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  • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
  • Y10S526/943—Polymerization with metallocene catalysts

Definitions

• the present invention relates to compounds of the group of cyclopentadienes substituted to form polycyclic structures, as well as a process for their preparation.
• the present invention relates to new polycyclic cyclopentadienyl compounds which can be used, in the form of anions, as penta-hapto ( ⁇ D -) ligands coordinated to transition metals to form metallocenes .
• Cyclopentadienyl complexes of transition metals of Groups 3 to 6, and particularly of Group 4 of the periodic table, combined with alummoxanes or particular salts of non-coordmating anions, are known to be capable of polymerizing ⁇ -olefms and have been widely used for this purpose m the recent past.
• Cyclopentadienyl compounds comprise the di-unsaturated cyclic group with five carbon atoms having the following general formula (I) :
• R groups represent general substituents, either the same or different.
• these can be converted to one another by the shifting, m the pentagonal cycle, of the two double bonds and the hydrogen atom linked to the sole saturated carbon atom, the various substituents of the cycle usually being hydrogen or linear or branched organic radicals, optionally substituted, which, m the more general version, can also form one or more covalent ligands with each other to obtain cy-hack or polycyclic structures condensed with said cyclopentadienyl ring.
• these structures (la), (lb), (Ic), (Id) and (Ie) can be considered as being equivalent, as they are precursors of the same cyclopentadienyl anion.
• cyclopentadienyl compounds represented by structural formulae of the type (I), which form one of the ob ects thereof comprises the five mesomeric structures defined above.
• Substituted cyclopentadienyl hydrocarbon compounds consisting of saturated and unsaturated rings condensed on the cyclopentadienyl ring are known m the art, and some of them are commercial products, such as, for example, mdene, tetrahydromdene, fluorene, azulene, 1, 2-benzofluorene .
• any one of said R or Z groups preferably one of the groups selected from Z 1 , Z ⁇ , Rt, Xr or R-, can be a diva- lent organic group further bound to another organic group having from 5 to 20 carbon atoms and comprising a cyclopentadienyl group, and "n" has any of the integer values from 1 to 10 extremes included, and preferably ranges from 1 to 3.
• the cyclopentadienyl group is conventionally represented by a structure which comprises all the mesomeric forms obtainable by shifting the double bonds and the hydrogen atom in the cycle as required by the valency regulations.
• This shifting is not only formal, bur can be easily obtained in practice by forming a cyclopentadienyl anion of any compound having formula (II), for example by treatment with lithium butyl, and by subsequently acidifying to obtain a mixture of all possible five isomers, said mixture being also included in the scope of the present invention.
• the present invention relates to compounds having formula (II) wherein all the R and Z groups are hydrogen.
• Z 1 and Z are hydrogen and only two of the groups Ri, R__ , Rj, R are linear or branched alkyl with from 1 to 4 carbon atoms .
• one of the R, s or R- groups is methyl or ethyl, more preferably methyl.
• Ri and R 5 are methyl, and "n" is 2 or 3.
• one of the R-, R restroom or R groups is a divalent hydrocarbon or silane group having from 2 to 6 carbon atoms, further linked to a second cyclopentadienyl group having from 5 to 20 carbon atoms, preferably selected from cyclopentadienyl, indenyl, fluorenyl and homologous groups thereof, in particular linked to said R 5 , Rr, or R- group by means of a carbon atom of the cyclopenta- dienyl ring.
• Non-limiting examples of compounds having formula (II; are those represented by the following formulae, which for the purposes of simplicity, are not numbered:
• the polycyclic cyclopentadienyl compounds according to the present invention are relatively stable compounds, thev can be exposed to air, even if it is not convenient to keep them for long periods due to the possibility of the forma- tion of the corresponding di e ⁇ c products, according to the well known Diels-Alder reaction. For this reason, when there is the possible necessity of keeping these products for some time, it is preferable to transform them into one of the corresponding salts of alkaline or earth-alkaline metals, which, although being sensitive to oxygen and humidity present m the air, do not undergo any chemical alterations if kept an inert atmosphere.
• polycyclic compounds although new, can be prepared by adapting known techniques of organic chemistry for the purpose, by analogy with synthetic methods of compounds and organic structures already known or similar, such as, for example, the synthesis method described the European patent application cited above EP-A 760,355.
