al. Chemical Reviews, 2000, Vol. 100, No. 4 1263 and
references herein cited.
Preferably the metallocene compounds object of the present invention are in their
racemic(rac) form.
A further object of the present invention is a catalyst system for the polymerization of
olefin obtainable by contacting:
a) a metallocene compound of formula (I);
b) at least an alumoxane or a compound able to form an alkylmetallocene cation; and
c) optionally an organo aluminum compound. Preferably the metallocene compounds have formula (II) or (Ha).

Alumoxanes used as component b) in the catalyst system according to the present invention can be obtained by reacting water with an organo-aluminium compound of formula HJA1U3-J or HjAkUe-j, where the U substituents, same or different, are hydrogen atoms, halogen atoms, Ci-C2o-alkyl, C3-C2o-cyclalkyl, C6-C2o-aryl, C7-C2o-alkylaryl or C7-C2o-arylalkyl radicals, optionally containing silicon or germanium atoms, with the proviso that at least one U is different from halogen, and j ranges from 0 to 1, being also a non-integer number. In this reaction the molar ratio of Al/water is preferably comprised between 1:1 and 100:1. The alumoxanes used in the catalyst system according to the invention are considered to be linear, branched or cyclic compounds containing at least one group of the type:

wherein the substituents U, same or different, are defined above. In particular, alumoxanes of the formula:

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

can be used in the case of cyclic compounds, wherein n is an integer from 2 to 40 and the U
substituents are defined as above.
Examples of alumoxanes suitable for use according to the present invention are
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 cocatalysts are those described in WO 99/21899 and in WOO 1/21674
in which the alkyl and aryl groups have specific branched patterns.
Non-limiting examples of aluminium compounds that can be reacted with water to give
suitable alumoxanes (b), described in WO 99/21899 and WO01/21674, are:

tris(2,3,3-trimethyl-butyl)aluminium, tris(2,3-dimethyl-hexyl)aluminium, tris(2,3-dimethyl-
butyl)aluminium, tris(2,3-dimethyl-pentyl)aluminium, tris(2,3-dimethyl-heptyl)aluminium,
tris(2-methyl-3-ethyl-pentyl)aluminium, tris(2-methyl«3-ethyl-hexyl)aluminium,
tris(2-methyl-3-ethyl-heptyl)aluminium, tris(2-methyl-3-propyl-hexyl)aluminium,
tris(2-ethyl-3-methyl-butyl)aluminium, tris(2-ethyl-3-methyl-pentyl)aluminium,
tris(2,3 -diethyl-pentyl)aluminium, tris(2-propyl-3-methyl-butyl)aluminium, tris(2-isopropyl-
3-methyl-butyl)aluminium, tris(2-isobutyl-3-methyl-pentyl)aluminium, tris(2,3,3-trimethyl-
pentyl)aluminium, tris(2,3,3-trimethyl-hexyl)aluminiuiTi, tris(2-ethyl-3,3-dimethyl-
butyl)aluminium, tris(2-ethyl-3,3-dimethyl-pentyl)aluminium, tris(2-isopropyl-3.,3-dimethyl-
butyl)aluminium, tris(2-trimethylsilyl-propyl)aluminium, tris(2-methyl-3-phenyl-
butyl)aluminium, tris(2-ethyl-3-phenyl-butyl)aluminium, tris(2,3-dimethyl-3-phenyl-
butyl)aluTninium, tris(2-phenyl-propyl)aluminium, tris[2-(4-fluoro-phenyl)-
propyl]aluminium3 tris[2-(4-chloro-phenyl)-propyl]aluminium, tris[2-(3-isopropyl-phenyl)-propyl]aluminium, tris(2-phenyl-butyl)aluminium5 tris(3-methyl-2-phenyl-butyl)aluminium, tris(2-phenyl-pentyl)aluminium, tris[2-(pentafluorophenyl)-propyl]aluminium, tris[2,2-diphenyl-ethyl]aluminiuTn and tris[2-phenyl"2-methyl-propyl]aluminium, as well as the corresponding compounds wherein one of the hydrocarby] groups is replaced with a hydrogen atom, and those wherein one or two of the hydrocarbyl groups are replaced with an isobutyl group.
Amongst the above aluminium compounds, trimethylaluminium (TMA), triisobutylaluminium (TIBA), tris(2,4,4-trimethyl-pentyl)aluminium (TIOA), tris(2,3-dimethylbutyl)aluminium (TDMBA) and tris(2,3,3-trimethylbutyl)aluminium (TTMBA) are preferred.
Non-limiting examples of compounds able to form an alkylmetallocene cation are compounds of formula D+E", wherein D+ is a Bronsted acid, able to donate a proton and to react irreversibly with a substituent X of the metallocene of formula (I) and E" is a compatible anion, which is able to stabilize the active catalytic species originating from the reaction of the two compounds, and which is sufficiently labile to be removed by an olefinic monomer. Preferably, the anion E" comprises one or more boron atoms. More preferably, the anion E" is an anion of the formula BAr/"\ wherein the substituents Ar which can be identical or different are aryl radicals such as phenyl, pentafluorophenyl or

bis(trifluoromethyl)phenyl. Tetrakis-pentafluorophenyl borate is particularly preferred
compound, as described in WO 91/02012. Moreover, compounds of formula BAr3 can be
conveniently used. Compounds of this type are described, for example, in the International
patent application WO 92/00333. Other examples of compounds able to form an
alkylmetallocene cation are compounds of formula BAr3P wherein P is a substituted or
unsubstituted pyrrol radical. These compounds are described in WO01/62764. Compounds
containing boron atoms can be conveniently supported according to the description of DE-A-
19962814 and DE-A-19962910. All these compounds containing boron atoms can be used in
a molar ratio between boron and the metal of the metallocene comprised between about
1:1 and about 10:1; preferably 1:1 and 2.1; more preferably about 1:1.
Non limiting examples of compounds of formula D+E" are:
Triethylammoniumtetra(phenyl)borate,
Tributylammoniumtetra(phenyl)borate,
Trimethylammoniumtetra(tolyl)borate,
Tributylammoniumtetra(tolyl)borate,
Tributylammoniumtetra(pentafluorophenyl)borate,
Tributylammoniumtetra(pentafluorophenyl)aluminate,
Tripropylammoniumtetra(dimethylphenyl)borate,
Tributylammoniumtetra(trifluoromethylphenyl)borate,
Tributylammoniumtetra(4-fluorophenyl)borate,
N,N-Dimethylbenzylammonium-tetrakispentafluorophenylborate,
N,N-Dimethylhexylamonium-tetrakispentafluorophenylborate,
N,N-Dimethylaniliniumtetra(phenyl)borate,
N,N-Diethylaniliniumtetra(phenyl)borate,
N,N-Dimethylaniliniumtetrakis(pentafluorophenyl)borate,
N,N-Dimethylaniliniumtetrakis(pentafluorophenyl)aluminate,
N,N-Dimethylbenzylammonium-tetrakispentafluorophenylborate,
N,N-Dimethylhexylamonium-tetrakispentafluorophenylborate,
Di(propyl)ammoniumtetrakis(pentafluorophenyl)borate,
Di(cyclohexyl)ammoniumtetrakis(pentafluorophenyl)borate,
Triphenylphosphoniumtetrakis(phenyl)borate,

