MXPA98009110A - Composition of supported catalyst and procedure for the polymerization of olef monomers - Google Patents

Abstract

A catalyst system comprising a carrier material, at least one transition metal complex and optionally at least one co-catalyst, the transition metal complex consists of a reduced transition metal (e.g., titanium ), chosen from groups 4-6 of the periodic table of the elements, with a multidentate monoanionic ligand and with two monoanionic ligands, the invention also relates to a process for producing polymers using the catalyst system, and to polymer products get

Description

COMPOSITION OF SUPPORTED CATALYST AND PROCEDURE FOR THE POLYMERIZATION OF OLEFIN MONOMERS BACKGROUND OF THE INVENTION 1. Field of the invention The present invention relates to supported catalyst systems and to the polymerization of α-alefine monomers using said supported catalyst systems. In particular, the invention relates to catalyst systems comprising a carrier material. at least one transition metal complex and one or more co-catalysts * as well as a process for producing polymers by the polymerization of ot-olefins using said supported catalyst systems and the polymer products obtained and their use. 2. BACKGROUND INFORMATION EP-A-548_257 discloses a supported catalyst system comprising an inert support and an onociclopentadienyl compound of a "group 4" transition metal and an aluminoxane. The disadvantages of supported catalyst systems according to EP-A-548 257 (the complete description of which is hereby incorporated by reference) are that with these catalysts only products with low molecular weight can be produced and that these systems catalyst have low activity. Commercial polymerization of α-olefin monomers with this catalyst system is not possible.

BRIEF DESCRIPTION OF THE INVENTION Thus? An object of the present invention is to solve the aforementioned problems associated with the related art? as well as satisfying the need expressed above. According to this object? The present invention provides a novel supported catalyst systems which are particularly suitable for the production of high molecular weight (co-) polymers which have high activity. The ability to achieve higher than normal molecular weights with the incorporation of a certain amount of camonomers under a certain set of polymerization conditions is called the superior "copolymer molecular weight capacity" of the present polymerization methods. In accordance with the principles of the present invention? this object is achieved by providing a catalyst composition and a process for the polymerization of at least one α-olefin in the presence of the present catalyst composition.

The catalyst composition includes at least one complex comprising a reduced valence transition metal (M) selected from groups 4-6 of the periodic table of the elements? a multidentate monoanionic ligand (X)? two onoanionic ligands (L) and? optionally? additional ligands (K). More specifically? the complex of the catalyst composition of the present invention is represented by the following formula (I.; X M (I) where the symbols have the following meanings! M a reduced transition metal selected from group 4? 5 or é of the periodic table of the elements? X a multidentate monoanionic ligand represented by the formulas (Af-Rt ~) "Y (~ Rt-DRí '" &";, and a cyclopentadieni lo-amido group - Rr-> or phosphido Í-PR'-) which is attached to the reduced transition metal M? At least one member selected from the group consisting of (i) a group connecting between the group Y and the group DR'n > and < ii) a group connecting between group Y and group Ar? wherein when the ligand X contains more than one group R. the groups R can be identical or different from one another D a heterogeneous electron donor atom selected from group 15 or i? > of the periodic table of the elements? R 'a substituent selected from the rump consisting of a portion containing hydrogen? hydrocarbon radical and heterogeneous atom? except that R 'can not be hydrogen when R' is directly attached to the electron donor heterogeneous atom D? whereby when the multidentate monoanionic ligand X contains more than a substituent R *? the substituents R "can be identical or different from one another? Ar an electron donor aryl group? L a monoanionic ligand linked to the reduced transition metal M? wherein the anaanionic ligand L na is a ligand comprising a cyclopentadienyl? amido group (-NR'-) or foefido (-PR * -)? And wherein the onoanionic ligands L can be identical or different from each other? K a neutral or anionic ligand attached to the reduced transition metal M. where when the complex transition metal contains more than one ligand K? the ligands can be identical or different from each other? m is the number of ligands K? where when the ligand K is an anionic ligand m is for M3 *? m is 1 for M * and m is 2 for Mß *? And when K is a neutral ligand m is increased by one for each neutral K ligand? N is the number of the R 'groups attached to the electron donor heterogeneous atom D? Whereby when D is selected from group 15 of the periodic table ca of the elements n is 2? and when D is selected from group 16 of the periodic table of elements n is 1? q? s and s are the number of groups (-Rt-DR'n) and groups (Ar-Rt_) joined to group Y? respectively? in dande q + s is an integer not less than 1. and t is the number of groups R that connect each of (i) the groups Y and Ar and < ii > the groups Y and DRr "? where t is independently selected as 0 or 1. These and other objects? characteristics and advantages of the present invention will become apparent from the following detailed description when taken in conjunction with the accompanying drawings that illustrate? as an example? the principles of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings illustrate the present invention. In said drawings? Fig. 1 is a schematic view of a cationic active site of a trivalent catalyst complex according to one embodiment of the present invention? and Figure 2 is a schematic view of a neutral active site of a trivalent catalyst complex of a dianionic ligand of a conventional catalyst complex according to WO-A-93 19104.

DESCRIPTION OF THE PREFERRED MODALITIES Next, several components (groups) of the transition metal complex are described in more detail. (a) The transition metal (M) The transition metal in the complex is selected from groups 4-6 of the periodic table of the elements. As mentioned here? all references to the periodic table of the elements refer to the version established in the new? UPAC notation found inside the cover of Handbook of Chemistry and Physics? 70th edition? 1989/1990? whose full description is incorporated herein by way of reference. In a very preferable way? the transition metal is selected from group 4 of the periodic table of the elements? and very preferably it is titanium (Ti). The transition metal is present in reduced form in the complex? which means that the transition metal is in a reduced oxidation state. As mentioned here? "Reduced oxidation state" means an oxidation state that is greater than zero but less than the highest possible oxidation state of the metal (for example, the reduced oxidation state is at most M ^ + for a metal, transitional from group 4? at most? ** for a transition metal from group 5 and at most Ms' * "for a transition metal from group 6). (b) The ligand X The ligand X in a multidentate monoanionic ligand represented by the formula? (Ar ~ Rt-) BY (-Rt-DR'r?) El. As mentioned here? a multidentate monoanionic ligand is linked with a covalent bond to the reduced transition metal (I) at a site (the anionic site Y) and is either linked to < i) with a coordinated junction to the transition metal at a different site (bidentate) or (ii) with a plurality of coordinated junctions at several other sites (tridentate, tetradentate, etc.). Can this coordinated union take place? for example? by means of the heterogeneous atom D or group (s) Ar. Examples of tri-toothed ionic ionic onoe include? without limitation? Y-Rt ~ DRr, _L-R * -DRr "and Y (~ R-D") 2.