• the Applicant however has developed an original synthetic method, by modifying or combining known techniques, which allow these compounds to be obtained with a good yield a limited number of steps .
• a second object of the present invention therefore relates to a method for the preparation of the polycyclic cy- clopentadienyl compounds having formula (II) starting from a benzoketone having the following general formula
• a suitable reactive metal alkyl comprising the R, group, for example lithium al- kyl, a Grignard reagent, a magnesium dialkyl, an aluminum trialkyl etc., to obtain the desired compound having general formula (II) object of the present invention.
• the above polycyclic cyclopentadienyl compounds can be used for the formation of organometallic complexes of transition metals, particularly of group 4 of the periodic table of elements, which can be advantageously used as catalysts in various synthetic processes, such as for example, hydrogenation, oxidation and polymerization of olefins.
• a further object of the present invention therefore relates to saline (ionic) compounds comprising at least one polycyclic cyclopentadienyl anion formally deriving from any of the previous compounds having formula (II) by the extraction of an H ⁇ acid anion from the cyclopentadienyl ring, and also metal complexes comprising at least one of said cyclopentadienyl anions coordinated to a transition metal by means of covalent bonds of the ⁇ type.
• an object of the present invention relates to an organometallic compound having the following general formula (X) :
• each Ri, R_, RNase, R_, R 5 , R D , R 7 , Z 1 and Z ⁇ group, and also "n”, has the same meaning, both general and preferred, as the corresponding symbol in formula (II) above;
• W represents any metal of the periodic table of elements having an oxidation state (or valence) "v" greater than zero; each Z' is independently a group of an anionic nature bound to the metal M " " as anion in an ionic couple or with a covalent bond of the " ⁇ " type;
• Z" represents an organic radical having from 5 to 30 carbon atoms, comprising a cyclopentadienyl anion bound to the metal M " ;
• m has the value 1 or 0 depending on whether Z" is present or absent in the compound having formula (X) ;
• the above formula (X) includes all compounds comprising a metal M in an oxidation state greater than zero and at least one anion deriving from a ligand having the previous formula (II) according to what is specified above.
• These compounds can be of a saline ionic nature, especially with non-transition metals, or, when low energy orbitals of the metal are available to form bonds of the " ⁇ " type, these compounds are preferably in the form of co-ordinated complexes of a se i-covalent or covalent nature.
• M is preferably selected from metals of groups 4 to 6, and is more preferably Ti, Zr or Hf in oxidation state +4.
• Z" group in formula (X) is a second cyclopentadienyl anion, optionally, but not necessarily, selected from compounds having formula (II) above.
• a preferred object of the present invention relates to a bis-cyclopentadienyl complex of a transition metal M "1 of group 4 of the periodic table, having the following formula (XI) :
• each Ri, Ri, R, R, R 5 , R 6 , R7, Z 1 and Z ⁇ group, and also "n”, has the same meaning, both general and pre- ferred, as the corresponding symbol in formulae (II) and (X) above;
• M represents a metal selected from titanium, zirconium and hafnium having an oxidation state (or valence) "q" equal to 3 or 4, preferably 4;
• t has the value of 1 se the valence "q” of M q is 4, and the value of 0 if the valence of "q" of M q is 3;
• X' and X" each independently represent a group of a monovalent anionic nature ⁇ -bound to the metal M q , preferably selected from hydride, halide, a Ci-Czo al- kyl or alkylaryl group, a C : --C_.
• alkylsilyl group a C--C_ cycloalkyl group, a C, -C aryl or arylalkyl group, a C -C alkoxyl or thioalkoxyl group, a C_-C_ carboxylate or carbamate group, a C_-C_ dialkylamide group and a C 4 -C , alkylsilylamide group.
• C ] represents any organic group containing a ⁇ ' -cy- clopentadienyl or rp-heterocyclopentadienyl ring, of an anionic nature, preferably having at least from 5 to 30 carbon atoms, coordinated to the metal M ⁇ .
• the groups X' and X" having formula (XI) each independently represent a group of an anionic nature ⁇ -bound to the metal M 1 .