Triethylphosphoniumtetrakis(phenyl)borate,
Diphenylphosphoniumtetrakis(phenyl)borate,
Tri(methylphenyl)phosphoniumtetrakis(phenyl)borate,
Tri(dimethylphenyl)phosphoniumtetrakis(phenyl)borate,
Triphenylcarbeniumtetrakis(pentafluorophenyl)borate,
Triphenylcarbeniumtetrakis(pentafluorophenyl)aluminate,
Triphenylcarbeniumtetrakis(phenyl)aluminate,
Ferroceniumtetrakis(pentafluorophenyl)borate,
Ferroceniumtetrakis(pentafluorophenyl)aluminate.
Triphenylcarbeniumtetrakis(pentafluorophenyl)borate, and
N,N-Dimethylaniliniumtetrakis(pentafluorophenyl)borate.
Organic aluminum compounds used as compound c) are those of formula HJA1U3-J or
HjAyJe-j as described above.
The catalysts of the present invention can also be supported on an inert carrier. This is
achieved by depositing the metallocene compound a) or the product of the reaction thereof
with the component b), or the component b) and then the metallocene compound a) on an
inert support. The support can be a porous solid such as talc, a sheet silicate, an inorganic
oxide or a finely divided polymer powder (e.g. polyolefin). Suitable inorganic oxides may
be found among the oxides of elements of groups 2, 3, 4, 5, 13, 14, 15 and 16 of the
Periodic Table of the Elements. Examples of oxides preferred as supports include silicon
dioxide, aluminum oxide, and also mixed oxides of the elements calcium, aluminum,
silicon, magnesium or titanium and also corresponding oxide mixtures, magnesium
halides, styrene/divinylbenzene copolymers, polyethylene or polypropylene. Other
inorganic oxides which can be used alone or in combination with the abovementioned
preferred oxidic supports are, for example, MgO, Z1O2, T1O2 or B2O3.
A suitable class of supports which can be used is that constituted by porous organic supports
ftinctionalized with groups having 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 application EP-633 272.
Another class of inert, supports particularly suitable for use according to the invention is that
of polyolefin porous prepolymers, particularly polyethylene.

A further suitable class of inert supports for use according to the invention is that of porous magnesium halides such as those described in International application WO 95/32995. The support materials used preferably have a specific surface area in the range from 10 to 1 000 m2/g, a pore volume in the range from 0.1 to 5 ml/g and a mean particle size of from 1 to 500 |im. Preference is given to supports having a specific surface area in the range from 50 to 500 m /g, a pore volume in the range from 0.5 to 3.5 ml/g and a mean particle size in the range from 5 to 350 |im. Particular preference is given to supports having a specific surface area in the range from 200 to 400 m /g, a pore volume in the range from 0.8 to 3.0 ml/g and a mean particle size of from 10 to 100 \xm. The inorganic support can be subjected to a thermal treatment, e.g. to remove adsorbed water. Such a drying treatment is generally carried out at from 80 to 300°C, preferably from 100 to 200°C, with drying at from 100 to 200°C preferably being carried out under reduced pressure and/or a blanket of inert gas (e.g. nitrogen), or the inorganic support can be calcined at from 200 to 1 000°C to produce the desired structure of the solid and/or set the desired OH concentration on the surface. The support can also be treated chemically using customary desiccants such as metal alkyls, preferably aluminum alkyls, chlorosilanes or SiCU, or else methylaluminoxane. Appropriate treatment methods are described, for example, in WO 00/31090.
The inorganic support material can also be chemically modified. For example, treatment of silica gel with (NH^SiFe leads to fluorination of the silica gel surface, or treatment of silica gels with silanes containing nitrogen-, fluorine- or sulfur-containing groups leads to correspondingly modified silica gel surfaces.
Organic support materials such as finely divided polyolefin powders (e.g. polyethylene, polypropylene or polystyrene) can also be used and are preferably likewise freed of adhering moisture, solvent residues or other impurities by means of appropriate purification and drying operations before use. It is also possible to use fiinctionalized polymer supports, e.g. supports based on polystyrene, via whose functional groups, for example ammonium or hydroxy groups, at least one of the catalyst components can be immobilized. The solid compound obtained by supporting the catalyst system object of the present invention on a carrier in combination with the further addition of the alkylaluminium compound either as such or prereacted with water if necessary, can be usefully employed in

the gas-phase or slurry polymerization.
Therefore a further object of the present invention is a catalyst system as described above,
further comprising d) an inert carrier.
The catalyst system comprising the metallocene compound of formula (I) can be used for
polymerizing olefins, in particular alpha-olefins in high yields to obtain polymers having
high molecular weight. Therefore a further object of the present invention is a process for
preparing a alpha-olefin polymer comprising contacting under polymerization conditions
one or more alpha-olefins of formula CH2=CHA wherein A is hydrogen or a C1-C20 alkyl
radical, in the presence of a catalyst system as described above.
Non limitative examples of alpha-olefins of formula CH2=CHA are: ethylene, propylene, 1-
butene, 1-hexene, 1-octene and 4-methyl-l-pentene, preferred alpha olefins are ethylene
propylene and 1 -butene.
The metallocene compounds of formula (I) object of the present invention are particularly
suitable for the homo and copolymerization of propylene. In fact, the metallocene-based
catalyst system of the present invention when used for homo or copolymerizing
propylene are able to give polymers having a high molecular weight in high yields also at
high temperatures rendering thus possible to use it in the industrial plants that use
polymerization temperatures higher than 50°C and that can be comprised between 60 and
120°C.
As said above the metallocene compounds of formula (I) are particularly suitable for the
copolymerization of propylene, therefore a farther object of the present invention is a
process for the preparation of propylene copolymers comprising the step of contacting,
under polymerization conditions, propylene with ethylene or one or more alpha olefins of
formula CH2=CHA1, wherein A1 is a C2-C20 alkyl radical, in the presence of a catalyst
system described above.
Examples of alpha olefins of formula CH2=CHA] are 1-butene, 1-hexene, 1-octene and 4-
methyl-1-pentene, preferred alpha olefins are ethylene and 1-butene; more preferred
alpha olefin is ethylene.
The content of alpha-olefins derived units in the propylene copolymer object of the
present invention ranges from 0.1 to 90% by mol; preferably it ranges from 5% by mol to
70% by mol; more preferably it ranges from 10% by mol to 60% by mol.