Nevertheless? it is noted that the heterogeneous atom (s) or aryl substituent (s) can be present on the group Y without coordinating the reduced transition metal! ? provided that at least one coordinated linkage is formed between an electron donating group D or an electron donating group Ar and the reduced transition metal M.R represents a linking or bridging group between the DRr "and Y? and / or between the aryl group (Ar) electron donor and Y. Since R is optional? "t" can be zero. The group R is described in more detail later in paragraph (d). < c) The group Y The group Y of the multidentate monoanionic ligand (X) is preferably a cyclopentadienyl group? amido (-NRr-> or phosphido (-PR'-). Most preferably, the group Y is a cyclopentadienyl ligand (Cp group). As referred to herein, the term "cyclopentadienyl group" encompasses substituted cyclopentadienyl groups such as indenyl? fluorenyl and benzoindenyl groups and other cyclic aromatic palms containing at least one 5-membered dienyl ring, provided that at least one of the substituents of the Cp group is a group Rt ~ DRrn or group R ^ -Ar which replaces one of the hydrogens attached to the five-member ring of the Cp group by means of an exocyclic substitution. Examplee of a multidentate monoanionic ligand with a Cp group such as the group Y (or ligand) include the following , 15 (with the substituent (-R-t-DR '") or (Ai - Rt) on the ring) s R-D R-Ar 2? The group Y can also be a heterogeneous cyclopentadienyl group. As referenced here? A heterogeneous cyclopentadienyl group means a heterogeneous ligand derived from a cyclopentadienyl group? but in which at least one of the atoms that define the five-membered ring structure of the cyclopentadienyl is replaced with a heterogeneous atom by an endocyclic reformation. The heterogeneous Cp group also includes at least one Rt-DR '"group or Rt-Ar group which replaces one of the hydrogens attached to the five-member ring of the Cp group by means of an exocyclic substitution. As with the group Cp? as referenced here? the heterogeneous Cp group includes groups, indenyl? fluorenyl and benzoindeni what? and other polycyclic aromatics containing at least one 5-membered dienyl ring? provided that at least one of the substituents of the heterogeneous Cp group is an Rt-DR '"group or Rt-Ar group which replaces one of the hydrogens attached to the five-membered ring of the heterogeneous Cp group by means of an exocyclic substitution. The heterogeneous atom can be selected from. group 14? 15 or 16 of the periodic table of the elements. If there is more than one heterogeneous atom present in the five-membered ring? These heterogeneous atoms can be either the same or different from each other. In a very preferable way? the heterogeneous atom (s) is selected from group 15? and even more preferable? the selected heterogeneous atom (s) (s> is / are phosphorus.) By way of illustration and without limitation, the heterogeneous ligands representative of the group X can be carried out in accordance with the present invention are heterogeneous cyclopentadienyl groups having the following structures en in which the heterogeneous cyclopentadienyl contains a phosphorus atom (i.e. the heterogeneous atom) substituted in the five membered ring? R-DR It is noted that? usually? the group of the transition metal M is attached to the group Cp by means of a bond l5. The other exacyclic substituents R7 (shown in formula (III)) on the ring of the heterogeneous Cp group can be of the same type as those present on the Cp group? as represented in formula (II). As in the formula (H)? at least one of the exocyclic substituents on the five-membered ring of the heterogeneous cyclopentadienyl group of the formula (III) is the group Rt-DR '"or the group R ^ -Ar. The numbering of the substitution sites of the indenyl group is in general and in the present description based on the IUPAC nomenclature of Organic Chemistry 1979? rule A 21.1. The numeration of the substitute sites for indene shows below. This numbering is analogous to an indeni lo group; Indeno The group Y can also be an amido group (-R'-) or a group fasfido (-PR'-). In these alternative modalities? the group Y contains nitrogen (N) or phosphorus (P) and is covalently bound to the transition metal ti? as well as the group R (optional) of the substituent (-Rt-DR '") or (Ar-Rt-). (d) The R group The R group is optional? so that he may be absent from group X. When group R is aueente? the group DR '"or Ar is directly attached to the group Y (ie the group DR'" or Ar is directly attached to the group Cp? amide to phosphide). The presence in the absence of a group R between each of the groups DR '"and / or groups Ar is independent. When at least one of the R groups is present? each of the group R constitutes the connecting junction between? On the one hand the group Y? and on the other hand the group DR '"or the group Ar. The presence and size of the group R determines the accessibility of the transition metal M in relation to the group DR ', _, or Ar? which gives the desired intramolecular coordination. If the group R (or bridge) is too short or absent? the donor may not coordinate well due to ring tension. The R groups are each independently selected? and generally can be? for example? a hydrocarbon group with 1 ~ 20 carbon atoms (eg, alkylidene, arylidene, aryl, ideno, etc.). Specific examples of said R groups include? without limitation? methylene? Ethylene? propylene? butylene? phenylene? whether or not with a substituted side chain. Preferably? Does the group R have the following structure? (-CR1 (IV) where p = 1-4. The groups of the formula (IV) can each be independently selected? and they may be the same as the groups R 'defined below in paragraph (g). In addition to carbon? the main chain of the R group may also contain eilium or germanium. Examples of such R groups are? dialqui Isi 1 i le or (-SiR'j, -)? dialqui Igermi to (- GeR'j, -)? tetra-alkylsilylene (-SiR '- »- SiR' s-) or tetraalkylsilyethylene (-SiR'jgCR '-, -)« The alkyl groups in said group preferably have 1-4 carbon atoms and most preferably are a methyl or ethyl group, (e) The group '"This donor group consists of a heterogeneous electron donor D selected from group 15 or 16 of the periodic table of the elements? and one or more substituents R 'linked to D. The number < n) of groups R 'is determined by the nature of the heterogeneous atom D? while n is 2 if D is selected from group 15 and n being 1 if D is selected from group 16. Substituents R 'linked to D may each be independently selected and may be the same as the R' groups defined below in paragraph (g)? with the exception that the substituent R 'linked to D can not be hydrogen. The heterogeneous atom D is preferably selected from the group consisting of nitrogen < N)? oxygen (0)? phosphorus (P) and sulfur (s)? very preferably? the heterogeneous atom is nitrogen (N). Preferably? he. group R 'is an alkyl group? most preferably an n-alkyl group having 1-20 carbon atoms and most preferably an n-alkyl having 1-8 carbon atoms. It is also possible that two groups Rr in the group DR '"are connected to each other to form a ring-shaped structure (whereby the group DR' ^ can be for example a pyrrolidinyl group). The group DR '"can form coordinated junctions with the transition metal M. (f) The Ar Group The selected electron donor group can also be an aryl group? Í ^ R '^)? such as phenyl? tolyl? xylyl? mesitila? cumenil? tetra eti Ifeni what? peta eti Ifeni la? a polycyclic group such as triphenylmethane? etc. Nevertheless? the electron donor group D of the formula (I) can not be a substituted Cp group such as an indenyl group? benzoindeni lo or fluorenyl. The coordination of this group Ar in relation to the transition metal li can vary from * 1 to r] 6. (g) The group R 'The R' groups can each be separately hydrogen or a hydrocarbon radical with 1-20 carbon atoms (e.g.? alkyl? aryl? arylalkyl and the like as shown in table 1) ) «Examples of alkyl groups are methyl? ethyl? propyl? butyl? Hexyl and decyl. Example of aryl group phenyl mesitila? tolyl and cumenyl. Examples of arylalkyl groups are benzyl? pentameti Ibencilo? xylyl? styryl and trityl. Example of other R 'groups are halides? such as chloride? bromide to fluoride and iodide? metaxi? ethoxy and phenoxy. Similarly? two adjacent hydrocarbon radicals of group Y can be connected to each other to define a ring system? therefore group Y can be an indenyl group? a fluorenyl group or a benzaindenyl group lo. The indenyl? Fluorenyl and / or benzoindeni may contain one or more R 'co or substituent groups. Rt can also be a substituent that instead of? or in addition to the carbon and / or hydrogen may comprise one or more heterogeneous atoms of groups 14-16 of the periodic table of the elements. In this way? a substituent can it be? for example? a group that contains Si? such as Si (CH3) 3. (h) Group L The transition metal complex contains two monoanionic L ligands attached to the transition metal M.

Examples of the L group ligands? which can be identical or different? include? without limitation? the following? a hydrogen atom? a halogen atom? an alkyl group? aryl or arylalkyl? an alkoxy or aryloxy group? a group that understands a heterogeneous atom selected from group 15 or 16 of the periodic table of the elements? including? for example? (i) a sulfur compound? such as sulfite? sulfate? thiol? sulfonate and tisalkyl and (ii) a phosphorus compound? such as phosphate and phosphata. The doe L groups can also be connected to each other to form a biannual dianionic ring system. These and other ligands can be tested to verify their suitability by means of simple experiments by a person skilled in the art.

Preferably? L is a halide and / or an alkyl or aryl group? very preferably? L is a Cl group and / or an alkyl group of Cj ^ -C ^. or a benci la group. Nevertheless? the group L can not be a group Cp? amido or phosphide. In other s? L can not be one of the groups Y. (i) The ligand The ligand K is a neutral or anionic group attached to the transition metal M. The group is a neutral or anionic ligand bound to li .. When K is a neutral ligand K can it be absent? But when is monoanionic K? the following is for m = for M3 * m = 1 for M ** = 2 for Ms * On the other hand? the neutral K ligands? which by definition are not anionic? na are subject to the same rule. Thus? for each neutral K ligand? the value of (ie, the number of total ligands) is greater than the value mentioned above for a complex having all the anoanilic K ligands. The ligand can be a ligand as described above for the L group or a Cp group (-CSR'B). an amido group (-NR'jj or a phosphide group (-PR '.-.) .The group I. can also be a neutral ligand such as an ether? An amine? A phosphine? A thioether? Among others.

If two K groups are present? the two groups can be connected to each other by means of a group R to form a bidentate ring system. As can also be seen from the formula (I)? group X of the complex contains a group Y to which are linked one or more donor groups (the group (s) Ar and / or croup (s) DR '^) by means of? optionally? a group R. The number of donor groups linked to the group Y is at least one and at most the number of sites of suetitución preeentes on a group Y. With reference? as an example? to the structure according to formula (II)? at least one substitution site on a group Cp is made by means of a group Rt-r or by means of a group Rt-DR '"(in which case q + s = 1). If all the groups Rr of the formula (II) were Rt-Ar? groups R-t-DR '"or any combination thereof? the value of (q + s) would be 5. A preferred embodiment of the catalyst composition according to the present invention encamises a transition metal complex in which a bi-dentate / monoanionic ligand is present? and in which the reduced transition metal has been selected from group 4 of the periodic table of the elements and has an oxidation state of +3. In this case? the catalyst composition according to the invention comprises a transition metal complex represented by the formula (V) X i M_III) - L. (V) I wherein the symbols have the same meaning as that described above for formula (I) and where li (III) is a transition metal selected from group 4 of the periodic table of the elements and is in oxidation state 3+. Said transition metal complex has no anionic ligands K (for an anionic K = 0 in case of li3 *). It should be noted that WO-A-93/19104 describes transition metal complexes in which a transition metal of group 4 is present in a reduced oxidation state (3+). The complexes described in WO-A-3/19104 have the general formula? Cp ^ (ZY) b) ILI (VI) The group Y in this formula (VI) is a heterogeneous atom? such as phosphorus? oxygen? sulfur or nitrogen covalently bonded to the transition metal M (see page 2 of WO-A-93/19104). This means that the group Cpra? (2Y) fcJ is dianofic in nature and has the anionic charges residing above the groups Cp and Y. Accordingly? the group Cp ^ iZY ^ of formula (VI) contains two covalent bonds; the first being between the ring of 5 members of group Cp and the transition metal M? and the second being between the group Y and the transition metal. By contrast? the group X in the complex according to the present invention is monoanionic in nature? so that a covalent bond between the group Y (eg, the group Cp) and the transition metal is present? and a coordinate link may be present between the transition metal M and one or more of the groups (Ar-Rt-) and (-Rt-D '"). This changes the nature of the transition metal complex and consequently the nature of the catalyst that is active in the polymerization. As referenced here? A coordinated union is a union (.v .gr ^ r H3.N-BH3) that when it is broken? produces either <i) two species with no net charge and no unpaired electrons (eg,? H3N? and BH-3) or (ii) doe species with net charge and with unpaired electrons (eg.? H3N- * y BH ^ -). On the other hand? Was it referred to here? A covalent bond is a union (eg,? CH3-CH3) that when broken produces either (i) two species with no net charge and with unpaired electrons (eg.? CH3- and CH3-) or ( ii) two species with net charges and no unpaired electrons (v «gr«? CH3 * and CH3? - ")» A description of coordinated and covalent bonds is established in Haaland et al. (Angew. Chem Int. Ed. Eng Vol. 28? 1989? P 992), the complete description of which is hereby incorporated by reference.