• Typical examples of X' and X" are hydride, halide, preferably chloride or bromide, a linear or branched alkyl group such as methyl, ethyl, butyl, isopropyl, isoamyl, oc- tyl, decyl, benzyl, an alkylsilyl group such as, for example, trimethylsilyl, triethylsilyl or tributylsilyl, a cycloalkyl group such as cyclopentyl, cyclohexyl, 4- methylcyclohexyl, an aryl group such as phenyl or toluyl, an alkoxyl or thioalkoxyl group such as methoxyl, ethoxyl, iso- or
• the two X' and X" groups can also be chemically bound to each other and form a cycle having from 4 to 7 atoms different from hydrogen, also comprising the metal M 1 .
• Typical examples of this aspect are divalent anionic groups such as the trimethylene or tetra ethylene group, or the ethylene- dioxy group.
• X' and X" groups which are particularly preferred for their accessibility and the easy preparation of the complexes which comprise them are chloride, C ⁇ -C £ alk- oxide, methyl, ethyl, C ⁇ -C: carboxylate.
• Each C- group in formula (XI) contains a ⁇ ⁇ -cy- clopentadienyl ring coordinated to the metal M ' , which formally derives from a cyclopentadiene molecule, substituted or non-substituted, by extraction of an H + ion.
• the molecular bond of the ⁇ type and also the electronic and coordi- native configuration of metallocene complexes of titanium, zirconium or hafnium, generally comprising two ⁇ 5 -cy- clopentadienyl groups, have been amply described in literature and are known to experts in the field.
• the C v group having formula (XI) according to the present invention is selected, in particular, from known cy- clopentadienyl, indenyl or fluorenyl groups, and their homologous products, in which one or more carbon atoms of the molecular skeleton (included or not included in the cyclopentadienyl ring) , are substituted with a radical selected from the group consisting of halogen, preferably chlorine or bromine, a linear or branched alkyl group having from 1
• - li to 10 carbon atoms optionally halogenated, such as methyl, trifluoromethyl, ethyl, butyl, isopropyl, isoamyl, octyl, decyl, benzyl, an alkylsilyl group such as, for example, t ⁇ methylsilyl, t ⁇ ethylsilyl or t ⁇ butylsilyl, a cycloal- kyl group such as cyclopentyl, cyclohexyl, 4-me- thylcyclohexyl, an aryl group having from 6 to 10 carbon atoms, optionally halogenated, such as phenyl, pentafluoro- phenyl or toluyl, an alkoxyl or thioalkoxyl group such as methoxyl, ethoxyl, iso- or sec-butoxyl, ethylsulfide .
• Said Cp group may also comprise several condensed aromatic rings, as the case, for example, of 4, 5-benzo denyl, and a particularly preferred embodiment, is selected from anions of polycyclic cyclopentadienyl compounds having formula (II) described above.
• the above groups of an anionic nature more specifically Z" the complexes having formula (X) with M a transition metal, and C L complexes having formula (XI), can be covalently bound to the polycyclic cyclopentadienyl group deriving from compounds having formula (II;, by means of a divalent hydrocarbon or silane group having from 1 to 15, preferably from 2 to 6, carbon atoms, to form a so-called "bridged" structure, according to the traditional terminology used in the field of metallocene compounds.
• Non-limiting examples of compounds having general for- mula (X) and (XI) are those represented by the structures indicated hereunder, which, for the sake of simplicity, are not numbered:
• the above complexes having formula (X) with certain transition metals can be advantageously used the formation of catalysts for the polym- erization and co-polymerization of olefms, combined with a suitable activator.
• a further object of the present invention therefore relates to, and is claimed herein as such, a catalyst for the (co) polymerization of ethylene and other ⁇ -olefms, i.e. for the homo-polymerization of ethylene and other ⁇ - olefms, the co-polymerization of ethylene with one or more other co-polyme ⁇ zable monomers, such as for example, ⁇ - olef s, conjugated or non-conjugated diolef s, styrene and its derivatives, etc., the co-polymerization of ⁇ - olefms with each other or with other monomers co- polymerizable therewith.
• This catalyst can be obtained from the combination (i.e.
• said catalyst m accordance with the present invention comprises the following two components contact with each otner, or the product of their reaction: (1) at least one metallocene complex having the previous formula (X) , wherein the metal M " " is a metal of groups 4 to 6, preferably 4, of the periodic table; (ii) a co-catalyst consisting of at least one organometallic compound of an element M' different from carbon and selected from elements of groups 2, 12, 13 or 14 of the periodic table as defined above.
• said element M' is preferably selected from boron, aluminum, zmc, magnesium, gallium and tm, more particularly boron and aluminum.
