MXPA98009115A - Procedure for the co-polymerization of an olefine and an aromat vinyl monomer - Google Patents

Abstract

A process for the co-polymerization of at least one x-olefin and at least one aromatic vinyl monomer: the co-polymerization is carried out in the presence of a catalyst composition which includes at least one co-catalyst and one reduced transition metal complex, the reduced transition metal complex contains a reduced transition metal selected from groups 4-6 of the periodic table of the elements, a multidentate monoanionic ligand, and at least two monoanionic ligands; mode, the reduced transition metal is selected as titan

Description

PROCEDURE FOR THE CP-PO IME LICENSE OF A QLEFINA AND AN AROM TICO VINYL MONOMER FIELD OF THE INVENTION The present invention relates to a process for the co-polymerization of an olefin, especially ethylene, and an aromatic vinyl monomer. In particular, the present invention relates to the co-polymerization process carried out in the presence of a catalyst composition comprising a transition metal complex and a co-cataphorator.

BACKGROUND OF THE INVENTION EP-A-416R815r discloses a process for the co-oliming of ethylene and an aromatic vinyl monomer in which a so-called restricted geometry catalyst is applied. The catalyst described in this reference has been successful? to a certain degree in the co-polymerization of aromatic monomers with ethylene. However, a disadvantage of the process described in this reference is the unfavorable molecular weight of the obtained coating materials, and the insufficient percentage of aromatic vinyl monomers incorporated in the resulting copolymers under a given series of polymerization conditions. Is it known how to increase this ratio, reducing the polymerization temperature? However, the reduction of the polymerization temperature decreases the activity of the catalyst and leads to a lower yield of free snowflake. Therefore, there is a need for a process which, under a given set of polymerization conditions, yields a copal which has, at a given molecular weight, a higher concentration of copolymer aromatic vinyl monomers, and which can obtained by the methods known above, carried out under similar treatment conditions.

BRIEF DESCRIPTION OF THE INVENTION Therefore, an object of the present invention is to solve the aforementioned problems associated with the prior art, and also addresses the need expressed above. In accordance with the principles of the present invention, this object is obtained by providing a process for the co-pal imerization of at least one ocherfin and at least one aromatic vinyl anomer in the presence of the present catalyst composition. The catalyst composition includes at least one complex comprising a transition metal (M) of reduced valence selected from groups 4-6 of the periodic table of the elements, a last-named onoanionic ligand (X), two onoanionic ligands < L) and, optionally, additional ligands (.) More specifically, the complex of the catalyst composition of the present invention is represented by the following formula (I)? X IM f (I) where the symbols have the following symbols? ñ? a reduced transition metal selected from group 4, 5 or 6 of the periodic table of the elements? X? a ligand anoani ni or uí ti dentado represented by the formula? (Ai-Rt -). And (-Rt-DRr "), _ ,? Y? a cyclopentadienyl group, amido (-NRT-) or phosphido (-PRr ~), which is attached to the reduced transition metal M? R? at least one member selected from the group consisting of (i> a linking group between the group Y and the group uR? -. r Y < ii > a linking group between the group Y and the group Ar, wherein if the ligand X contains more than one group R, the groups R may be identical or different one of the other? D? an electron donating heteratam selected from group 15 or 16 of the periodic table of the elements? Rt? a substituent selected from the group consisting of a hydrogen, hydrocarbon radical and a portion containing a hetero to, except that Rr can not be hydrogen when R "is attached directly to the electron donating hetero atom D, where if the multidentate monoanionic ligand X contains more than one substituent R ', the substituents R' can be identical or different from one another? Ar? A donated aryl group r of electrons? L; a monoanionic ligand bound to the reduced transition metal M, wherein the monoanionic ligand L is not a ligand comprising a cyclopentadienyl group, amido < - NR'-) or phosphide < -PR '~), and where the monoanionic ligands L can be identical or different from one another? K? a neutral or anionic ligand bound to the reduced transition metal M, wherein if the transition metal complex contains more than one K-ligand, the K-ligands can be identical or different from one another? m; is the number of ligands K, where if the ligand K is an anionic ligand, m is 0 for M3 *, m is 1 for M *** and m is 2 for M85 *, and if K is a neutral ligand, m increases in one for each neutral K ligand? n! is the number of Rr groups attached to the electron donating hetero atom D, where if D is selected from group 15 of the periodic table of the elements, n is 2, and if D is selected from group 16 of the periodic table of the elementas, n is 1? q, s? qys are the number of groups (-Rt-DR ""> and groups (Ar-R, _.) attached to the rump Y, respectively, where q + s is an integer no less than i? and t? is the number of R groups that connect each of (i) the groups Y r, and (ii) the groups Y and DR '", where t is independently selected as or 1. Some non-limiting examples of transition metal complexes according to the invention are presented below in Table 1. In the process according to the present invention, a higher catalytic activity is observed in the co-reaction reaction between a process employing ethylene and an aromatic vinyl monomer. Accordingly, the copolymer prepared according to the process of the present invention also has a higher concentration of aromatic vinyl monomers incorporated in the copolymer than can be obtained for a copal of the same molecular weight? prepared according to the known procedures mentioned above and carried out under similar treatment conditions. Another object of the present invention is the provision of a copolymer of at least one α-olefin and at least one aromatic vinyl monomer, obtained by means of the aforementioned polymerization process using the catalyst composition according to the invention. These and other objects, features and advantages of the present invention will become apparent from the following detailed description when taken in conjunction with the accompanying drawings which illustrate, by way of 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 W0-A-93 / 191O4.