IO Is the following explanation proposed? although it is clarified that the present invention is not limited in any way to this theory. Referring now more particularly to Figure 2? The transition metal complexes described in WO-A-93/19104 are ionic after interaction with the cocatalyst. Nevertheless? the transition metal complex according to WO-A-93/19104 which is active in the polymerization contains a complete neutral charge (based on the assumption that the transition metal complex of polymerization comprises a transition metal M ( III) - a dianionic ligand and a growing monaanionic palmeric chain (POL)). By contrast? as shown in figure 1? the active transition metal complex in the polymerization of the catalyst composition according to the present invention is cationic in nature (assuming that the polymerization transition metal complex - based on the structure of the formula (V) - comprises a transition metal M (III)? a bidentate manaanio ligand and a growing monoanionic polymer (POL)). The complexes of transition metal in which the transition metal is in a state of reduced oxidation? but who have the following structure? Cp M.III. L. (vri) are generally not active in co-polymerization reactions. Is it precisely the presence? in the transition metal complex of the present invention? of the group DR ', or Ar (the donor)? optionally linked to the group Y by means of the group R. which gives a stable and suitable transition metal complex for polimerization. Said intramolecular donor will be preferred over an external donor (intermolecular) taking into account the fact that the former shows a more stable and stronger coordination with the transition metal complex. It will be appreciated that the catalyst system can also be formed in situ if the components thereof are added directly to the polymerization reactor system? and if a salvente or diluent is used? including liquid monomer? in said polymerization reactor. The catalyst composition of the present invention also contains a co-catalyst. For example? the co-catalyst may be an organometallic compound. The metal of the organometallic compound can be selected from group 1? 2? 12 or 13 of the periodic table of the elements »Suitable metals include? for example and without limitation? sodium? lithium? zinc? Agnesium and aluminum? aluminum is preferred. At least one hydrocarbon radical is attached directly to the metal to provide a carbon-etal bond. The hydrocarbon group used in said compounds preferably contains 1-30? most preferably 1-10 carbon atoms. Examples of suitable compounds include? without limitation? amilo-sadio? Butyl lithium? diethyl zinc? buti l-magnesium chloride and dibuti Imagnesium. Is preference given to organoalumium compounds? including? for example and without limitation? the following? trialqui lalu inia compounds? such as triethylaluminum and tri-isabuti lauminum? hydrides of alqui laluminia? such as di-isobutyl hydride laluminum? Alkylalkoxy organoaluminum compounds? and organoaluminum compounds that contain halogen? such diethylaluminum chloride bed? di-isobu and aluminum chloride and sesquiclorura of etiumuminia. Preferably? linear or cyclic aluminoxanes are selected as the organoalu inium compound. In addition to? or as an alternative for organometallic compounds such as co-catalyst? the catalyst composition of the present invention can include a compound that contains or that produces in a reaction with the transition metal of the present invention? an anion not coordinated or poor coordination coordination. Such compounds have been described, for example, in EP-A-426? 637? whose full description is incorporated herein by way of reference. This anion is united in a way unstable enough to be replaced by an unsaturated monomer during the codend! imerization. Said compounds are also mentioned in EP-A-277? 003 and EP-A-277,004? whose full descriptions are incorporated herein by way of reference. Said compound preferably contains a triarylborane or a tetraarylborate or an aluminum equivalent thereof. Examples of suitable co-catalyst compounds include? without limitation? the following? - tetrakis (pentafluoropheni 1) borate dimeti lani 1 inio CC -.ßN_CH3_ßH3 * Z B iC ^ F ^ ^ l-í - bis <; 7? 8-dicarbaundecaborate) -cobalt tato < I I I) of di-ethylanilinium-tetrafeni-Iborate of tri (n-butyl) ammonium? - tetrakis (pentafluoropheni 1) tri-phene-1-carbenium borate? - Tetrafeni dimethyl anilineium Iborate? - tris (pentafl uarof ni 1) orano? and - tetrakis (eg af1 uorof i1) borate. If the non-coordinating anion or deficient coordination mentioned above is used? it is preferable that the transition metal complex be alkylated (ie, that the L group is an alkyl group). As described for example in EP-A-500? 944? whose full description is incorporated herein by way of reference? can the reaction product of a halogenated transition metal complex and an organometallic compound also be used? such as, for example, triethylaluminium (TEA). The molar ratio of the co-catalyze in relation to the transition metal complex? in case an organometallic compound is selected as the co-catalyst? is usually on a scale of about 1? 1 to about 10? 000? 1? and preferably it is on a scale of about 1? 1 to about 2? 500? 1. If a compound containing or producing a noncoordinating anion or poor coordination is selected as the co-catalyst? the molar ratio is usually on a scale of about 1? 100 to about 1? 000? 1? and preferably on a scale of about 1? 2 to about 250? 1. How could a person skilled in the art notice? the transition metal complex? as well as the co-catalyst may be present in the catalyst composition as a single component or as a mixture of component parts. For example? can a mixture be desired when there is a need to influence the molecular properties of the polymer? such as molecular weight and in particular molecular weight distribution. The inert support component can be any finely divided porous support? including? but not limited to? MgClj ,? zeolites? mineral clays? Inorganic oxides such as talc? silica? alumina? s lice-alumina? Inorganic hydroxides? phosphates? sulfates? etc.? or resinous materials such as polyolefins? including polystyrene? or mixtures thereof. Can these vehicles be used as such or modified? for example by silanes and / or aluminum alkyls and / or aluminoxane compounds? etc. The transition metal complex to the ca-catalyst is supported on a vehicle. It is also possible that both the transition metal complex and the co-catalyst are supported on a vehicle. The carrier material for the transition metal complex and for the co-catalyst may be the same material or a different material. It is also possible to support the transition metal complex and the co-catalyst on the same vehicle. The supported catalyst systems of the present invention can be prepared as separate compounds? which can be used as such in polymerization reactions? or the supported catalyst systems can be formed in situ just before a polymerization reaction is initiated. The supported catalyst systems of the invention can be prepared by various methods. The transition metal complex of group 4-6 and the aluminoxane component / can be mixed before the addition of the soup material? or the mixture can be added to the support material. The mixture can be prepared in a conventional solution in an alkane or aromatic solvent nor in liquid form. These solvents include? but are not limited to? linear or branched alkanes such as pentane? hexane »heptane» pentamethyl-heptane? isobutane and isopene and aromatic solvents such as toluene. The solvent is preferably also suitable for use with a poly erization diluent for the liquid phase polymerization of an olefin onomer. As an alternative? the inau alu can they be placed on the support material followed by the addition of the transition metal complex? or in an inverea way? the transition metal complex can be applied to the support material followed by the addition of the alu i oxanoe. Can aluminoxanes be used as commercially available? or can they be generated in situ on the solid support? for example? by adding a trialqui laluminium compound to a hydrated support? for example? with the addition of tetramethi aluminum to a silica moistened to dehydrated. The supported catalyst can be pre-mixed. Further? third components can be added at any stage of the preparation of the supported catalyst. The third components can be defined as compounds containing acidic or Lewis base functionalities exemplified but not limited by such compounds as N? N-dimethanol? tetraetoxisi tin? phenyl trietoxisi tin? bis-ter-but i Ihi droxi tol ueno (BHT) and ei ires. It has been discovered that the transition metal components in which the metal is titanium impart beneficial properties to a catalyst system? which is unexpected in view of what is known about the properties of the cyclopentadienyl titanium compounds that are ca-catalyzed by aluminoxanoe. While titanocenoe in their soluble form are generally unstable in the presence of aluminum alkyls? The metal components of this invention generally exhibit greater stability (ie, longer catalyst life)? resulting in higher catalyst activity rates (expressed as kg of polymer produced per g of Ti per hour). A higher tx-olefin comonomer incorporation at a high molecular weight are also surprisingly advantageous features of the catalyst systems according to the invention ("molecular weight capacity of the comonomers"). In summary? the supported catalyst systems of the invention comprise a reduced transition metal complex? a vehicle and optionally one or more organoaluminum compounds and / or a compound that contains or produces a non-co-ordinating anion or deficient coordination in a reaction with the transition metal composite. E the procedure according to the invention? The polymerization of tx-olefin monomers is carried out using a supported catalyst system as described above. In particular? the manomer (s) of "-olefin is / are appropriately selected from the group comprising ethene? propene »butene? Pentene? heptena? hexene? octene and styrene (substituted or unsubstituted). Mixtures of these compounds can also be used. In a very preferable way? ethene and / or propene are used as the OI-olefin. Does the use of said olefins result in the formation of meroe polypropylene (semi) crietalinoe homo- and copol? high as well as low density (HDPE? LDPE? LLDPE? et.)? and homo- and copolymer polypropylenes (PP and EtiPP (polypropylene modified with elastomer)). Ethylene is very preferably used as the α-olefin in combination with butene? hexene or octene. The monomers necessary for said products and the methods to be used are known to those skilled in the art. The process according to the invention is also suitable for the preparation of amorphous or rubber-like copal or ethereal or other olefin-based copal. It is preferably used prapßno as the other oc-ale ina? by which EPM rubber is formed. It is also possible to use other dienes that are not ether and other "-olefins". in such a way that a so-called EADM polymer (terpolymer of ethylene-olefin-diene) is formed? in particular EPDM (ethene-propene-diene rubber). The polymerization of the α-olefin monomer (s) can be carried out in a known manner. in the gas phase? as well as in a liquid reaction medium. Both the polymerization of solution and suspension are adequate for use in a liquid reaction medium. The supported catalyst systems according to the invention mainly operate in gas phase and suspension processes. The amount of transition metal that will be used is generally such that its concentration in the dispersing agent is between about 10_ß and 10-3 mol / l? preferably between about 10 ~ "f 'and 10 ~ * mol / L. The invention will be described hereinafter with reference to polymerizations of" -olefins known per se which are representative of the polymerization referred to. In the present description, for the preparation of other polymers on the basis of "-alphafin monomers, the reader will be referred to the multitude of publications in this material." The process of the present invention can be carried out as a phase polymerization. of gas (eg in a fluidized bed reactor) as a suspension polymerization as a solid Jase powder polymerization or as a so-called intermittent polymerization process using excess alefinic monomer as the reaction medium. can properly use dispersion agents for polimerization which can be chosen from (but not limited to) straight or branched aliphatic hydrocarbons? ee as butanes? pentanes? hexanes? heptanes? pentamet i Iheptana or fractions of mineral oil such as light or regular oil? naphtha? kerosene or gas oil. Similar fluorinated or liquid hydrocarbons are also suitable for this purpose. Can aromatic hydrocarbons also be used? for example benzene and toluene? but due to the considerations of costro and security »it is preferable not to use said solvents for the production on a technical scale. In polymerization procedures on a technical scale? Is it preferred to use inexpensive aliphatic hydrocarbons or mixtures thereof as solvents? talee like those marketed by the petrochemical industry. If an aliphatic hydrocarbon is used as a solvent? can the solvent also contain minor amounts of an aromatic hydrocarbon? for example toluene. Of eeta way? if for example methyl aluminoxane (MAO) co or co-catalyst is used? toluene can be used as a solvent for the MAO to supply the MAO in dissolved form to the polymerization reactor. Drying or purification of solvents is desirable if such solvents are used? this can be achieved using procedures known to those skilled in the art. In the procedure of the invention? the catalyst and co-catalyst are used in a catalytically effective amount? that is to say? any amount that successfully results in the formation of the polymer. Said amounts can be easily determined by routine experimentation by the person skilled in the art. It will be appreciated that the catalyst system can also be formed in situ if the components thereof are added directly to the polymerization reactor system? and a solvent or diluent is used? including liquid monomer? in the polymerization reactor. If you were going to use a solution or global policy? Is it necessary to carry it out at temperatures well above the melting point of the polymer that will be produced? typically? but not limited to? Are temperatures between 120 ° C and 260 ° C_ According to a preferred embodiment of the invention? the process is carried out under suspension or gas phase polymerization conditions which typically take place at temperatures well below the melting temperature of the polymer to be produced? typically? but not limited to? temperatures below 105 ° C. The polymer resulting from the polymerization can be made by methods known to the person skilled in the art. In general? the catalyst is deactivated at the same point during polymer processing. Disabling is also carried out in a way known per se? v.gr. by means of water or an alcohol. The removal of catalyst residues can normally be omitted because the amount of catalyst in the polymer? in particular the content of halogen and transition metal? is very low when using the catalyst system according to the invention. The polymerization can be carried out at atmospheric pressure? at subatmospheric pressure or at high pressure up to 500 MPa? continuously or discontinuously. Preferably, the polymerization is carried out at pressures between O.Ol and 500 MPa? very preferred between 0.01 and IO MPa? in particular between 5 and 30 bar (. - 0.5-3 MPa). Higher pressures of up to about 500 MPa can be applied. In a procedure of such high pressure? the process according to the present invention can also be used with good results. Does the polymerization of suspension and solution usually take place at lower pressures? preferably below 20 MPa. Can polymerization also be carried out in several steps? serially? as well as in parallel. If required? the composition? temperature »concentration of hydrogen? pressure »residence tie pa? etc. of the catalyst can vary from step to step. In this way? it is also possible to obtain products with a broad molecular weight distribution. The invention also relates to a polyolefin polymer obtainable by the polymerization process according to the invention. The invention will now be described by means of the following non-restrictive examples. All the tests in which organometallic compounds were involved were carried out in an atmosphere of inert nitrogen? using normal Schlenk equipment. A method for the synthesis of < dimeti laminoet i l) -tetrameti Iciclopentadienilo was published by P. Jutzi and otroe? Synthesis 1993? 684 (whose full description is incorporated herein by way of reference). The TiCljs? the used esters and the lithium reagents »2-bromo-2-butene and 1-chloroscyclohexene were obtained from Aldrich Chemical Company. The TiCl3,3THF was obtained by heating TiCl-5 for 24 hours in THF (tetrahydrofuran) with reflux.