• the component (ii) is an organo-oxygenated derivative of aluminum, gallium or tm.
• This can be defined as an organic compound of M' , m which the latter is bound to at least one oxygen atom and to at least one organic group consisting of an alkyl group having from 1 to 6 carbon atoms, preferably methyl.
• component (ii) is more preferably an alum oxane.
• alu- mmoxanes are compounds containing Al-O-Al bonds, with a varying 0/A1 ratio, which can be obtained, under controlled conditions, by the reaction of an aluminum alkyl or aluminum alkyl halide, with water or other compounds containing pre-established quantities of water available, such as, for
• Alummoxanes preferably used for the formation of the polymerization catalyst of the present invention are oligo- poly-meric, cyclic and/or linear compounds, characterized by the presence of repetitive units having the following formula (XII) :
• R is a C -C, alkyl group, preferably methyl.
• Each dialuminoxane molecule preferably contains from 4 to 70 repetitive units which may also not all be equal to each other, but contain different R groups.
• Said alummoxanes, and particularly methylalummoxane are compounds which can be obtained by known methods m organometallic chemistry, for example, by the addition of aluminum trimethyl to a suspension hexane of aluminum sulfate hydrate.
• component (ii) in addition to the above alummoxanes, the definition of component (ii) according to the present invention also comprises galloxanes (in which, in the previous formulae, gallium is present instead of aluminum) and stannoxanes, whose use as cocatalysts for the polymerization of olefins in the presence of metallocene complexes is known, for example, from patents US 5,128,295 and US 5,258,475.
• said catalyst can be obtained by putting component (i) consisting of at least on complex having formula (X), in contact with component (ii) consisting of at least one compound or a mixture of organometallic compounds of M' capable of reacting with the complex having formula (X) , extracting from this a ⁇ -bound group Z' or Z" to form, on the one hand at least one neutral compound, and on the other hand an ionic compound consisting of a metallocene cation containing the metal M v and an organic non- coordinating anion containing the metal M' , whose negative charge is delocalized on a ulticentric structure.
• Components (ii) suitable as ionizing systems of the above type are preferably selected from the voluminous organic compounds of boron and aluminum, such as for example, those represented by the following general formulae: [ (R.) NH-- ] " [B(R:),] _ ; B (R, ) ; [ Ph-C] ⁇ [B (R. ) , ] " ;
• each R group independently represents an alkyl or aryl radical having from 1 to 10 carbon atoms and each R r group independently represents an aryl radical partially or, preferably, totally fluorinated, having from 6 to 20 carbon atoms .
• Said compounds are generally used in such quantities that the ratio between the atom M' of component (ii) and the atom M l in the metallocene complex is within the range of 0.1 to 15, preferably from 0.5 to 10, more preferably from 1 to 6.
• Component (ii) can consist of a single compound, nor- mally an ionic compound, or a combination of this compound with MAO, or, preferably, with an aluminum trialkyl having from 1 to 8 carbon atoms in each alkyl residue, such as for example AlMe_,, AlEt , Al(i-Bu) 3 .
• the formation of the ionic metallocene catalyst in accordance with the present invention, is preferably carried out in an inert liquid medium, more preferably hydrocarbon.
• an inert liquid medium more preferably hydrocarbon.
• R " is a linear or branched C -C alkyl group, or one of their mixtures
• X is a halogen, preferably chlorine or bromine
• m is a decimal number ranging from 1 to 3 extremes included
• Non-limiting examples of complex-cocatalyst combinations suitable for the preparation of ionic catalytic sys- tems m accordance with the present invention are schematized hereunder table (I), with reference to the respective precursors from whose combination they can be obtained. Any compound of any column can be combined, if necessary, with any compound of the remaining ones, according to the method indicated.
• Catalysts of the present invention based on mixtures of complexes having different catalytic activities can be advantageously used m polymerization when a wider molecular weight distribution of the polyolefms thus produced is desired.
• the metallocene component (i) of said catalyst consists of a complex selected from those represented by the previous formula (XI), especially with the metal M 1 m oxidation state +4, or a mixture of these complexes.
• the above complexes can also be supported on inert solids, preferably consisting of oxides of S_- and/or Al, such as, for example, silica, alumina or silica-alummates .
• inert solids preferably consisting of oxides of S_- and/or Al, such as, for example, silica, alumina or silica-alummates .