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 set forth in the new IUPAC notation found inside the cover of the Handbook of Chemistry and Physics, 70th edition, 1989/1990 , whose full description is incorporated herein by way of reference. Most preferably, the transition metal is selected from group 4 of the periodic table of the elements, and most preferably 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 herein, "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 M3. transition metal of group 4, when much M *** for a transition metal of group 5 and at most M55 * for a transition metal of group 6). ib) The ligand X The ligand X in a monoanionic ligand mutant represented by the formula? (Ar ~ Rt-) ßY (-Rt.-D 'n) q. As mentioned herein, a multidentate monoanionic ligand is linked with a covalent bond to the reduced transition metal (M) at one site (the anionic site, Y) and at is linked either (i) with a coordinated link to the transition metal at a different site (bidentate), or (ii) with a plurality of coordinated links at several other sites (tridentate, tetradentate, etc). Such coordinated links can take place, for example, by means of heteroatom D or group (s) Ar. Examples of tri-dentate monoanionic ligands include, without limitation, Y-Rt-DR * r? _. L? -Rt. ~ DRlr "and Y (-R-DR" ") 2., it is noted that the heteroatam (s) or aryl substituent (s) can (are) present on the group Y without coordinating the reduced transition metal M, provided that it is formed at minus a coordinate link 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. 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) Co or referred to herein, the term lopentadieni group encompasses substituted cyclopentadienyl groups such as indenyl, fluarenyl and benzoindenyl groups, and other polycyclic aromatic compounds containing at least one dienyl ring of 5 members, provided that at least one of the substituents of the Cp group is an Rt-DRT "group or a Rt ~ Ar group that replaces one of the hydrogens attached to the five-member ring of the Cp group by means of an exocyclic substitution. Examples of a monoanionic ligand terminated with a Cp group as the group (or ligand) Y include the following (with the substituent <-R-1-D • ""> (Ar-Rt) on the ring); R R 'R R-DR R-Ar The group Y can also be a heterocyclopentadienyl group. As referred to herein, a heterocyclopentadienyl group means a heterogeneous ligand derived from a cyclopentadienyl group, but in which at least one of the atoms defining the five-membered ring structure of the cyclopentadienyl, is replaced with a heteroatom by a substitution endocyclic The heterogeneous Cp group also includes at least one Rt-D '^ group or an 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 Cp group, as referred to herein, the heterogeneous Cp group encompasses indenyl, fluaren and benzaindeni lo groups, and other polycyclic aromatic compounds that contain at least one 5-membered dienyl ring, as long as minus one of the substituents of the heterogeneous Cp group is a group Rt-DR '"or a group R ^ -Ar which replaces one of the hydrogens attached to the five-membered ring of the heterogeneous Cp group by means of an exocyclic substitution. The heteroatom can be selected from group 14, 15 or 16 of the periodic table of the elements. If there is more than one heteroatom present in the five member ring, these heteroatoms may be either the same or different from each other. Most preferably, the heteroatom (s) is selected from group 15, and even more preferably, the heterate a (s) selected is / are phosphorus. By way of illustration and without limitation, the heterogeneous ligands representative of group X which can be carried out in accordance with the present invention, are heterocyclopentadienyl groups having the following structures, in which the heterocyclopentadiene is contained by a phosphorus atom ( that is, the heteratama) substituent on the five-membered ring? R R R-DR It is noted that, generally, the transition metal group M is linked to the group Cp by means of a ha bond. The other exocyclic substituents R '(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 (II), at least one of the exocyclic substituents in the five-membered ring of the heterocyclopentadienyl group of the formula (III) is the group Rt-DR ',,, or the group Rt- r. The numbering of the substitution sites of the indenila group is based in general and in the present description, in the Organic Chemistry nomenclature of the IUPAC of 1979, rule A 21.1. The numbering of substituent sites for indene is shown below. This numbering is analogous to a group inden what? Indeno (IV) The group Y can also be an amido group (-NR'-) or a phosphide group (-PR'-). In these alternative embodiments, the group Y contains nitrogen (N) or phosphorus (P) and is covalently linked to the transition metal M, as well as to the R group (optional) of the substituent (-Rt-DR '"> (Ar -R ^ .