In the following examples? "Me" means "methyl"? "iPr" means "isopropyl"? "Bu" means "butyl"? "iBu" means "isobutyl"? "terBu" means "tertiary butyl"? "Ind" means "indenyl"? "Flu" means "fluorenyl" »" Ph "means" phenyl "? Cp = cyclopentadienyl »Cp * - tetra ethylcyclopentadienyl? with sueti listeners that are not fixed to me additionally. The pressures mentioned are absolute pressures. SEC-DV = size exclusion chromatography. DPM = molecular weight distribution? defined as PmF, / Pm ". P,. »Pm" and Pm are molecular weights determined by universal calibration of SEC-DV. P.m,,,*? Pro ^ ** and PrV * are molecular weights determined by conventional calibration of SEC-DV.

EXAMPLE I Preparation of a supported catalyst system comprising (dimethylaminoeti 1) tetramethyl dichloride I cyclopentadieni 1-ti-tanium (III) < CwMe "(_CHa> 3NM _ =, 8) TiCla. to. Preparation of 4-hydroxy- (dimethyloxyethyl) -3,5-dimethyl 1-2,5-heptadiene 2-Bromo-2-butene (108 g »0.800 mol) was added to 10. O g of lithium ( 1.43 moles) in diethyl ether (300 ml) in about 30 minutes with reflux. After stirring overnight (17 hours) »3 was added < N, N-dimethylamino) ethyl propionate (52. g, 0.359 mol) to the reaction mixture in about 15 minutes. After stirring for 30 minutes at room temperature, 200 ml of water were added dropwise. After separation, the water phase was extracted twice with 50 ml of CH 2 Cl 4. The organic phase was reduced by evaporation and the residue was distilled under reduced pressure. The yield was 51.0 g (67%). b. Preparation of (di-ethylaminoeti-1) tetra-ethyl-cyclopentadiene The compound (21.1 g / 0.10 oles) prepared as described under a) was added in a single portion to p-toluenesulfonic acid.H-aO (28.5 g? 0.15 mol) »dissolved in 200 ml of diethyl ether. After stirring for 30 minutes at room temperature the reaction mixture was poured into a solution of 50 g of a-aCO-s .1 Hg.0 in 250 ml of water. After separation, the water phase was extracted twice with 100 ml of diethyl ether. The combined ether layer was dried < NaESO ^. > »Filtered and evaporated. After the residue was distilled under reduced pressure. The yield was 11.6 g (60%). c. Preparation of (dimethylaminoethyl) -tetramethyl-cyclopentadienyl titanium dichloride < I) 1.0 equivalent of n-BuLi (1.43 mL? 1.6 M) was added (after cooling to -60 ° C) to a solution of CßMeJ, H < CH¡s) ¡sNMess¡ of b) (0.442 g? 2.29 mmoles) in THF (50 ml)? after which the cooling bath was removed. After warming to room temperature the solution was cooled to -100 ° C and then TiCl3.THF (0.85 g, 2.3 mmoles) was added in a single portion. After stirring for 2 hours at room temperature the THF was removed under reduced pressure. After the addition of special boiling point gasoline? the complex (a green solid) was purified by repeated washing of the solid? followed by filtration and retro-drying of the solvent. It was also possible to obtain the pure complex through sublimation. d. Preparation of supported catalyst system A 1453 g of SiO-j. (obtained from Grace Davissn under the code W952)? drying for 4 hours at 4000C under a flow of dry nitrogen was added 10 ml of dry toluene. Then 16 ml of methylaluminoxane (MAO of Witco? 30% in toluene) was added over a period of 10 minutes? with constant ezclado at a temperature of 300 K. Then? the sample was dried under vacuum for 2 hours under constant mixing. Then 25 ml of an alkane mixture (C6 fraction) was added and the suspension was added for an additional 12 hours to 300 K. A suspension of the metal organ complex of Example 1 was then added under continuous mixing. After drying the obtained mixture the catalyst system showed 27.9% by weight of Al and an Al / Ti ratio of 328.

EXAMPLE II Preparation of an ethylene / octene copolymer with bimodal DPM using a supported catalyst system comprising dichloride of < dimethi laminoeti 1) tetramethi cyclopentadieni l-titanium (III) (CwMe_, ((CH? t) rNMe.) TiCl_t) Procedure .gener l? Octene was distilled and dried on a 13x type molecular sieve. 600 ml of an alkane mixture were brought as a solvent under dry nitrogen in a stainless steel rector having a content of 1.5 liters. For the etheno-octene polymerizations, 10 grams of dry octene were added to the reactor. The reactor was deepuée heated under constant mixing to the necessary temperature under an absolute pressure of ethene of 8 bar (SOO kpa). In a catalyst dosing vessel containing 100 ml? 25 l of an alkane mixture were metered in as dispersion medium. The amount of catalyst added was then introduced. The catalyst suspension obtained in this way was subsequently metered into the reactor. The polymerization reaction was initiated in this manner and carried out under isothermal conditions. The ethene preeion remained constant at 8 absolute bariae. The addition of ethene was interrupted after t minutes and the reaction mixture was combined and quenched with methanol. Then Irganox 1076 (MR) was added to the product as an antioxidant to stabilize the palí. The polymer was dried under vacuum at 70 ° C for 24 hours. Using this general procedure 18 g of octene were introduced into the reactor. Then, 20 romals (based on Ti) of the supported catalyst system of Example Id were added to the reactor. The polymerization took place at a pressure of 8 bars at 80 ° C. The obtained polymer (28050 kg / to Ti # hour) was analyzed by SEC-DV and showed a bimodal molecular weight distribution (DPM-15). The molecular weight averaged (R ^) was 400 kg / l at an octene content of 9.9 mol% (as shown by 1 H-NMR > EXAMPLE III Preparation of an ethylene / octene copolymer with unimodal DPM »using a supported catalyst system comprising (di-dimethylaminoethyl) tetramethylcyclapentadienyl-titanium dichloride.III) (C ^ e,. ((CH-ff) 1tNMe ^ TiCl) Applying the procedure described in Example II above? using, however, 10 micromoles (based on the Ti) of catalyst and a polymerization temperature of 120 ° C, a polymer with a uni-modal molecular weight distribution DPM = 7.3 was obtained.