• the known supporting techniques can be used, normally comprising contact, a suitable inert liquid medium, between the carrier, optionally activated by heating to temperatures exceeding 200°C, and one or both of components (I) and (ii) of the catalyst of the present invention.
• both components it is not necessary for both components to be supported, as it is also possible for only the complex having formula (X) , or preferably (XI), or the organic compound of B, Al, Ga or Sn as defined above, to be present on the surface of the carrier. In the latter case, the component which is not pres- ent on the surface is subsequently put contact with the supported component, at the moment of the formation of the catalyst active for the polymerization.
• a particular method for the formation of a supported catalyst according to the present invention comprises pre- polymeriz g a relatively small fraction of monomer or mixture of monomers m the presence of the catalyst, so as to include this m a solid micro-particulate, which is then fed to the actual reactor itself for completing the process m the presence of an additional ⁇ -olefm. This provides a better control of the morphology and dimensions of the polymeric particulate obtained at the end.
• One or more other additives or components can be optionally added to the catalyst according to the present m- vention, as well as the two components (I) or (ii) , to ob- tain a catalytic system suitable for satisfying specific requests.
• the catalytic systems thus obtained should be considered as being included m the scope of the present invention.
• Additives or components which can be included m the preparation and/or formulation of the catalyst of the present invention are inert solvents such as, for example, aliphatic and/or aromatic hydrocarbons, aliphatic and aromatic ethers, weakly coordinating additives (Lewis basesj selected, for example, from non-polymerizable olefms, ethers, tertiary amines and alcohols, halogenatmg agents such as silicon halides, halogenated hydrocarbons, preferably chlorinated, and the like, and again all other possible components normally used m the art for the preparation of the traditional homogeneous catalysts of the metallocene type for the (co) polymerization of ethylene and ⁇ -olefms.
• solvents such as, for example, aliphatic and/or aromatic hydrocarbons, aliphatic and aromatic ethers, weakly coordinating additives (Lewis basesj selected, for example, from non-polymerizable olefms,
• Components (l) and (ii) form the catalyst of the present invention by contact with each other, preferably at temperatures ranging from room temperature to 60°C and for times varying from 10 seconds to 1 hour, more preferably from 30 seconds to 10 minutes.
• the catalysts according to the present invention can be used with excellent results m substantially all known
• a further object of the present invention therefore relates to a process for the (co) polymerization of ⁇ - olefms, comprising polymerizing said ⁇ -olefm, or copolym- erizmg one or more of said ⁇ -olefms, under suitable pressure and temperature conditions, the presence of at least one of the catalysts according to the present invention, as described above.
• a liquid diluent normally consisting of an aliphatic or cycloaliphatic saturated hydrocarbon, having from 3 to 8 carbon atoms, but which can also consist of a monomer as, for example, the known co-polymerization process of ethylene and propylene m liquid propylene.
• the quantity of catalyst introduced into the polymerization mixture is preferably selected so that the concentration of the tran- sition metal M or M 5 ranges from 10 "5 to 10 " moles/liter.
• the polymerization can be carried out m gas phase, for example, m a fluid bed reactor, normally at pressures ranging from 0.5 to 5 MPa and at temperatures ranging from 50 to 150°C.
• Said ⁇ -olefms comprise ethylene and its higher homologous products, preferably having from 3 to 15 carbon atoms, such as, for example, propylene, 1-butene, butadiene, 1-hexene, 1-octene, 1, 4-hexad ⁇ ene and styrene.
• Particular non-primary olefms, having the double bond included m a stretched ring, such as for example, dicyclo- pentadiene, can be equally (co) polymerized the presence of the catalyst of the present invention.
• the catalyst for the (co) polymerization of ⁇ -olefms is prepared separately (preformed) by contact of components (I) and (ii) , and is subsequently introduced into the polymerization environment.
• the catalyst can be charged first into the polymerization reactor, followed by the reagent mixture containing the olef or mixture of olefms to be polymerized, or the catalyst can be charged into the reac- tor already containing the reagent mixture, or finally, the reagent mixture and the catalyst can be contemporaneously fed into the reactor.
• the catalyst is formed " situ", for example by mtroduc- mg components (I) and (n) separately into the polymenza- tion reactor containing the selected olefinic monomers.