-). (d) Group R Group R is optional, so it may be absent from group X. When group R is absent, group DR'n or Ar is directly linked to group Y (ie, group DR ' "Or Ar is directly attached to the Cp, amido or phosphide group). The presence or absence of a group R between each of the groups DR ',, and / or groups A, is independent. When at least one of the groups R is present, each of the groups R constitutes the linker between, on the one hand, the group Y, and on the other hand the group DR ', -, on 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 may generally be, for example, a hydrocarbon group with 1-20 carbon atoms (e.g., alkylidene, arylidene, arylalkylidene, etc.). Specific examples of said R groups include, without limitation, methylene, ethylene, propylene, butylene, phenylene, either with or without a substituted side chain. Preferably, the group R has the following structure? Í-CR '-), (IV) where p = 1-4. The R "groups of the formula (IV) may each be independently selected, and may be the same as the R 'groups defined below in paragraph (g). In addition to the carbon, the main chain of the R group may also contain silicon or Examples of such R groups are dialkyl Isiil or (-SiR'j., -), dial for the wood (-BeR'j -, -), tetra-alk lsi lileno (-SiR'-g-SiR 'j, -) or tetraalkylsilyethylene (-SiR'-jCR' -, -) The alkyl groups in said group have preferably 1-4 carbon atoms and most preferably are a methyl or ethyl group. (e) The group DR '"This donor group consists of an electron donor heteratoma D selected from group 15 or 16 of the periodic table of the elements, and from one or more substituents R' attached to D. The number (n) of groups R 'is determined by the nature of the hetero atom D, in that n is 2 if D is selected from group 15 and n is 1 if D is selected from group 16 »Substituents R' linked to D can each be independently selected and they can be the same as the Rr groups defined below in paragraph (g), with the exception that the substituent R 'linked to D na can be hydrogen. The heteroate or D is preferably selected from the rump consisting of nitrogen (N), oxygen (O), phosphorus (P) and sulfur (S)? most preferably, the hetero atom is nitrogen (N). Preferably, the group R 'is an alkyl group, most preferably an n-alkyla group having 1-20 carbon atoms, and most preferably an n-alkyla having 1-S carbon atoms. It is furthermore possible that two rupes R 'in the group DR', are connected to each other to form a ring-shaped structure (whereby the group DR '"can be, for example, a pyrrolidini group). The group DR ',, can form coordinated bonds with the transition metal M. (f) The group Ar The electron donor group (or donor) selected may also be an aryl group, such as phenyl, tolyl, xylloyl, mesityl, cumenyl, tetramethylphenol, pentamethyl Ifenyl, a polycyclic group such as triphenylmethane, etc. However, the electron donating group D of formula (I) can not be a substituted Cp group such as an indenyl group, benzaindeni lo a fluoreni lo. The coordination of this group Ar in relation to the transition metal M, can vary from h1 to h ***. (g) The group R 'The R' groups can each be separately, hydrogen to a hydrocarbon radical with 1-20 carbon atoms (e.g., alkyl, aryl, arylalkyl and the like as shown in the table) 1). Examples of alkyl groups are methyl, ethyl, prapila, butyl, hexyl and decyl. Examples of aryl groups are phenyl, mesit lo, tolyl and cumenyl. Examples of arylalkyl groups are benzyl, penta eti Ibencila, xylyl, styryl and triyl. Examples of other R 'groups are halides, such as chloride, bromide or fluoride and iodide, methoxy, ethoxy and phenoxy. Likewise, two adjacent hydrocarbon radicals of group Y can be connected to each other to define a ring system? for both the group Y may be an indenyl group, a fluorenyl group or a benzoindenyl group. The indenyl, fluorenyl and / or benzoindeni may contain one or more R 'groups as substituents. R 'may also be a substituent which, in place of or in addition to carbon and / or hydrogen, may comprise one or more heteroatoms of groups 14-16 of the periodic table of the elements. In this manner, a substituent can be, for example, a group containing Si, such as S i (CH--.) .... (h) The group L The transition metal complex contains ligand L ligands linked to the transition metal M.