EXAMPLE IV Preparation of a very high molecular weight polyethylene using a supported catalyst system comprising dichloride of (dimeti the inoeti 1) tetramethi cyclopentadieni 1-ti tanium (III) (C ^ Me., < < CH ^) - t Me.TiCl ^ > ) to. Preparation of the supported catalyst system 2.646 g MAO / SiO2 of Witco? based on PQMS3O40 SiOz? 21. 7% by weight of Al) were weighed in a Schlenk container.

IO 20 ml of a mixture of dry alkane (fraction C6) was added to 300 k? followed by the addition of a solution of the metal complex of example le. This mixture was dried under vacuum at 300 k. A powder having an Al / Ti ratio of 178 was obtained. 1. 0417 g of this powder were weighed in a Schlenk container and washed with toluene 300 K and dried for 20 minutes under «Vacuum at room temperature. b. Polymerization 5 micromoles (based on Ti) of the supported catalyst system prepared in Example IVa were used to carry out a polymerization using the procedure of Example II at a temperature of 800 ° C. The ethene pressure was maintained at 600 kPa . The obtained oatomer of ethene was analyzed by SEC-DV using standard calibration l. The _5 polyethylene had a very high molecular weight? a bimodal DPIi of 10.4 and a Pmp * of 1.4 * 10 ^, g / mol.

EXAMPLE V Preparation of a mere copolymer of etheno-styrene using a supported catalyst system comprising dichloride of (dimethyleneti-1) tetramethyl-cyclopentadienylthio-tanium (III) (C ^ Me ((CH ^ -M e ^ TiCl ^ Following the procedure described in Example II, the co-llenation of ethene and styrene was carried out using the same supported catalyst. Styrene was distilled under vacuum from CaHa. 45 g of styrene was added to the reactor. Twenty micromoles (based on Ti) of the catalyst were then introduced into the reactor. The polymerization was carried out at a temperature of S ° C? at an ethene pressure of 8 bar. The obtained polymer (1450 kg / o Ti * hour) was analyzed by SEC-DV. The molecular weight Pmp was shown to be 490,000 g / mol with a styrene content of 3.1 mol% (shown by NMR-H).

EXAMPLE VI Preparation of a high molecular weight polymer using a supported catalyst system comprising CP * (EtNMe ^) TiClf; > .LiCl to. Preparation of the metal complex Using the procedure described in the example la-c », Cp * < EtNMea!) TiCl = .. LiCl by recovering the solid green compound without removing all the LiCl b. Preparation of the supported catalyst system and homopolymerization of ethene 20 ml of dry toluene was added to 3.9 g of MAO / SiO., (From Witco) as described in example IV? Y «Sufficiently 4.4 ml of a solution of the catalyst complex of the example Via in toluene? containing 2.5 10 ~ ß mol / ml were added at room temperature. The mixture was then evacuated for 45 minutes under constant mixing. A suspension was obtained from the resulting dry supported catalyst. Was the polymerization carried out under the conditions described in Example IV? for 10 minutes at 95 ° C. The polymer particles produced were stabilized with Irganox 1076 and dried under vacuum for 24 h at 70 ° C. The copolymer was analyzed by SEC-DV using conventional calibration. Was it determined that P ^ * was 105 kg / mal? Pmp * 700 kg / ol and Pm,. * 1780 kg / mol. No reactor fouling occurred.

EXAMPLE VII Synthesis of the catalyst Cp iPr).,) (EtNMeJT) TiCl.

Reaction of cyclopentadiene with aqueous isopropyl bromide KOH (50% J 1950 g.ca. 31.5 moles in 2.483 l of water) and Adoben 464 (31.5 g) were placed in a 3 loc. Tree loe flask equipped with a condenser? mechanical agitator? heating cover? thermometer and an input adapter. Freshly ground cyclopentadiene (55.3 g? 0.79 mol) and isopropyl bromide (364 g? 2.94 mol) were added and stirring was started. The mixture turned brown and warmed (50 ° 0. The mixture stirred vigorously overnight? after which the upper layer containing the product was removed. Water was added to this layer and the product was extracted with hexane. The combined Hexane layer was washed once with water and once with brine? and after drying (MgSO 4) the salve was evaporated leaving a yellow-brown oil. The GC and GC-MS analyzes showed that the product mixture consisted of di isopropyl-cyclopentadiene (iPr2-Cp? 40%) and tri isopropy I cyclopentadiene (iPr ^ -Cp »60%). They were isolated (iPrj, -Cp and iPr-j-Cp by distillation under reduced pressure (20 mmHg). Performance depending on the accuracy of the distillation? approximately 0.2 moles iP ^ - p (25%) and 0.3 moles iPr ^ -Cp Reaction of lithium l »2» 4-triisopropylcyclopentadienyl with dimethylaminoethyl chloride In a 500 ml dry flask under dry nitrogen containing a magnetic stirrer was added a solution of 62.5 ml of n-butyllithia (1.6 M in n-hexane. 10O mmoles) to a solution of 19.2 g (100 mmolee) of iPr3-Cp in 250 ml of THF at -60 ° C. The solution was allowed to warm to room temperature (for about i hour) after which the solution was stirred during the nache. After cooling to -60 ° C, dimethylaminoethyl chloride (11.3 g → 105 mmol) »liberated from HCl was added by the method of Ress W.S. Jr. & Dippel K.A. in GPPI BRIEFS vol 24? No 5 »1992) by means of a drip funnel in 5 minutes. The solution was allowed to warm to room temperature after which it was stirred overnight. The progress of the reaction was monitored by GC. After the addition of water (and petter) »the organic layer was separated? dried and evaporated under reduced pressure. After the patented material i P ^ -C (30%) 5 isomers of the product (dimet i laminset i l) tri isopropylcyclapentadiene (LH »70%) san visible in GC. Two isomers are geminal (together 30%). The removal of gemomic isomers was possible by precipitation of the potassium salt of the iPr3-Cp anion and filtration and washing with petter (3x). Total yield (relative to iPr3-Cp of 30 moles (30%).

Reaction sequence for Cl-2 »4-tri isopropyl 1-3 dichloride < dimethylenol) -cyclopentadeni 13 titanium (II I) Solid TiCl-, 3THF (18.53 g? 50.0 mmolee) was added to a solution of the potassium salt of i Pr ^ -p in 160 ml of THF at -60 ° C at once »after which the solution was allowed to warm to room temperature» The color changed from blue to green. After all the TiCl3.3THF had disappeared the reaction mixture was again cooled to -0 ° C. After heating to room temperature again? Was the solution stirred for an additional 30 minutes? time after which the THF was removed under reduced pressure.

Preparation of the supported catalyst system and polymerization using the supported catalyst A supported catalyst was prepared according to the method described in Example VI. Nevertheless? the Ti component was the metal complex of the Vlla example. The Al / Ti ratio in the supported catalyst was determined to be 285 using neutron activation analysis and atomic absorption spectrometry. Under the conditions described in Example IV, actena and ethene were polymerized at 80 ° C. The formed copolymer was stabilized and dried and characterized using SEC-DV. The molecular weight distribution (DPM) of the product was determined using universal calibration and was 6.8. The molecular weight of the polymer was determined using the same method to have the high value of 1"2 * 10 < 6 > g / mol The Pm.,. It was 5.6-H-10? g / bad EXAMPLE VIII Preparation of an ethene / octene copolymer using a supported catalyst system comprising CP (iPr), (EtNMe ^) TiCla at a relatively high temperature The ethene / octene copolymerization was carried out or described in Example VII but now at 121 ° C. 9.1 kg of cspol number per g of Ti was produced every 5 minutes. He P ,, was determined as described in Example VII and was found to be equivalent to 180 kg / mol. He ,. was 450 kg / mol and the molecular weight distribution was 2.5.

EXAMPLE IX Preparation of an ethene / octene copolymer using a supported catalyst system comprising CP (iPr) rr (EtNMea.) TiCla in the presence of a scrubber An ester / octene copolymerization was carried out as described in example VIII except that triethylaluminium (TEA) was introduced into the reactor before the supported catalyst was removed. The amount of the TEA scavenger used was such that the Al / Ti reaction was 40. The yield of the copolymer was 8.4 kg / gTi.f-5 min. The molecular weight distribution was 2.2% P. kg / mol and the Pm of 180 kg / mol.

EXAMPLE X Preparation of a UHMMPE polymer using a supported catalyst system comprising Cp (2-enti 1) a (EtNMe-t) TiCl. a) Preparation of the metal complex Under a nitrogen-containing atmosphere, a solution of n-butyllithium in hexane (24.0 ml, 1.6 moles / L, 38 mmoles) was added dropwise to a cooled (0 ° C) solution. di- (2-pentyl) cyclopentadiene (7.82 g? 38.0 mmoles) in dry tetrahydrofuran (125 ml) in a 250 ml three-necked round bottom flask equipped with a magnetic stirrer and a dropping funnel. After a stirring of 24 hours at room temperature, 2-dimethylaminoet -latenilate is added. 38.0 mmol) in situ. After 18 hours of stirring it was found that the conversion was 92% and water was added carefully by dropping (100 ml) into the reaction mixture and the tetrahydrofuran was then distilled. The crude product was extracted with ether and the combined organic strengths were then dried (sodium sulfate) and evaporated to dryness. The residue was purified on a column of silica gel? Which resulted in 8.2 g of (dime i lami noeti l) -di (2-pentyl) ci lopentadiene. In a Schlenk container? 1.60 g (5.77 mmoles) of (dimethylaminoet i) i (2-pentyl) cyclopentadiene were dissolved in 40 L of diethyl ether and the solution was cooled to -60 ° C.