• the catalysts according to the present invention can be used with excellent results m the polymerization of ethylene to give linear polyethylene and m the copolymeri- zation of ethylene with propylene or higher ⁇ -olefms, preferably having from 4 to 10 carbon atoms, to give copolymers having different characteristics depending on the specific polymerization conditions and on the quantity and structure of the ⁇ -olefm.
• linear polyethyl- enes can be obtained, with a density ranging from 0.880 to
• the ⁇ -olefms preferably used as comonomers of ethylene the production of low or medium density linear polyethylene are 1-butene, 1-hexene and 1-octene .
• the catalyst of the present invention can also be conveniently used m copolymerization processes of ethylene and propylene to give saturated elastomeric copolymers vul- canizable by means of peroxides and extremely resistant to agmg and degradation, or m the terpolymerization of ethylene, propylene and a non-conjugated diene, having from 5 to 20 carbon atoms, to obtain vulcanizable rubbers of the EPDM type.
• m copolymerization processes of ethylene and propylene to give saturated elastomeric copolymers vul- canizable by means of peroxides and extremely resistant to agmg and degradation, or m the terpolymerization of ethylene, propylene and a non-conjugated diene, having from 5 to 20 carbon atoms, to obtain vulcanizable rubbers of the EPDM type.
• the catalysts of the present invention al- low the production of polymers having a particularly high diene
• the dienes which can be used for the preparation of said terpolymers are preferably selected from:
• linear chain dienes such as 1, 4-hexad ⁇ ene and 1,6- octadiene
• dienes with a single ring such as 1, 4-cyclohexad ⁇ ene; 1, 5-cyclo-octad ⁇ ene; 1, 5-cyclododecad ⁇ ene;
• dienes having bridged condensed rings such as dicyclo- pentadiene; bicyclo [2.2.1] hepta-2, 5-d ⁇ ene; alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norborne- nes such as 5-methylene-2-norbornene, 5-ethyl ⁇ dene-2- borbornene (ENB) , 5-propenyl-2-norbornene .
• dienes containing at least one double bond a stretched ring are preferred, even more preferably 5-ethyl ⁇ dene-2-norbornene (ENB), and also 1,4- hexadiene and 1, 6-octad ⁇ ene .
• ENB 5-ethyl ⁇ dene-2-norbornene
• 3 ⁇ - content on the otner han ⁇ ranges from 20 to 50° o by weight.
• the catalysts of the present invention can also be used homo- and co-polymerization processes of ⁇ -olefms according to the known techniques, giving, with excellent yields, atactic, isotactic or syndiotactic polymers, depending on the structure and geometry of the metallocene complex having formula (XI) .
• ⁇ -olefms suitable for the purpose are those having from 3 to 20 carbon atoms, optionally also comprising halogens or aromatic nuclei such as, for example, propylene, 1-butene, 1-hexene, 4-methyl-l- pentene, 1-decene and styrene.
• the measurement of the molecular weights of the ole- finic polymers was carried out by means of Gel-Permeation Chromatography (GPC) .
• the analyses of the samples were effected in 1, 2, 4-trichlorobenzene (stabilized with Santonox) at 135°C with a WATERS 150-CV chromatograph using a Waters differential refractometer as detector.
• the chromatographic separation was obtained with a set of ⁇ -Styragel HT columns (Waters) of which three with pore dimensions of 10 " , 10 , 10" A respectively, and two with pore dimensions of IX A, establishing a flow-rate of the eluant of 1 ml/min.
• the data were obtained and processed by means of Maxima 820 software version 3.30 (Millipore) ; the number (M n ) and weight (M w ) average molecular weight calculation was carried out by universal calibration, selecting polystyrene standards with molecular weights within the range of 6,500,000-2,000, for the calibration.
• the determination of the content of units deriving from propylene and possible diene in the polymers is carried out (according to the method of the Applicant) by means of IR on the same polymers in the form of films having a thickness of 0.2 mm, using an FTIR Perkin-Elmer spec- trophotometer model 1760.
• the intensity of the characteris- tic peaks is measured, of propylene at 4390 cm “ and ENB at 1688 cm “ respectively, m relation to the peak at 4255 cm " , and the quantity is determined using a standard calibration curve.
• the Melt Flow Index (MFI ) of the polymers is determined m accordance with the regulation ASTM D-1238 D.
• reagents and/or solvents used and not indicated above are those commonly used both m bench and on industrial scale and can be easily found at all commercial operators specialized m the field.