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 ranging from 5 to 50% by mol. Particularly preferred are ethylene/1-butene copolymer having a content of 1-butene derive units ranging from 5 to 50% by mol. Said copolymers can be obtained in high yields by using a gas phase process such a fluidized bed or stirred bed reactor. The process for the polymerization of olefins according to the invention can be carried out in slurry or in the gas phase. The hydrocarbon solvent can either be aromatic such as toluene, or aliphatic such as propane, hexane, heptane, or isobutane.
The polymerization temperature is generally comprised between -100°C and +200°C and, particularly between 10°C and +100°C. The polymerization pressure is generally comprised between 0,5 and 100 bar.
The lower the polymerization temperature, the higher are the resulting molecular weights of the polymers obtained.
The polymerization yields depend on the purity of the metallocene compound. The metallocene compounds obtained by the process of the invention can therefore be used as such or can be subjected to purification treatments.
When the metallocene compounds of the present invention are used as catalyst component in a polymerization process the activity of the catalyst system is strongly activated by the presence of hydrogen. This feature is even more important if it is considered that the molecular weight of the obtained polymer is not influenced in a considerable way by this addiction and it remains quite high for industrial use even in the presence of high amount of hydrogen. Thus a further object of the present invention is a process for preparing a alpha-olefin polymer comprising contacting under polymerization conditions one or more alpha-olefins of formula CH2=CHA wherein A is hydrogen or a C1-C20 alkyl radical, in the presence of a catalyst system as described above wherein the polymerization reaction I scarried out in the presence of hydrogen. Preferably the amount of hydrogen ranges from 0.5 NL (normal liter) to 10 NL; even more preferably it ranges from 4.5 NL to 8 NL. In view of the optimum behavior of the metallocene compounds of formula (I) when used for the homo and copolymerization of propylene, the catalyst system based on the metallocene compounds object of the present invention can be used in a multistage

process for preparing heterophasic propylene copolymers. Therefore a farther object of the present invention is a multistage polymerization process comprising the following steps:
a) polymerizing propylene with optionally ethylene or one or more alpha olefins of formula CH2=CHA1, wherein A1 is a C2-C20 alkyl radical, in the presence of a catalysts system described above;
b) contacting, under polymerization conditions, propylene with ethylene or one or more alpha olefins of formula CH2=CHA1, and optionally with a non-conjugated diene, in the presence of the polymer obtained in step a) and optionally in the presence of an additional organo aluminum compound;
provided that the polymer produced in step a) is different from the copolymer produced in step b) for the comonomer derived units amount or comonomer derived units structure; wherein the amount of the polymer obtained in step a) ranges from 2% to 98% by weight of the polymer obtained in the whole process and the amount of polymer obtained in step b) ranges from 98% to 2% by weight of the polymer obtained in the whole process. Preferably step a) further comprises a prepolymerization step a-1).
The prepolymerization step a-1) can be carried out by contacting the catalyst system described above with one ore more alpha olefins of formula CH =CHA wherein A is hydrogen or a C1-C20 alkyl radical; preferably said alpha olefin is propylene or ethylene, at a temperature ranging from -20°C to 70°C, in order to obtain a prepolymerized catalyst system containing preferably from 5 to 500 g of polymer per gram of catalyst system. Step a) of the present invention can be carried out in liquid phase, in which the polymerization medium can be an inert hydrocarbon solvent or the polymerization medium can be liquid propylene optionally in the presence of an inert hydrocarbon solvent, and of ethylene or one or more comonomer of formula CH2=CHA1, or step a) can be carried out in a gas phase. Said hydrocarbon solvent can be either aromatic (such as toluene) or aliphatic (such as propane, hexane, heptane, isobutane, cyclohexane and 2,2,4-trimethylpentane). Preferably the polymerization medium is liquid propylene. It can optionally contains minor amounts (up to 20% by weight, preferably up to 10% by weight, more preferably up to 5% by weight) of an inert hydrocarbon solvent or of ethylene or one or more comonomer of formula CH2=CHA1.

Step a) can be carried out in the presence of hydrogen. The amount of hydrogen present during the polymerization reaction is preferably more than 1 ppm; more preferably from 5 to 2000 ppm; even more preferably from 6 to 500 ppm with respect to the propylene present in the reactor. Hydrogen can be added either at the beginning of the polymerization reaction or it can also be added at a later stage after a prepolymerization step has been carried out.
The propylene polymer obtained in step a) is a propylene homopolymer or a propylene copolymer containing up to 20% by mol preferably from 0.1 to 10% by mol, more preferably from 1 % to 5% by mol of derived units of ethylene or one or more alpha olefins of formula CF^CHA1. Preferred comonomers are ethylene or 1-butene. Preferably in step a) a propylene homopolymer is produced.
The content of the polymer obtained in step a) preferably ranges from 5% to 90% by weight of the polymer produced in the whole process, more preferably it ranges from 10% to 70% by weight and still more preferably from 25% to 65% by weight of the total polymer produced in the whole process.
Step b) can be carried out in liquid phase, in which the polymerization medium can be an inert hydrocarbon solvent or the polymerization medium can be liquid propylene optionally in the presence of an inert hydrocarbon solvent, and of ethylene or one or more comonomer of formula CH2=CHA1, or step a) can be carried out in a gas phase. Preferably step b) is carried out in a gas phase, preferably in a fluidized or stirred bed reactor. The polymerization temperature is generally comprised between -100°C and +200°C, and, preferably, between 10°C and +90°C. The polymerization pressure is generally comprised between 0,5 and 100 bar.
In step b) a propylene copolymer containing from 5% to 90% by mol, preferably from 10% to 50% by mol, more preferably from 15% to 30% by mol of derived units of ethylene or one or more alpha olefins of formula CH2=CHA1 is produced. Examples of comonomer of formula CF^CHA1 that can be used in step b) of the present invention are: 1 -butene, 1 -pentene, 4-methyl-l-pentene, 1 -hexene, 1 -octene, 4,6-dimethyl-1 -heptene, 1 -decene, 1 -dodecene, 1 -tetradecene, 1 -hexadecene, 1 -octadecene and 1-eicosene. Preferred comonomers are ethylene or 1-butene.

The content of polymer obtained in step b) preferably ranges from 10 to 95% by weight of the polymer produced in the whole process, preferably it ranges from 30% to 90% by weight and more preferably from 35% to 75% by weight.
The polymer obtained in step b) can optionally contains up to 20% by mol of a non conjugated diene. Non conjugated dienes can be a straight chain, branched chain or cyclic hydrocarbon diene having from 6 to 20 carbon atoms. Examples of suitable non-conjugated dienes are:
- straight chain acyclic dienes, such as 1,4-hexadiene and 1,6-octadiene;
- branched chain acyclic dienes, such as 5-methyl- 1,4-hexadiene, 3,7 -dimethyl-1,6-octadiene, 3,7-dimethyl-l,7-octadiene and mixed isomers of dihydro myricene and dihydroocinene;
single ring alicyclic dienes, such as 1,3-cyclopentadiene, 1,4-cyclohexadiene, 1,5-cyclooctadiene and 1,5-cyclododecadiene;
- multi-ring alicyclic fused and bridged ring dienes, such as tetrahydroindene, methyl tetrahydroindene, dicyclopentadiene, bicyclo-(2,2,l)-hepta-2, 5-diene; and
- alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes, such as 5-methylene-2-norbornene (MNB), 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene,5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene and norbornadiene.
Preferred dienes are 1,4-hexadiene (HD), 5-ethylidene-2-norbornene (ENB), 5-
vinylidene-2-norbornene (VNB), 5-methylene-2-norbornene (MNB) and
dicyclopentadiene (DCPD). Particularly preferred dienes are 5-ethylidene-2-norbornene
(ENB) and 1,4-hexadiene (HD).
When present the non-conjugated dienes are preferably incorporated into the polymer in
an amount from 0.1% to about 20% by mol, preferably from 0.5% to 15% by mol, and
more preferably from 0.5% to 7% by mol. If desired, more than one diene may be
incorporated simultaneously, for example HD and ENB, with total diene incorporation
within the limits specified above.
A further multistage polymerization process process comprises the following steps:

al) polymerizing propylene with optionally ethylene or one or more monomers selected from alpha olefins of formula CT^CHA1, wherein A1 is a C2-C20 alkyl radical, in the presence of a catalysts system described above; bl) contacting, under polymerization conditions, ethylene with propylene or one or more alpha olefins of formula CH2=CHA\ and optionally with a non-conjugated diene, in the presence of the polymer obtained in step a) and optionally in the presence of an additional organo aluminum compound; provided that the polymer produced in step al) is different from the copolymer produced in step bl) for the comonomer derived units amount or comonomer derived units structure;
wherein the amount of the polymer obtained in step al) ranges from 2% to 98% by weight of the polymer obtained in the whole process and the amount of polymer obtained in step bl) is ranges from 98% to 2% by weight of the polymer obtained in the whole process.
Preferably step al) further comprises a prepolymerization step al-1). The prepolymerization step al-1) can be carried out by contacting the catalyst system described above with one ore more alpha olefins of formula CH2=CHA wherein A is hydrogen or a C1-C20 alkyl radical; preferably said alpha olefin is propylene or ethylene, at a temperature ranging from -20°C to 70°C, in order to obtain a prepolymerized catalyst system containing preferably from 5 to 500 g of polymer per gram of catalyst system. Step al) can be carried out in liquid phase, in which the polymerization medium can be an inert hydrocarbon solvent or the polymerization medium can be liquid propylene optionally in the presence of an inert hydrocarbon solvent, and ethylene or one or more comonomer of formula CH2—CHA1, or step al) can be carried out in a gas phase. Said hydrocarbon solvent can be either aromatic (such as toluene) or aliphatic (such as propane, hexane, heptane, isobutane, cyclohexane and 2,2,4-trimethylpentane).
Preferably the polymerization medium is liquid propylene. It can optionally contains minor amounts (up to 20% by weight, preferably up to 10% by weight, more preferably up to 5% by weight) of an inert hydrocarbon solvent or of ethylene or one or more comonomer of formula CH2=CHA1.

Step al) can be carried out in the presence of hydrogen. The amount of hydrogen present during the polymerization reaction is preferably more than 1 ppm; more preferably from 5 to 2000 ppm; even more preferably from 6 to 500 ppm with respect to the propylene present in the reactor. Hydrogen can be added either at the beginning of the polymerization reaction or it can also be added at a later stage after a prepolymerization step has been carried out.
The propylene polymer obtained in step al) is a propylene homopolymer or a propylene copolymer containing up to 20% by mol preferably from 0.1 to 10% by mol, more preferably from 1% to 5% by mol of derived units of ethylene or one or more alpha olefins of formula CP^CHA1. Preferred comonomers are ethylene or 1-butene. Preferably in step al) a propylene homopolymer is produced.
The content of the polymer obtained in step al) preferably ranges from 5% to 90% by weight of the polymer produced in the whole process, more preferably it ranges from 10% to 70%) by weight and still more preferably from 25% to 65% by weight of the total polymer produced in the whole process.
Step bl) can be carried out in liquid phase, in which the polymerization medium can be an inert hydrocarbon solvent or the polymerization medium can be a liquid monomer such as ethylene, propylene or one or more comonomer of formula CT^CHA1 optionally in the presence of an inert hydrocarbon solvent, or step bl) can be carried out in a gas phase. Preferably step bl) is carried out in a gas phase, preferably in a fluidized or stirred bed reactor. The polymerization temperature is generally comprised between -100°C and +200°C, and, preferably, between 10°C and +90°C. The polymerization pressure is generally comprised between 0,5 and 100 bar.
In step bl) an ethylene copolymer containing from 5% to 90% by mol, preferably from 10% to 50% by mol, more preferably from 15% to 30% by mol of derived units of propylene or one or more alpha olefins of formula CH2=CHA1 is produced. Examples of comonomer of formula CH2=CHA1 that can be used in step bl) of the present invention are: 1 -butene, 1 -pentene, 4-methyl-l-pentene, 1 -hexene, 1 -octene, 4,6-dimethyl-1 -heptene, 1 -decene, 1 -dodecene, 1 -tetradecene, 1 -hexadecene, 1 -octadecene and 1-eicosene. Preferred comonomers are propylene or 1-butene.

The content of polymer obtained in step bl) preferably ranges from 10 to 95% by weight of the polymer produced in the whole process, preferably it ranges from 30% to 90% by weight and more preferably from 35% to 75% by weight.
The polymer obtained in step bl) can optionally contains up to 20% by mol of a non conjugated diene. Non conjugated dienes can be a straight chain, branched chain or cyclic hydrocarbon diene having from 6 to 20 carbon atoms. Examples of suitable non-conjugated dienes are:
straight chain acyclic dienes, such as 1,4-hexadiene and 1,6-octadiene;
- branched chain acyclic dienes, such as 5-methyl-1,4-hexadiene, 3,7-dimethyl-l,6-
octadiene, 3,7-dimethyl-l,7-octadiene and mixed isomers of dihydro myricene and
dihydroocinene;
single ring alicyclic dienes, such as 1,3-cyclopentadiene, 1,4-cyclohexadiene, 1,5-cyclooctadiene and 1,5-cyclododecadiene;
- multi-ring alicyclic fused and bridged ring dienes, such as tetrahydroindene, methyl tetrahydroindene, dicyclopentadiene, bicyclo-(2,2,l)-hepta-2, 5-diene; and
- alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes, such as 5-methylene-2-norbornene (MNB), 5-propenyl-2-norbomene, 5-isopropylidene-2-norbornene,5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene and norbornadiene.
Preferred dienes are 1,4-hexadiene (HD), 5-ethylidene-2-norbornene (ENB), 5-
vinylidene-2-norbornene (VNB), 5 -methylene-2-norbornene (MNB) and
dicyclopentadiene (DCPD). Particularly preferred dienes are 5-ethylidene-2-norbornene
(ENB) and 1,4-hexadiene (HD).
When present the non-conjugated dienes are preferably incorporated into the polymer in
an amount from 0.1% to about 20% by mol, preferably from 0.5% to 15% by mol, and
more preferably from 0.5% to 7% by mol. If desired, more than one diene may be
incorporated simultaneously, for example HD and ENB, with total diene incorporation
within the limits specified above.
The processes of the present invention can be carried out in one reactor or in two or more
reactors in series.
Further object of the present invention is a ligand of formula (III)



wherein L, R1, R4, R5, R6, R7, R8, R9, R11 and R12 have the meaning reported above. A further preferred ligand has formula (Illb)

or its double bond isomers
wherein L, R1, R4, R14, R15, R16, Rn and R12 have the meaning reported above.
The metallocene compounds of formula (I) can be obtained with a process comprising the
steps of reacting the dianion with a suitable transition metal source such as metal
tetrahalide as for example zirconium tetrachloride. The dianion can be obtained for
example by the deprotonation of the ligand of formula (III), for example by using an
organolithium compound such as buthyl or methyl lithium.
The ligand of formula (III) can be easily prepared starting from the cyclopentadienyl
moiety of formula (IV)


wherein R1, R2, R3, R4 and W have the meaning described above with a process comprising the following steps:
a) Contacting the compound of formula (IV) and/or its double bond isomers with a base selected from TjB, TMgT1, sodium and potassium hydride, metallic sodium and potassium; wherein T, j, B and T1 are defined as above, and wherein the molar ratio between said base and the compound of the formula (IV) is at least 1:1; excess of said base can be used;
b) contacting the anionic compound obtained in step a) with a compound of formula LY2 wherein L is defined as above and Y is chlorine, bromine and iodine, preferably Y is chlorine or bromine; to form a compound of formula (IVa)