Then 3.6 ml of n-butyllithium I1.6M in hexane were added dropwise? 5.77 mmoles). The reaction mixture was brought slowly to room temperature? followed by agitation for 2 hours. In a second container Schlenk? 40 mL of tetrahydrofuran were added to 2.14 g of Ti (I I I) Cl3.3THF (5.77 mM). Both Schlenk vessels were cooled to -600C and the anal-thio compound was then added to the Ti (I II> Cl3.) The re-accia mixture was then stirred for 18 hours at room temperature. from which the solvent was evaporated. 'To the residue were added 50 L of petroleum ether, which were subsequently evaporated to dryness, leaving 1.60 g of a green solid containing l- dihydrochloride (dimeti la inoeti 1) -2 » 4-di (2-pentyl) cycle-pe tadie il-ti tanioí III). b) Preparation of the supported catalyst system A supported Ti catalyst was synthesized as described in Example IV. A suspension of 1.6 g of MAO / SiOj, (Witco? See example IV) was formed in 12 ml of dry toluene. 4.6 * 100 moles of the transition metal complex of Example Xa were added under stirring at 300 K. The resulting suspension was dried under vacuum for 2 hours at 300 K. A fine, free-flowing powder was obtained. c) Polymerization # 10_ = s Moles (based on Ti) of the catalyst of Example Xb were used for a polymerization experiment under the conditions described in Example IV. The ethene pressure was 600 kPa? the polymerization temperature of 96 ° C »The polymer formed was drained from the reactor» extinguished with ethanol »stabilized with irganox 1076 (MR)? dried at 70 ° C for 24 hours and studied with SEC-DV using convention calibration l The polymer PDM was 6.4? Pm ^, * of i.l- »10 < s > g / mol and Pm * of 2.? -"10fe g / mol.

EXAMPLE XI Preparation of an ethene / octene copolymer using a supported catalyst system comprising CP (2-pepti Dat (EtNMea) TiCla A polymerization reaction was carried out as described in Example X with the difference that 5 ml octene was now introduced into the reactor before starting the polymerization reaction. The polymer formed was studied as described in example X. Pm ^ * of 430 kg / mol? P ,, * of 1.2 * 10 ** g / mol and the copolymer DPM was 4.6.

EXAMPLE X I Preparation of a polyethene with high molecular weight using a supported catalyst system comprising two metal complexes In the same way as that described in example X? a supported catalyst was synthesized. The difference was that the catalyst consisted of two Ti complexes supported on the same support. A 3.6 g MAO / SiOj, (see example X) »27 ml of toluene were added with stirring at 300 K? followed by 4 * 10- * S moles of the metal complex of Example Xa and 6 * 10 ~! S of the metal complex of the example Via. The suspension that formed was dried with stirring at 30 ° C for 90 minutes? under vacuum. A polymerization was carried out with the catalyst that was synthesized. The polymerization conditions were the same as in Example X. The polymer formed had an extended molecular weight distribution of 8.2? a P ^, * of 840 kg / mol and an Mp,. * of 2.5 * 10 <; £ > g / mol EXAMPLE XIII Preparation of an ethene / octene copolymer with high octene content using a supported catalyst system comprising two metal complexes Was the polymerization carried out under the conditions described in Example X? but with the catalyst that was synthesized in example XII. The difference with the reaction conditions described in example X was that 25 ml of octene were introduced into the reactor before the start of the polymerization reaction. The polymer that formed during the polymerization reaction was treated as described in Example X and was a copolymer with a content of octene in the polymer chains of 19% by weight? as determined using 1 H-NMR. Despite this high content of octene? the Pm,. * was as high as 1 »3 * 10? g / mol? Pr * was 560 kg / mol and the DPM was 4.8.

EXAMPLE XIV Preparation of an ethene homopolymer using a catalyst system comprising (dimethylaminoetiI) tetramethyl I cyclopentadienyl-titanip (III) dichloride A supported catalyst was prepared in the following manner. 40 ml of dry toluene was added to 1.04 g of SiO-2 (Aerosil 380 (MR) and dried 4 hours at 400 ° C under dry nitrogen). Susecue feared that 18.5 ml of a 1.5 M solution of MAO in toluene (Witco) was added over a period of 10 minutes under constant stirring at room temperature. The mixture was evacuated overnight under constant mixing. In a next step, 12.05 ml of dry toluene was added to 1026 g of MAO / SiO-j. like the one obtained above. Are you often? 2.6 ml of a 0.025 mal / 1 solution of reduced transition metal complex of example 1 were added at room temperature. The mixture was evacuated for 60 minutes under continuous mixing. A suspension was obtained from the resulting dry supported catalyst. With this supported catalyst a homopolygation with ethene was carried out as described in Example X for 10 minutes at 96 ° C. The polymer was studied by SEC-DV using universal calibration. The P ^ equaled to 230 kg / mol »the P ^, of approximately 1120 kg / mol and the P z of approximately 2500 kg / mol.

EXAMPLE XV Preparation of an ethylene homogen using a catalyst system comprising (dimethylaminoeti 1) tetramethyl cyclopentadienyl-titanium (III) dichloride (C ^ e., ((CHrt) ^ NMe ^) TiCl ^ r) supported on Cl ^ A catalyst was prepared in the following manner. 20 ml of toluene eeco was added to 3.05 g of MgCl-eeco (average particle size 30 microns) and subsequently 30 ml of a solution of 1.5 mol / l of methyl aluminoxane (MAO / Wico) in toluene were added during a period of 15 minutes under continuous stirring at room temperature. The mixture was evacuated for 2 hours under constant mixing. 50 ml of an alkane mixture (C ^ fraction) was added and the suspension mixed well. To 20 ml of this mixture was added, at room temperature, 6.3 ml of an O.Oi ñ solution of the reduced transition metal complex of the example in toluene. The mixture was evacuated under constant mixing. 50 ml of an alkane (fraction C ^ were added to the solids thus obtained) and the suspension was washed with a large excess of a C6 fraction and finally evacuated under constant stirring with a suspension of the powder which had been obtained in this way a polymerization experiment was carried out as described in example X. The polymer formed was studied by SEC-DV, the Pm "was determined with universal calibration as 175 kg / mol? P ,, of 970 kg. / mol and Pm, of 2250 kg / mol.

EXAMPLE XVI Preparation of a homopolymer of ethene using a supported catalyst system comprising CP (iPr) -t (EtNMe11,) TiCl- A supported catalyst was prepared in the following manner. 10 ml of dry toluene was added to 1.45 g of MAO / SiO ,, (Witco) and subsequently 4.1 ml of a 0.01 M solution of the transition metal complex reduced from. Example VII were added at room temperature. The mixture was then evacuated under continuous stirring at room temperature. 50 ml of dry toluene was added and the suspension was mixed. The suspension was washed with an excess of dry toluene and evacuated under constant mixing. A suspension was obtained in an alkane medium (Cfe fraction from the resultant free-flowing powder and a polymerization experiment was carried out following the procedure described in Example X. The resulting polymer particles, which showed excellent morphology and showed no reactor fouling at all, were studied by SEC-DV using universal calibration to determine moler weight characteristics.Pm "of the polymer was 210 kg / mol »Pm 800 kg / mol and Pm, 1800 kg / sl.

EXAMPLE XVII to. Synthesis of supported catalyst 182 mg of MA0 / SI02 were weighed into a 100 mL Schlenk 5 container (MAO on silica PQ MS3040? Obtained from Witca GmbH »21.7% by weight Al). 10 L of a solution was added to 1 * 10-2 M of Cß e ^ < CHS) -, NMe _,) Ti e2 in toluene to MAO / SiOjj, solid? stirring at room temperature. The catalyst was prepared according to example I (A-C). The catalyst was methylated with MeLi in diethyl ether. In the next step, 20 L of a solution of N-N-dimethylanilinium tetramethylamino pentafluorophenyl) borate was added to the suspension. The resulting suspension was dried under vacuum at room temperature »stirring? until a free flowing, dry powder was obtained »50 mL of a dry hexane fraction was added to the free flow powder to obtain a catalyst suspension with CTiH = 2 * 10-6 a / mL. b. Polymerization with supported catalyst _0 In a catalyst dosing vessel, a suspension was formed with 10-5 moles of the supported catalyst (based on the Ti? Of Eeta way Al / Ti = 15? B / Ti = 2) in 100 mL of pentamethylheptane for 1 minute. The suspension was introduced into an IL reactor that had been filled with 0.75 L _5 of PMH at 95 ° C and maintained at a constant ethylene pressure of 6 bar. The activity was immediate and remained constant during the time. The activity of the catalyst was equivalent to 1535 gPE / g of catalyst per hour. The resulting polymer was analyzed using CFG. P p of 960 kg / mol? m ^ of 260 kg. ol » DPM = 3.7.