• the mixture is then heated to 80-90°C and 38 ml of ⁇ - tetralone (0.28 moles) diluted 80 ml of toluene are added, m about 3 hours, by means of a drip funnel.
• the re- action mixture is maintained at 90°C and the trend is periodically controlled by means of thm layer chromatography (T.L.C.) on samples removed for the purpose. After about 24 hours, the complete disappearance of ⁇ -tetralone is observed.
• the reaction mixture is carefully poured into about 1 kg of ice containing 50 ml of glacial acetic acid.
• the phases are separated and the aqueous phase is repeatedly extracted with ethyl ether, the organic extracts are subsequently washed with water saturated with NaHC0_ and then with water until neutrality.
• the NMR spectrum shows that the product is present in solution in ketonic and enolic forms in a ratio of 55/45 respectively.
• the mixture is kept at reflux temperature for about 3 hours and is then cooled to room temperature and left under stirring for the whole night. In this phase there is the progressive disappearance of the yellow milky solid with the formation of a colorless crystalline solid.
• About 400 ml of EtOH are removed by evaporation at reduced pressure, the mixture is subsequently hydrolyzed with water and ice and extracted with various portions of ethyl ether. The ether extracts are joined, washed with water until neutrality and dried on anhydrous NaSO,. The solvent is then evaporated at reduced pressure and 45 g of an oily reddish-brown residue is obtained, consisting of 70% by weight of the desired product (XIV) (GC analysis, 70% yield) .
• the aqueous suspension is cooled to room temperature and extracted with various portions of ethyl ether, the organic fractions are joined and subsequently washed with wa- ter saturated with NH 4 C1, then with water until neutrality and dried on anhydrous Na 2 S0 4 .
• the solvent is removed under vacuum and 26.5 g of an oily red residue are obtained, which contains 65% (GC analysis) of the product (XVII)
• the colourless solid thus obtained is dispersed in 200 ml of toluene, the ketoester (XIX) is added, the suspension is then heated to 80°C and 31 ml (0.295 moles) of propargyl chloride in a solution at 70% in toluene are added, by means of a drip funnel, in about an hour. After 24 hours, G.C. analysis of the reaction mixture shows that all the ketoester (XIX) has been converted. The reaction mixture is then hydrolyzed with water and ice and extracted with various portions of ethyl ether. The ether extracts are joined and subsequently washed with water and dried on anhydrous Na ' S0.
• the suspension is cooled to room temperature and extracted with various portions of ethyl ether.
• the ether extracts are subsequently washed with water saturated with NHC1 and subsequently with water until neutrality, then dried on anhydrous Na 2 S0, .
• 13 g of an oily red liquid are obtained, which is purified by means of flash chromatography on a column, using a 70/30 (by volume) mixture of hexane/ethyl acetate as eluant and Si0 2 (Merck) 32-60 as stationary phase.
• 2.2 g of the desired pure prod ⁇ uct (XXII) are obtained at the end.
• EXAMPLE 3 Synthesis of bis- (7, 9-di-methyl-4, 5-dihydro-benzo [d] indenyl) zirconium dichloride (XXX) 3a) Synthesis of 5, 7-dimethyl-l-oxo-2-ethoxycarbonyl- 1,2,3, 4-tetrahydronaphthalene (XXV)
• a suspension of 12.2 g (0.53 moles) of sodium hydride in a liter of toluene are maintained under stirring in a 2 liter flask for 2 hours at room temperature, and 85 ml (0.69 moles) of diethylcarbonate are then added.
• the mixture is heated to 90°C and 25 g of 5, 7-dimethyl-l-tetralone (0.14 moles) dissolved in 150 ml of toluene are added, in about 2 hours.
• the reaction mixture is kept under stirring for a further 8 hours at 90°C until the reagent disappears. At the end the reaction mixture is hydrolyzed by pouring it into ice containing 50 ml of glacial acetic acid.
• This lithium salt (1.48 mmoles) is suspended in 100 ml of anhydrous ethyl ether in a 250 ml flask and, after cooling to -20°C, 0.16 g (0.69 mmoles) of ZrCl are added. The temperature is left to rise to 25°C and the mixture is then kept under stirring for 4 hours. A light-coloured solid is formed which can be easily decanted. The suspension is filtered, the resulting ether solution is then dried and the solid thus obtained is re-crystallized from tolu- ene/pentane. The desired metallocene complex having formula (XXX) is thus recovered.