c) contacting the compound of formula (IVa) with the anionic derivative of compound of formula (IV) obtained as described in step a). The process described above can be carried out also "one pot" by reacting a calculate amount of the compound of formula LY2 with the dianionic derivative formed in step a). The above processes are preferably carried out in an aprotic solvent, either polar or apolar. Said aprotic solvent is preferably an aromatic or aliphatic hydrocarbon, optionally halogenated, or an ether; more preferably it is selected from benzene, toluene, pentane,

hexane, heptane, cyclohexane, dichloromethane, diethylether, tetrahydrofurane and
mixtures thereof. The above process is carried out at a temperature ranging from -100°C
to +80°C, more preferably from -20°C to +70°C.
The following examples are given to illustrate and not to limit the invention.
Examples
General characterization
Intrinsic viscosity (IV) in decahydronaphthalene
The intrinsic viscosity in Decahydronaphthalene (DHN) was determined on an
Ubbelohde viscometer PVS 1 with an S 5 measuring head (both from Lauda) in decalin at
135°C. To prepare the sample, 20 mg of polymer were dissolved in 20 ml of decalin at
135°C over a period of 2 hours. 15 ml of the solution were placed in the viscometer; the
instrument carried out a minimum of three running-out time measurements until a
consistent result had been obtained. The IV was calculated from the running-out times
according to IV = (t/t0-l)*l/c where t: mean of the running-out time of the solution, tO:
mean of the running-out time of the solvent, c: concentration of the solution in g/ml.
Intrinsic viscosity (IV) in tctrahydronaphthalcnc
The measurement for examples 1-5 were done in tetrahydronaphthalene (THN) solution
obtained by dissolving the polymer at 135°C for 1 hour as described above.
Xylene soluble fraction at 25°C
2.5g of polymer were dissolved in 250 ml of o-xylene under stirring at 135°C for 30
minutes, then the solution was cooled to 25°C and after 30 minutes the insoluble polymer
was filtered. The resulting solution was evaporated in nitrogen flow and the residue was
dried and weighed to determine the percentage of soluble polymer.
Melting Temperature Tm
Calorimetric measurements were performed by using a differential scanning calorimeter
DSC Mettler. The instrument is calibrated with indium and tin standards. The weighted
sample (5-10 mg), was sealed into aluminum pans, heated to 200°C and kept at that
temperature for a time long enough (5 minutes) to allow a complete melting of all the
crystallites. Successively, after cooling at 20°C/min to 0°C and standing for 5 minutes at
0°C, the sample was heated to 200°C at a rate of 20°C/min. In this second heating run,

the peak temperature was assumed as melting temperature (Tm) and the area as the global
melting enthalpy (AH).
Gel permeation chromatography
Gel permeation chromatography (GPC) was carried out at 145 °C in 1,2,4-
trichlorobenzene using a GPC apparatus 150C from Waters. The data were evaluated
using the software Win-GPC from HS-Entwicklungsgesellschaft fiirwissenschaftliche
Hard- und Software mbH, Ober-Hilbersheim. The calibration of the columns was carried
out by means of polypropylene standards having molar masses of from 100 to 107 g/mol.
Mass average molar masses (Mw) and number average molar masses (Mn) of the
polymers were determined.
Chemicals and characterization.
All chemicals were handled using standard Schlenk techniques.
Methylalumoxane (MAO) was received from Albemarle as a 30% wt/V toluene solution
and used as such and the silica was received from INEOS ( ES70Y, 100 microns).
Synthesis of rac-(i-{bis-[ri5-2-methyl-4-(4-terr-butylphenyl)-l,5,6,7-tetrahydro-5-
indaccn-l-yl]dimcthylsilancdiyl}dichlorozirconium (IV). (A-l)

a) Synthesis of Dimethyl[bis(2-methyl-4-(4-te#tf-butylphenyI)-l,5,6,7-tetrahydro-s-indacen-l-yl)]silane
Solution of 6-methyl-4-(4-?er?-butylphenyl)-l,2,3,5-tetrahydro-1y-indacene prepared as described in PCT/EP2004/013827 (4.06 g, 13.4 mmole) in Et20 (50 ml)) was cooled to -

40 °C, and n-BuLi in hexane (1.6M, 8.57 ml, 13.7 mmole) was added. Resulting mixture was allowed to warm to room temperature, stirred for 2 h, cooled to -60 °C, and CuCN (74 mg, 0.8 mmole) was added. After 15 min SiMe2Cl2 (0.81 ml, 6.71 mmole) was added. Resulting mixture was allowed to warm to room temperature, stirred for 16 h. H20 (5 ml) and hexane (200 ml) were added, organic phase was separated, dried over MgS04, passed through silica gel and evaporated. The residue was dried in vacuo. The product was used without purification.
!H NMR (CDC13, 20 °C) 5: 7.60-7.30 {groups of m, 10H, Aryl}; 6.72 (bs, 2H, -CH=); 3.87 (s); 3.86 (s) {2H, >CH-}; 3.12-2.89 (m); 2.14 (m) {12H, -CH2-}; 2.33 (s); 2.27 (s) {6H, C-CH3}; 1.50 (s, 18H, -C(CH3)3); -0.10 (bs, 6H, Si-CH3). b) Synthesis of (a-{bis-fti5-2-methyl-4-(4-ferr-butylpheiiyl)-l,5,6,7-tetrahydro-1$-indaccn-l-yI]dimcthylsilancdiyl}dichlorozirconium (TV). (A-l)
Obtained dimethyl[bis(2-methyl-4-(4-^ert-butylphenyl)-l,5,6,7-tetrahydro-.s'-indacen-l-
yl)]silane(4.65 g, 7.03 mmole) was dissolved in Et20 (40 ml), cooled to -40 °C, and n-BuLi (1.6M in hexane, 9.23 ml, 14.8 mmole) was added. Reaction mixture was allowed to warm to room temperature, stirred for 3 h, and evaporated. Resulting orange-yellow powder was suspended in pentane (100 ml), cooled to -60 °C, and ZrCU (1.73 g, 7.39 mmole) was added. After 5 min Et20 (1 ml) was added. Resulting mixture was allowed to warm to room temperature with stirring, stirred for additional 16 h, and filtered. Resulting orange-yellow powder was dried, DME (90 ml) and LiCl (0.2 g) were added, and resulting mixture was refluxed with stirring for 6 h. The solvent was evaporated Recrystallization of the residue from Et20 leads racemic form of metallocene. The yield 0.84 g (29%)
]H NMR (CD2CI0, 20 °C) 5: 7.44 (bs, 10H, Ph); 6.62 (s, 2H, -CH=); 2.98-2.70; 2.00-1.91 (group of m,12H, -CH2-); 2.19 (s, 6H, C-CH3); 1.34 (s, 18H, -C(CH3)3); 1.30 (s, 6H, Si-CH3).
rflc-dimethylsilyIbis(2-methyl-4-0?flrfl-tert-butylphenyl)-indenyl)-zirconium dichloride (rac-Me2Si(2-Me-4(4rBuPh)Ind)2ZrCl2) (C-l) rac-dimethylsilylbis(2-methyl-4-(para-tert-butylphenyl)-indenyl)-zirconium dichloride (rac-Me2Si(2-Me-4(4tBuPh)Ind)2ZrC12) (C-l) was prepared according to WO 98/40331 (example 65). Preparation of supported catalyst system