EXAMPLE XVIII to the. Preparation of bis (trimethyl Isyl) cyclopentadiene A round-bottom flask with a content of 5 liters equipped with an agitator, thermometer, crawling funnel and an inlet for. it was filled with 550 mL of dry THF. Was 66 g (1.0 mol) of freshly ground cyclopentadiene added to the iodine? after which the reaction mixture was cooled to -40 ° C. During cooling? slow addition of an equivalent (625 mL / l »6 li) of butyl lithium was started» The complete addition was completed after 45 minutes. Subsequently, the reaction mixture was stirred for 1.5 hours? later in 15 minutes. 130 mL (1.0 mole) of trimethyl chloride was added. With CG it was shown that the conversion to mono substituted Cp was completed after 1 hour. In 30 minutes an equivalent (625 ml / l or M) of but i lithium was added at -40 ° C. After 1.5 hours of stirring, 130 L (1.0 moles) of trimethyl chloride Isi 1 ila was added at -40 ° C. After stirring for 12 hours, CG showed that 10% of mono- and 90% bis-trimethylsilyl 1-Cp were present in the reaction mixture.

The reaction mixture was distilled at 4.4 mbar and 61 ° C. Deepuée of the distillation obtained 138 g of bistrimeti Isili l-Cp. The product was characterized with CG? CG-MS »* = 5C- and * H-NMR.

Preparation of bis (trimethylsilyl) -N »N-dimethylethoxyethylcyclopentadiene A round bottom flask with a content of 250 mL equipped with a thermometer» a dropping funnel and inlet for Njg- was filled with 80 L of THF »They were added to the same 15 g »(71.43 m sles) of bistrimeti Isi lil-Cp? after which it was cooled to -30 ° C. Subsequently an equivalent (44.6 mL / 1.6 M) of butyl lithium was added in 10 minutes. The reaction mixture was allowed to warm to room temperature. A round bottom flask with a content of 500 mL equipped with a thermometer, a dropping and inlet funnel for Ns, was filled with 100 L of dry THF and 6.4 g. (71.9 mmol) of tosyl chloride. After the addition, a white suspension formed which disappeared at 0 ° C during cooling down to -30 ° C. Subsequently, the reaction mixture was added with the bistrimeti Isyl i-Cp. The whole reaction was stirred for 12 hours. With CG it was shown that 94.4% of bistrimeti Isi l i-N? N ~ dimeti laminoeti l-Cp was present in the reaction mixture. The product was distilled at 0.6 m bar and 103 ° C. After distillation, 10.5 g (> 95% pure) of bis (trimethyl Isyl i) -N were obtained. N-dimeti laminoeti l-Cp »The product was characterized with CG? CG-MS »l3C- and * H-NMR. b. Synthesis of supported catalyst 2.2 g MAO / YOS02 were weighed in a 100 L Schlenk vessel (MAO on silica? Grace XPO 2409, obtained from Grace GmbH? 14.3% p Al). 20.1 mL of a mixture of dry hexane »0" 4 mL of a 0.1M solution of ((Cp (SiMe 3) s (EtNMe))) TiCl 2 in a mixture of dry hexane were added to the suspension. of MAO / SiO-g with stirring at room temperature The resulting suspension with CTi3 = 2 * 10 ~ * ol / mL was used to polymerize ethylene. c. Polymerization with supported catalyst In a catalyst dosing vessel, a suspension was formed with 10-5 moles of the supported catalyst (based on Ti »Al / Ti = 284) in 100 L of pentamethyl iron for 1 minute. The suspension was introduced into a 1L reactor which had been filled with 0.75 L of PMH and 4 *! 13 moles of triocti aluminum (TOA) at 40 ° C and maintained at a constant ethylene pressure of bar. The activity was immediate. The contents of the reactor were heated from 40 to 80 ° C in 8 minutes? starting immediately after the catalyst had been introduced. The catalytic activity was equal to 183 gPE / g of catalyst per hour. A nice, finely divided, free flowing polyethylene powder was obtained. Contamination of the reactor has occurred.

EXAMPLE XIX to. Synthesis of supported catalyst 1 of MA0 / Si0z were weighed in a Schlenk 100 L vessel (MAO on silica PQ MS3040? 24.7% by weight of Al? Obtained from Witca GmbH). .32 L of a dry toluene solution of ((Cp (SiMe3) S2 (EtNMeE)) TiCla (example XVIII al) was added to the MAO / SiO ^ powder with stirring at room temperature. it had remained dry during the synthesis? was stirred for 90 minutes under Ns. Then 15.9 L of dry toluene was added. The resulting suspension? with CTi3 = 2 * i "" "*» mol / mL was used to polymerize ethylene. b. Polymerization with supported catalyst In a catalyst dosing vessel, the •• - formed a suspension with 10-5 moles of the supported catalyst (based on Ti »Al / Ti = 284) in 100 L of pentameti Iheptana for 1 minute. The suspension was introduced into a reactor of 1 liter that had been filled with 0.75 L of PMH and 4 * 10- * mole of triocti aluminum (TOA) at 40 ° C and maintained at a constant ethylene pressure of 6 bar »The activity was immediate. The contents of the reactor were heated from 40 to 80 ° C in 8 minutes »starting immediately after the The catalyst had been introduced »The catalytic activity was equivalent to 405 gPE / g of catalyst per hour. Was a nice polyethylene powder obtained? finely divided and free flow. No reactor fouling occurred.

EXAMPLE XX to. Synthesis of C ^ e., (SiMea.CH ^ PPHj) TiCla A 1.57 g of (4.15 mmoles) € (2-difeni Ifosfino-1- ei la-1? 1-dimeti l) eti 1.}. etrameti Iciclopentadieno? dissolved in lO mL of diethyl ether "8.3 L of lithium diisopropylamide (O.SM in diethyl ether? 4.15 mmole) was added at -78 ° C. After 18 hours of stirring at room temperature a cloudy yellow / orange solution was formed. . The diethyl ether was evaporated and the residue was washed twice with petroleum ether. After that had been boiled well? 1.41 g of a light yellow crystalline product containing C (2-di f or 1-phosphite or-1-si-1-di-1-di eti-1) ethyl-5-tetramethyl-cyclopentadienyl. The organolithium compound was dissolved in 20 L of tetrahydrofuran. Then the yellow / nara solution was added at ~ 78 ° C? at 1.36 g (3.76 mmoles) of Ti (I II) C1-B »3THF. The reaction mixture was stirred for 3 hours in the cold bath and then for 18 hours at room temperature. A dark green solution was formed which was boiled and washed twice with 10 L of petroleum ether. 1.5 g of a green solid containing 1-i (2-difeni Ifosfino-1-sx-1-dimeti-1) dichloride and i l remained} 2? 3? 4 »5 ~ tetramethyl cyclopentadienyl thienium (III). b. Synthesis of supported catalyst 1.5 g of MAO / SiO.- were weighed into a Schlenk 100-ml container (MAO on silica PQ MS3040? 24.7% by weight of Al »obtained from Witca GmbH) and dried under vacuum for 90 minutes . 0.58 L of a solution of dry toluene at 0.08 M (CßMe ^ (SiMeíaCHa.PPh¡a £) TiCl¡e was added to the MAO / SiG powder, remaining with stirring at room temperature, the light yellow powder that had remained. The mixture was stirred for 90 minutes under N at room temperature, then 22.8 L of dry taluene was added in. The resulting suspension with CTil = 2 * 10"" <s> mol / mL was used to polymerize. ethylene. c. Polymerization with supported catalyst In a catalyst dosing vessel, a suspension was formed with 3 * 10 ~ 'of the supported catalyst (based on Ti »Al / Ti = 284) in 100 L of pentamethylheptane for 1 minute. The suspension was introduced into an IL reactor which had been filled with 0.75 L of PMH and 4 * 10-oles of trioct and aluminum (TOA) at 90 ° C and maintained at an ethylene constant pressure of 6 bar. The activity was immediate »The reactor temperature was set at 1000C. A powder of free flow was obtained. No reactor fouling occurred. The P ^ of the polymer produced was determined by CFC as 87 kg / mol »Pm" = 30 kg / mol »DPM = 2.9.

EXAMPLES X I-X I I The preparation of supported catalysts I) The so-called wet method A x grams of MAO / s lice PQMS3040 (Witco GmbH) was added 5-20x ml of KPB (hydrocarbon of fraction C ^,). Then the necessary amount of metallocene was added »usually in toluene or KPB. It was ensured that the concentration of transition metal in the resulting suspension was typically 5 * 10_fe mol / ml. The suspension was used for poly erization experiments. The complete synthesis was carried out in the glove box under nitrogen.

II) The so-called filling or pore method X grams of MAO / PG MS3040 were evacuated during 1.5 hours (typical weight loss of 5% »mainly organic solvents). Then a metallocene solution was added »typically about 30% of the total pore value of the AO / silica. After the addition of catalyst the solids were stirred for 1.5 hours. Then a catalyst suspension was prepared. All the syntheses were carried out in the box of mani pulaicon with gloves.

General polymerization process A catalyst suspension with a Zr-Ti concentration of about 1 * 10 ~ s mol / ml was prepared. The polymerization was carried out in a Büchi glass reactor. To the 1.5 L reactor were added 750 mL of pentamethylheptane »followed by 4 * 10_: that of triocti lauminum (TOA) as a scavenger. The necessary amount of catalyst? usually between 5 * 10 - "** moles and 2 * 10-ß moles on the basis of the transition metal, was introduced into the reactor at 40 ° C by means of a catalyst dosing vessel, the reactor was heated to T0 ° C This took approximately 10 minutes, after which the polymerization was carried out for another 10 minutes, with a total poly erization time of 20 minutes, the ethylene pressure in the reactor was kept constant at 5 minutes and the flow was determined. of ethylene required to maintain the pressure at 5 ° C. The polymerization was stopped and the palm tree suspension was drained from the reactor The palm tree suspension was stopped using methanol, stabilized by the sight of Irganox 1076 and dried under reduced pressure at 50 ° C. C. The yield of the polymer was determined and the molecular weight was studied by CFC.