• EXAMPLES 4-14 copolymerization of ethylene with MAO as co- catalyst .
• Examples 4 to 14 refer to a series of co- and ter- polyme ⁇ zation tests for the preparation of elastome ⁇ c polymers of the EP(D)M type based on ethyl- ene/propylene/ethylidenenorbornene (ENB) , carried out using a catalytic system comprising one of the metallocene complexes, obtained as described above m examples 1 and 2, and methylalumoxane (MAO) as cocatalyst.
• EMB ethyl- ene/propylene/ethylidenenorbornene
• Table (II) The specific polymerization conditions of each example and the results ob- tamed are indicated Table (II), which specifies m succession, the reference example number, the metallocene complex used, the quantity of zirconium used, the atomic ratio between aluminum m MAO and zirconium m the metallocene, the total polymerization pressure, the initial concentra- tion of ENB, if present, the activity of the catalytic sys- tern as kilograms of polymer per gram of metal zirconium per hour (kg r ;./g- r xh), the relative quantity, by weight, of the C monomeric units and ENB in the polymer, the weight average molecular weight M. and the molecular weight dispersion M K /M P .
• Table (II) specifies m succession, the reference example number, the metallocene complex used, the quantity of zirconium used, the atomic ratio between aluminum m MAO and zirconium m the
• the polymerization is carried out in a 0.5 liter pressure reactor, equipped with a magnetic anchor drag stirrer and an external jacket connected to a heat exchanger for the temperature control.
• the reactor is previously flushed by maintaining under vacuum (0.1 Pascal) at a temperature of 80°C for at least 2 h.
• MAO as a 1.5 M solution (as Al) in toluene and the desired quantity of one of the above metallocene complexes, as a toluene solution having a concentration generally ranging from 3 x 10 " to 1 x 10 M, are charged into a suitable tailed test-tube, maintained under nitrogen.
• the catalyst solution thus formed is maintained at room tem- perature for a few minutes and is then transferred under a stream of inert gas to a metal container from which it is introduced into the reactor, by means of an overpressure of nitrogen.
• the polymerization reaction is carried out at 40°C, care being taken that the total pressure is kept constant by continuously feeding ethylene to compensate the part which has reacted m the meantime. After 15 minutes the feeding of ethylene is interrupted and the polymerization is stopped by the rapid degassing of the residual monomers. The polymer is recovered, after washing it with ethyl alcohol and drying at 60°C, at a reduced pressure of 1000 Pa, for at least 8 hours, m order to completely eliminate any possible residual monomers. The solid thus obtained is weighed and the catalytic activity is calculated as de- scribed above.
• Examples 15 to 19 refer to copolymerization tests of ethylene with propylene for the preparation of the corresponding elastomeric polymers of the EPR type, carried out using a catalytic system comprising the metallocene complex having formula (XVIII) obtained as described above in example 1, an aluminum alkyl and an appropriate compound of boron as co-catalyst (catalytic system of the cationic type) .
• Table III specifies in succession, the reference example number, the quantity of zirconium used, the atomic ratio between aluminum and zirconium, the atomic ratio between boron and zirconium, the total polymerization pressure, the activity of the catalytic system with reference to the zirconium, the relative quantity, by weight, of the Cj monomeric units in the polymer, the weight average molecular weight M- and the molecular weight dispersion M w /M r , .
• the polymerization is carried out in a 0.5 liter pressure reactor, equipped with a magnetic anchor drag stirrer and an external jacket connected to a heat exchanger for the temperature control.
• the reactor is previously flushed by maintaining under vacuum (0.1 Pascal) at a temperature of 80°C for at least 2 h.
• the catalytic system is introduced from a suitable con- tamer connected tc the reactor, by means of an overpressure of nitrogen.
• the polymerization reaction is carried out using the same procedure and under the same conditions as the previous examples 4 to 14.
• the polymer thus obtained is weighed and the catalytic activity is calculated as kilograms of polymer per gram of metal zirconium per hour (kg t i /g -t xh) .
• the content of propylene units is measured on the dried and homogenized solid, by means of the known techniques based on IR spectroscopy, together with the weight (M ; and number (M r ) average molecular weight. The results are indicated m Table (III) .

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