6,3 g SiOs are placed in a round flask equipped with a KPG stirrer and suspended at 0 °C in 30 ml toluene. Via a dropping funnel 15.1 ml MAO are slowly added at 0 °C. After addition, the suspension is allowed to come to room temperature (RT), and is then stirred for 2 h. The reaction mixture is placed in a stirred glass flask equipped with filter (size P3), where the solvent is filtered off. The residual is suspended in 20 ml toluene, stirred for 15 min at room temperature, and filtered. The support is suspended in 20 ml toluene, then brought to 80°C, and stirred for 30 min at this temperature before hot filtration. Again, the support is suspended in 20 ml toluene, then brought to 80°C, and stirred for 30 min at this temperature before hot filtration. The MAO/silica is suspended at 15 °C in 20 ml toluene. Under stirring, a solution of 0.25 mmol (207 mg, 40|amol/g carrier) of the metallocene indicated in table 1 in 2 ml MAO and 2 ml toluene is slowly added. The reaction mixture is stirred for 1 h at 15 °C, and after raising the temperature to 40 °C, again stirred for 2 h. Then, it is filtered. The residual solid is washed 3 times at 60 °C with 20 ml toluene each (stirring: 3 x 30 min). After the last filtration, the reaction product is transferred with some toluene into a glass frit (size P3), and filtered again. The catalyst is transfer after drying at RT in high vacuum until weight constant. Polymerization examples 1-2 (multistep polymerization) Step a)
A 2.5 L autoclave, previously kept overnight under nitrogen purge, is added with 2 mmol Triethylaluminum (TEA) (as 10% w/v hexane solution) as reactor scavenger. Also 0.5 bar-g of propylene are fed to prevent air insertion in the reactor.
Prepolymerization: 252 g propylene are fed in the autoclave at 0°C. The catalytic system is injected in the reactor and propylene is prepolymerized at 30°C for 5 minutes. At the end of this step the reactor temperature was raised from 30 to 70°C (in 10 minutes). During the temperature increase also 59 cc H2 are fed, corresponding to 2.63 mmol H2. Propylene polymerization in bulk this step is carried out at 30bar-g pressure and 70°C until the liquid propylene is totally consumed, and the pressure inside the reactor starts to decrease. When this step is completed, the PP matrix polymerization time is recorded and the pressure is released down to 0.1 bar-g propylene; at the same time the temperature decreases to 30°C. Step b)

Ethylene and propylene at a molar ratio ethylene(C2)/propylene(C3)-i-ethylene(C2) of 0.3
are feed in the reactor to reach the pressure of 21 bar-g then the temperature is raised to
60°C and the ethylene/propylene mixture is feed at constant pressure until 232g of
monomers are consumed.
Then the reactor is vented and cooled down to room temperature; thus, the reaction is
stopped. The polymer is collected and dried at reduced pressure and 60°C.
The resulting polymer has been subjected to xylene extraction at 25°C according to the
procedure described above. The fraction of polymer soluble in xylene at 25°C has been
taken as the amount of ethylene propylene copolymers produced in the process. The
polymerization data are reported in table 1

* comparative
EPR propylene ethylene polymer
Activities are referred to the catalyst as a whole, i.e. metallocene + MAO + Silica
Polymerization example 4 (mulstistep polymerization)
Step a)
A 2.5 L autoclave, previously kept overnight under nitrogen purge, is added with 2 mmol Triethylaluminum (TEA) (as 10% w/v hexane solution) as reactor scavenger. Also 0.5 bar-g of propylene are fed to prevent air insertion in the reactor.
Prepolymerization: 134 g propylene are fed in the autoclave at 0°C. The catalytic system is injected in the reactor and propylene is prepolymerized at 30°C for 5 minutes. At the end of this step the reactor temperature was raised from 30 to 80°C (in 10 minutes). Propylene polymerization in gas phase: this step is carried out at 21 bar-g pressure and 80°C until 70 grams of propylene are consumed and the pressure inside the reactor starts to decrease. When this step is completed, the PP matrix polymerization time is recorded and the pressure is released down to 0.1 bar-g propylene; at the same time the temperature decreases to 30°C.

Step b) In examples 4-6 the procedure used in examples 1 -3 has been repeated excepting that the Ethylene propylene molar ratio (ethylene(C2)/propylene(C3)+ethylene(C2)) fed was 0.2 and the polymerization in step b) was stopped when 232 grams of monomers were consumed. The results are reported in table 2

EPR propylene ethylene polymer
From table 1 clearly results that the polymerization activity of the catalyst system based on the metallocene compound of the present invention show an activity higher than the metallocene compound having the closest structure, both in propylene polymerization and propylene/ethylene copolymerization. Moreover the molecular weight of the propylene copolymer obtained with the metallocene of the present invention is considerably higher. Example 6 propylene homopolymcrization Preparation of the catalyst system
0.206mmol of a metallocene dichloride (A-l) were added at room temperature to 4.33mmol of MAO (30% strength solution in toluene, from Albemarle). The solution was allowed to stand overnight at room temperature and was subsequently diluted with 10.9ml of toluene. The diluted solution was carefully added to lOg of silica (Sylopol 948, calcined at 600°C, from Grace). Particular attention was paid to the colored solution being uniformly distributed over the support material. After 10 minutes, the flask containing the catalyst suspension was connected to a vacuum line and dried until the content of volatile material had been reduced to less than 5% by weight. Propylene homopolymcrization
Homopolymerizations were carried out in a 10 1 reactor charged with 3.5kg of liquid propene. The reactor was made inert by means of nitrogen before being charged. 8ml of a 20% strength by weight solution of triethylaluminum in Exxsol (from Witco) were introduced into the reactor and the mixture was stirred at 30°C for 15 minutes. A

suspension of the respective catalyst as indicated in table 3 in 20ml of Exxsol was introduced into the reactor. The reactor temperature was increased to 65°C and maintained at this temperature for 60 minutes. The polymerizations were stopped by venting the reactor. The polymers were dried overnight under reduced pressure before being analyzed. The polymerization results are reported in table 3

Polymerization examples 7-13 propylene/ethylene copolymcrization
Step a)
A 11.7 L autoclave, previously kept overnight under nitrogen purge, is added with 8
mmol Triisobutylaluminum (TIBA) (as 20% wt/wt in Exxsol, 0.77mol/L) as reactor
scavenger. The autoclave is filled with 550 g Propylene and 70 mg Hydrogen.
Still at room temperature the catalytic system obtained as described above (the
metallocene used is A-l amounts indicated in table 4) is injected in the reactor by using
additional 150 g liquid propylene,.
The temperature is increased at 40°C, in 2-3 minutes, and the propylene is polymerized at
this temperature for 5 minutes.
Step b)
At the end of the prepolymerization step the monomer is totally flashed out. The reactor
is filled with the fresh Ethylene/Propylene monomer mixture and the t emperature is
increased to 60°C in order to reach the desired polymerization pressure (21 barg). This
step needs about 10 minutes.
Step c)