EXAMPLE XXla The combination of Cp (SiMe? R) -t (EtNMe ^,) TiCla (TMS-cat) and (CP *) (SiMe.-CHt) PPH ^) TiCl-t (PPH-cat) The TMS-cat was obtained according to the preparation method described in Example XVIIa and the PPH-cat was obtained according to the method described in Example XXa. Synthesis? follow the synthesis route II) »solutions of both catalysts were added in toluene or simul- taneously to dry MAO / silica under vigorous stirring. A light yellow powder was obtained. A catalyst pellet in toluene (2 * 10-0 mol / ml) was prepared. Under the normal conditions described in the general polymerization process »but now at 40 to 5 100 ° C and with 4 * 10 ~ '* moles of TOA» was carried out a polymerization with 20 micromales of catalyst? based on Ti. Na was observed dirty reactar. 43.4 g of PE were formed in 20 minutes. Pm_ - 1500 kg / mol? P "= 165 kg / hr» Pma 3500 Í0 kg / mol. The yield was 1.5 times higher than under XXIb.

EXAMPLE XXIb The same catalyst was introduced at 80 ° C? CTOA3 4 * 10"" * mol / 1? while the polymerization took 15 minutes.

The molecular weights of the particles formed were? P p - 950 kg / mol? Pmp = 56 kg / mol? Pm, = 2400 kg / mol.

EXAMPLE XXII Combination of TMS-cat with rac-Et (i-Ind) -. GrCl., The (Et (l-Ind) 5SZrClS? Had been obtained from Witco GmbH). A series of catalysts were prepared? varying from the pure TMS catalyst to the pure zirconocene. Similarly? two synthetic procedures? Two silicas and two levels of scrubber were compared. It is clear from the CFG that both metalacenas remain intact when combined. to. Synthesis of pure TMS catalyst supported on MAO / PQ Ms3Q40 silica from Witca Following the synthesis route I) »a catalyst was prepared with Al / Ti-200? in kbp? suspension concentration 5 * 10- * • mol / ml. A light green suspension was obtained in a colorless solvent. The catalyst was tested at 40-800C? CT0A3 = 4 * 10"* mol / l total polymerization time 20 min.» Catalyst yield 279 gPE / gcat.hr.Prip, = 2600 kg / mol? Pm "870 kg / mol? Pm, = 4800 kg / mol. b. Synthesis of the pure TMS catalyst supported on Grace Sylopol 2104 silica. MOA / silica prepared by Witca Following the synthesis route I) »a catalyst was prepared with Al / Ti = 284? in kpb? suspension concentration 5 * 10- * mol / ml. A light green suspension was obtained in a colorless solvent. The catalyst was tested at 40-80 ° C. CT0A3 = 4 * 10-3 mol / l? Total polymerization time 20 min. »Catalyst yield 250 g PE / g cat.hr. P p = 2100 kg / mol? Pm "= 390 kg / mol; P,. = 4000 kg / mol. c. Synthesis of pure rae-Et (i-Ind) -, rCl-r supported on MAO / silica PQMS3Q40 from Witco Synthesis path I) was followed »concluding with a yellow suspension in KBP with concentration of 2 * 10- * ' mol / ml and Al / Zr = 284. The catalyst was tested with 4 * i0-3 moles of TOA »of 40-? 0oC» 20 minutes of poly-bristle time. The catalyst yield was 435 gPE / g cat.hr. Pmp = 205 kg / mol? Pm "= 47 kg / mol? P, = 790 kg / mal. d. Synthesis of TMS / Et (1-Ind) _gZ Cl ^ in the ratio 80/20 on MAO / silica PQMS304Q Following synthesis route I) the catalyst was synthesized by simultaneously adding solutions of both metallocenes to the MAO / silica suspension. obtained a suspension of a yellowish / light green powder in a colorless solvent with a transition metal concentration of 5 * 10 - ^ * mal / l. The catalyst was first tested with 4 * 10- * mol / 1 of TOA? of 40-800C? 20 min. of polymerization time. The product had an IV (decalinated? 135 ° C) of 11.5 dl / g. Subsequently »the catalyst was tested in the same way with 4 * 10 ~ 3 mol / l of TOA. Pmp = 1400 kg / mol? ' Pm "= 83 kg / mol? m, = 40OO kg / mol. and. Synthesis of TMS / Et (l-ind) gZrCl ^. in the 50/50 ratio on MAO / silica PQMS304Q Following the synthesis route I) the catalyst was synthesized by simultaneously adding solutions of both metallocenes to the MAO / silica suspension. A bright particle particle suspension was obtained? light green / yellowish in solvent with a transition metal concentration of 2 * 10- * mol / ml. The catalyst was tested as described in d. »With CT0A3 = 4 * 10-3 mol / l» No reactor fouling occurred. Pmp = 740 kg / mol? Pm "= 55 kg / al? Pm, = 3300 kg / mol.

F. Synthesis of TMS / Et (l-Ind) aZrCl; r in the ratio 20/80 on MAO / silica PQMS3040 according to the wet method described in the synthesis route I) The catalyst was synthesized and tested as described in e » The tests lasted 20 minutes. No reactor fouling occurred. P = 340 kg / mol? Pm "= 43 kg / mol? Pm, = 2000 kg / mol. g. Synthesis of the catalyst described in F) using the pore filling method described in synthesis route II) The catalyst was synthesized according to synthesis route II). A yellowish powder was obtained. Was a polymerization carried out with 1.5 micramoles of transition metal? follow the polymerization procedure described in e). The constant polymerization profile gave as a result a catalyst yield of 1080 gPE / g cat.hr.

TABLE 1 Axis of transitional lethal coplexes according to the invention (see I and Yl probes)

Claims (1)

1. NOVELTY OF THE INVENTION CLAIMS 1 ~ A catalyst composition comprising a porous and finely divided solid carrier material? at least one transition metal complex and one or more cocatalyst? further characterized in that said reduced transition metal complex has the following structure; X! M - L ^ 1 ?? in dande? M is a reduced transition metal selected from group 4? 5 or 6 of the periodic table of the elements? X is a multidentate monoanionic ligand represented by the formula? (Ar-Rt-) "Y (-Rt-DR '") ",? And is a member selected from the group consisting of a cyclapentadienyl group? amido (-NR'-) or phosphido (-PR'-)? R at least is a member selected from the group consisting of (i) a rump connecting between the rump Y and the group DR '^' and < ii) a connecting group between the group Y and the group Ar? where when Li X contains more than one group R? What group can R be identical or different from each other? D ee a heterogeneous electron donor atom selected from group 15 or 16 of the periodic table of the elements »R * of a target selected from the group consisting of a portion containing hydrogen? hydrocarbon radical and heterogeneous atom? except that R 'can not be hydrogen when R' is directly bonded to the electron donor heterogeneous atom D 'whereby when the multidentate onananionic ligand X contains more than one substituent R' »the substituents Rr may be identical or different one of the other? Ar is an electron donor aryl group. "L is a monoanionic ligand attached to the reduced transition metal M" wherein the onanoanionic ligand L is not a ligand comprising a cyclopentadienyl group? amido (-NR'-) or phosphido (-PR'-)? and where the monoanionic ligands L can be identical or different from each other? K is a neutral or anionic ligand bonded to the reduced transition metal M? where when the transition metal complex contains more than one ligand K? Can the K lines be identical to one another? m is the number of ligands K? where when the ligand K is an anionic bond is M for M3 *? m is 1 for M ** and m is 2 for 85 *? and when K is a neutral ligand m increases by one for each neutral K ligand? n is the number of the Rr groups bound to the electron donor heterogeneous atom D? whereby when D is selected from group 15 of the periodic table of the elements n is and when D is selected from group 16 of the periodic table of the elements n is i »q and are the number of groups (-Rt-DR ' ") And groups (Ar- Rt_) joined to group Y? Respectively? where q + s is an integer no less than 1? yt. is the number of R groups that connect each of (i) the Y and Ar circles and (ii) the Y and DR ',, "groups where t is independently selected as or 1. 2.- A system of catalyst according to claim 1 »further characterized in that the group Y is a cyclapentadienyl rump. 3 - A catalyst system according to claim 2 »characterized in that the cyclapentadienyl group is a substituted or unsubstituted fluororenyl or benzylindenyl indenyl group. 4. A catalyst system according to claim 2 »characterized in that said reduced transition metal complex has the following structure? 5 X M (III) 0 where M (III) is a transition metal of group 4 of the periodic table of the elements in oxidation stage 3+. 5. A catalyst system according to claim 2? further characterized in that said reduced transition metal is titanium. 6 »- A catalyst system according to claim 2? further characterized in that said electron donor heterogeneous atom D is nitrogen. 7. - A catalyst system according to claim 2 »further characterized in that the group R 'in the group DR'" is an n-alkyl group. 8. A catalyst system according to claim 2 »further characterized in that said group R has the following structure? Í-CR '^ -),,? where p is 1? 2? 3 or 4. 9. A catalyst system according to claim 2? further characterized in that said monoanionic ligand L is selected from the group consisting of a halogenide? an alkyl group and a benzyl group. 10. A catalyst system according to claim 2? further characterized in that said cocatalyst comprises a linear or cyclic inaxane alu? or an Iborane triari or tetraar i Iborato. 11. A catalyst system according to claim 2? further characterized in that at least one member selected from the group consisting of said reduced transition metal composite and said co-catalyst is supported on at least one vehicle. 12.- A process for the polymerization of monomer (s) of «-olefin? which comprises contacting a mixture of said "olefin monomer (s) in a liquid alkane or aromatic solvent with a catalyst system according to any of claims 1-12. 13. The process according to the claim further characterized in that the olefin (s) are selected from the group consisting of ethene »propene» butene »pentene» heptene »hexene? octene »substituted styrene» substituted na styrene and mixtures thereof. 14. The process according to claim 13 »further characterized in that said« -defines comprise ethene and butene. 15. The method according to claim 13 »further characterized in that said« -defines comprise etena and hexene. 16. The method according to claim 13 »characterized in that said defines comprise ethene and octene.