The ethylene/propylene mixture is fed at constant pressure for 60 minutes. Then the reactor is vented and cooled down to room temperature; thus, the reaction is stopped. The polymer is collected and dried at reduced pressure and 60°C.
The resulting polymer has been subjected to xylene extraction at 25°C according to the procedure described above. The fraction of polymer soluble in xylene at 25°C has been taken as the amount of ethylene propylene copolymers produced in the process. The polymerization data are reported in table4

C3= propylene ; C2= ethylene
In examples 7-13 it is shown that the molecular weight of the polymer does not
substantially change by increasing the ethylene content.
Polymerization examples 14-24 propylene polymerization in slurry with hydrogen
The catalyst system was prepared according to example 6 above by using A-l, Propylene homopolymcrization
Homopolymerizations were carried out in a 10 1 reactor charged with 3.5kg of liquid propene and an hydrogen amount as indicated in table 5. The reactor was made inert by means of nitrogen before being charged. 8ml of a 20% strength by weight solution of triethylaluminum in Exxsol (from Witco) were introduced into the reactor and the mixture was stirred at 30°C for 15 minutes. An amount indicated in table 5 of the catalyst system in suspension of 20ml of Exxsol was introduced into the reactor. The reactor temperature was increased to 65°C and maintained at this temperature for 60 minutes. The polymerizations were stopped by venting the reactor. The polymers were dried

overnight under reduced pressure before being analyzed.

In table 5 it is shown that the metallocene compounds object of the present invention increase in a considerable way the activity when hydrogen is added, but at the same time the molecular weight of the polymer obtained is still at an industrial applicable level.












Claims
1. A bridged metallocene compound of 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 in the Periodic Table of the Elements;
X, equal to or different from each other, is a hydrogen atom, a halogen atom, a R,
OR, OR'O, OSO2CF3, OCOR, SR, NR2 or PR2 group wherein R is a linear or
branched, cyclic or acyclic, Ci-Cw-alkyl, C2-C40 alkenyl, C2-C40 alkynyl,
C6-C4o-aryl, C7-C4o-alkylaryl or C?-C4o-arylalkyl radical; optionally containing
heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; and
R' is a Ci -C2o-alkylidene, C6-C2o-arylidene, C7-C2o-alkylarylidene, or
C7-C2o-arylalkylidene radical;
L is a divalent bridging group selected from C1-C20 alkylidene, C3-C20
cycloalkylidene, C6-C20 arylidene, C7-C20 alkylarylidene, or a C7-C20 arylalkylidene
radicals, optionally containing heteroatoms belonging to groups 13-17 of the
Periodic Table of the Elements, or it is a silylidene radical containing up to 5 silicon
atoms;
R1 is a linear C1-C40 hydrocarbon radical optionally containing heteroatoms
belonging to groups 13-17 of the Periodic Table of the Elements such as methyl or
ethyl radical or an alpha branched aryl or arylalkyl radical containing from 2 to 20

carbon atoms optionally containing O, N, S, P and Se atoms;
R and R , are part of 4-7 membered ring condensed to the benzene ring of the
indenyl moiety; said ring optionally containing heteroatoms belonging to groups 13-
16 of the Periodic Table of the Elements; the valence of each atom forming said ring
being filled with R18 radicals, wherein R18, equal to or different from each other,
are hydrogen atoms or Ci-Qo hydrocarbon radicals;
R4 is a hydrogen atom or a C1-C40 hydrocarbon radical optionally containing
heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements;
W is an aromatic 5 or 6 membered ring that can contain heteroatoms belonging to
groups 13-16 of the Periodic Table of the Elements; the valence of each atom of said
ring is substituted with hydrogen atom or it can optionally be substituted with R5
groups wherein R5, equal to or different from each other, are C1-C40 hydrocarbon
radicals optionally containing heteroatoms belonging to groups 13-17 of the
Periodic Table of the Elements.
2. The metallocene compound according to claim 1 wherein M is zirconium, titanium or haftnum; X is a hydrogen atom, a halogen atom, a OR'O or R group; L is SiCR1 ] )2 wherein Rn is a linear or branched, cyclic or acyclic, Ci-C4o-alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C6-C4o-aryl, C7-C4o-alkylaryl or C7-C4o-arylalkyl radical; R1 is a Ci-Cio-alkyl radical.
3. The metallocene compound according to claims 1 or 2 wherein R and R , are part of 5-6 membered ring condensed to the benzene ring of the indenyl moiety; said ring being substituted with R18 radicals wherein R18 is a hydrogen atom or a linear or branched, Ci-C2o-alkyl radical, R4 is a hydrogen atom, a Ci-Qo-alkyl or a C6-C4o-aryl radical.
4. The metallocene compound according to anyone of claims 1-3 wherein W is selected from the group comprising the following moieties of formula (Wa), (Wb) and (Wc):


wherein the * represents the point in which the moiety bound the indenyl moiety of the compound of formula (I);
R6, R7, R8, R9 and R10, equal to or different from each other, are hydrogen atoms or Ci-C4o hydrocarbon radicals optionally containing heteroatoms belonging to groups 13-17 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 CR group; 77 is a nitrogen atom or a CR group; Z~ is a nitrogen atom or a CR group; provided that not more that 2 groups among Z , Z , Z , Z and Z5 are nitrogen atoms;
Z is an oxygen atom, a sulfur atom, a NR group or a CR group; Z is an oxygen atom, a sulfiir atom, a NR14 group or a CR14 group; Z8is an oxygen atom, a sulfur atom, a NR15 group or a CR15gr°uP; Z9 is an oxygen atom, a sulfur atom, a NR16 group or a CR16 group;
Z10 is a nitrogen atom or a carbon atom that bonds the indenyl moiety of the structure of formula (I); with the proviso that not more than 1 group among Z6, Z7, Z8, Z9 or Z10 is a sulfiir atom, an oxygen atom or a nitrogen-containing group atom selected from NR13, NR14, NR15, NR16, and a nitrogen atom; R13, R14, R15 and R16, equal to or different from each other, are hydrogen atoms or C1-C40 hydrocarbon radicals optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; J. The metallocene compound according to anyone of claims 1-4 wherein W has formula (Wa) and R7 is a Ci-Cio-alkyl radical and R10, R6, R7 and R9 are hydrogen atoms.

The metallocene compound according to anyone of claims 1-4 wherein W has
formula (Wa) and R10 and R8are C]-C40-alkyl radicals and R6, R7 and R9are
hydrogen radicals.
The metallocene compound according to anyone of claims 1-4 wherein 4 wherein
W has formula (Wa) R6, R7 and R8 are Ci-Qo-alkyl radicals and R10 and R9 are
hydrogen atoms.
The metallocene compound according to anyone of claims 1-4 wherein 4 wherein
W has formula (Wa) R10, R6, R7, R8 and R9 are hydrogen atoms.
The metallocene compound according to anyone of claims 1-8 wherein W has
formula (Wb), Z1 is a nitrogen atom and Z2, Z3, Z4 and Z5 are respectively CR6,
CR7, CR8 and CR9 wherein R6, R7, R8, and R9 are defined as in claims 1-8.
The metallocene compound according to anyone of claims 1 -8 wherein W has
formula (Wb), 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 are defined as in
claims 1-8.
The metallocene compound according to anyone of claims 1-8 wherein W has
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 R9are defined as in
claims 1-8.
The metallocene compound according to anyone of claims 1-4 wherein Whas
formula (Wc), Z6 is an oxygen atom, a sulfur atom, a NR16 group, and Z7, Z8, Z9
and Z10 are respectively a CR14, CR15, CR16 and a carbon atom groups, wherein
R14 is a Ci-C4o-alkyl radical such as methyl or ethyl; and R15 and R16 are hydrogen
atoms.
The metallocene compound according to claim 12 wherein Z6 is an oxygen atom, a
sulfur atom.
The metallocene compound according to anyone of claims 1-13 having formula
(Il)or(IIa):


wherein M, L, X, R1, R4, R10, R6, R7, R8 , R14, R1S and R16 and R9 have the
11 19
meaning reported in claims 1 -7 and R and R , equal to or different from each other, are hydrogen atoms or G-C40 hydrocarbon radicals optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements.
15. A catalyst system for the polymerization of olefin obtainable by contacting:
a) a metallocene compound of formula (I) as described in claims 1-14;
b) at least an alumoxane or a compound able to form an alkylmetallocene
cation; and
c) optionally an organo aluminum compound.
16. The catalyst system according to claim 15 further comprising
d) an inert carrier.
17. A process for preparing a alpha-olefin polymer comprising contacting under
polymerization conditions one or more alpha-olefins of formula CH2=CHA
wherein A is hydrogen or a C]-C2o alkyl radical, in the presence of a catalyst
system as described in claims 9-10.

18. The process according to claim 17 wherein the alpha olefins are ethylene
. propylene and 1-butene.
19. The process according to claims 17 or 18 for the preparation of propylene copolymers comprising the step of contacting, under polymerization conditions, propylene with one or more alpha olefins of formula CH2=CHA1, wherein A1 is hydrogen or a C2-C20 alkyl radical, in the presence of a catalyst system as described in claims 9-10.
20. The process according to claim 19 wherein the alpha olefin is ethylene or 1-butene.
21. The process according to claims 13 or 14 carried out in slurry, or gas phase.
22. A multistage polymerization process comprising the following steps:

a) polymerizing propylene with optionally one or more monomers selected from alpha olefins of formula CH^CHA1, wherein A1 is hydrogen or a C2-C20 alkyl radical, in the presence of a catalysts system as described in claims 9-10;
b) contacting, under polymerization conditions, propylene with ethylene or one or more alpha olefins of formula CH2=CHA1, and optionally with a non-conjugated diene, in the presence of the polymer obtained in step a) and optionally in the presence of an additional organo aluminum compound;
provided that the polymer produced in step a) is different from the copolymer produced in step b) for the comonomer derived units amount or comonomer derived units structure; wherein the amount of the polymer obtained in step a) ranges from 2% to 98% by weight of the polymer obtained in the whole process and the amount of polymer obtained in step b) ranges from 98% to 2% by weight of the polymer obtained in the whole process.
23. The multistage polymerization process according to claim 22 wherein step a) further comprises a prepolymerization step a-1).
24. The multistage polymerization process according to claims 22-23 wherein in step a) propylene homopolymer or propylene/ethylene copolymer is produced and in step b) propylene/ethylene is produced.
25. A multistage polymerization process comprising the following steps:

al) polymerizing propylene with optionally ethylene or one or more monomers selected from alpha olefins of formula CH2=CHA1, wherein A1 is a C2-C20 alkyl radical, in the presence of a catalysts system as described in claims 9-10; bl) contacting, under polymerization conditions, ethylene with propylene or one or more alpha olefins of formula CH2-CHA1, and optionally with a non-conjugated diene, in the presence of the polymer obtained in step a) and optionally in the presence of an additional organo aluminum compound; provided that the polymer produced in step al) is different from the copolymer produced in step bl) for the cdmonomer derived units amount or comonomer derived units structure; wherein the amount of the polymer obtained in step al) ranges from 2% to 98% by weight of the polymer obtained in the whole process and the amount of polymer obtained in step bl) is ranges from 98% to 2% by weight of the polymer obtained in the whole process.
26. The multistage polymerization process according to claim 25 wherein step al)
further comprises a prepolymerization step al-1).
27. The multistage polymerization process according to claims 25-26 wherein in step
al) propylene homopolymer or propylene/ethylene copolymer is produced and in
step bl) ethylene/1-butene copolymer is produced.
28. The multistage polymerization process according to anyone of claims 23-27 wherein the content pf the polymer obtained in step a) or step al) ranges from 5% to 90% by weight of the polymer produced in the whole process.
29. The process according to anyone of claims 23-28 wherein step b) or step bl) is carried out in a gas phase.
30. The process according to anyone of claims 23-29 wherein step a) or step al) is
carried out in a gas phase or in slurry.
31. The process according to claim 17 wherein it is carried out in the presence of
hydrogen.


Documents:

4109-CHENP-2007 AMENDED CLAIMS 22-05-2014.pdf

4109-CHENP-2007 POWER OF ATTORNEY 22-05-2014.pdf

4109-CHENP-2007 AFFIDAVIT 09-09-2014.pdf

4109-CHENP-2007 AMENDED CLAIMS 09-09-2014.pdf

4109-CHENP-2007 AMENDED PAGES OF SPECIFICATION 09-09-2014.pdf

4109-CHENP-2007 CORRESPONDENCE OTHERS 04-07-2014.pdf

4109-CHENP-2007 CORRESPONDENCE OTHERS 03-09-2013.pdf

4109-CHENP-2007 EXAMINATION REPORT REPLY RECEIVED 22-05-2014.pdf

4109-CHENP-2007 EXAMINATION REPORT REPLY RECIEVED 09-09-2014.pdf

4109-CHENP-2007 POWER OF ATTORNEY 09-09-2014.pdf

4109-chenp-2007-abstract.pdf

4109-chenp-2007-claims.pdf

4109-chenp-2007-correspondnece-others.pdf

4109-chenp-2007-description(complete).pdf

4109-chenp-2007-form 1.pdf

4109-chenp-2007-form 3.pdf

4109-chenp-2007-form 5.pdf

4109-chenp-2007-pct.pdf


Patent Number 263162
Indian Patent Application Number 4109/CHENP/2007
PG Journal Number 42/2014
Publication Date 17-Oct-2014
Grant Date 10-Oct-2014
Date of Filing 18-Sep-2007
Name of Patentee BASELL POLYOLEFINE GmbH
Applicant Address BRUHLER STRASSE 60, 50389 WESSELING, GERMANY.
Inventors:
# Inventor's Name Inventor's Address
1 NIFANT'EV, ILYA 26 BAKINSKIKH KOMMISSAROV ST., APPT. 60, 12/3, 117526 MOSCOW, RUSSIA.
2 IVCHENKO, PAVEL V 60 LET OKTYABRYA AVENUE 23-1, APT. 40, MOSCOW 117036, RUSSIA.
3 OKUMURA, YOSHIKUNI 2-26-1-1109, KITIMIKATA, TAKATSU-KU, KANAGAWA 213-0005, JAPAN.
4 CIACCIA, ELEONORA VIA URBANO III, 21, I-44100 FERRARA, ITALY.
5 RESCONI, LUIGI VIA PALESTRO, 101, I-44100 FERRARA, ITALY.
PCT International Classification Number C08F 4/64
PCT International Application Number PCT/EP2006/060767
PCT International Filing date 2006-03-15
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 05102189.7 2005-03-18 EUROPEAN UNION