Examples of the group L ligands, which may be identical or different, include, but are not limited to, the following? a hydrogen atom? a halogen atom? an alkyl, aryl or arylalkyl group? an alkoxy or aryloxy group? a rump comprising a heterata or selected from rump 15 or 16 of the periodic table of the elements, including, for example, (i) a sulfur compound, such as sulfite, sulfate, thiol, sulfonata and thioalkyl and (ii) a phosphorus compound, such as phosphate coma and phosphate. The two L groups can also be connected to each other to form a bidentate dianionic ring system. These and other ligands can be tested to verify their convenience by average of simple experiments by one skilled in the art. Preferably, L is a halide and / or an alkyl or aryl group? most preferably, L is a Cl group and / or an alkyl group of Ct-C ^ or a benzyl group. However, the group L na can be a Cp, amide or fasfido group. In other words, L can not be one of the Y groups. (i) The ligand K The ligand K is a neutral or anionic group attached to the transition metal M. The group K is a neutral or anionic ligand bound to M. When K is a neutral ligand, K may be absent, but when K is monoanionic, the following is for Km? m = for M-3 * = 1 for M *** = 2 for Ms * On the other hand, neutral K-bonds, which by definition are not anionic, are not subject to the same rule. Therefore, for each neutral K-ligand, the value of m (ie, the number of K-ligands in tatal) is greater than the value mentioned above for a complex having all monoanionic K-bonds. The ligand K can be a ligand co or that described above for the group L or a Cp group (-C3R'ß), an amido group (-NR '; -.) Or a fastened group (-PR' .- » ). The group K 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 K groups can be connected to one another by means of a group R to form a bidentate ring system. As can also be seen from formula (I), group X of the complex contains a group Y to which one or more donor groups (the rump (s) Ar and / or rump (s) are linked). DR '") by means of, apically, a group R. The number of donor groups linked to the group Y is at least one and at most the number of substitution sites present on a group Y. With reference, by way of For example, to the structure according to formula (II), at least one substitution site on a group Cp is made by means of a group R ^ -Ar or by means of a group R ^ -DR '"(in whose case q + s = 1). If all the groups R 'of the formula (II) were groups Rt-Ar, groups R * -DR', -, or any combination thereof, the value of (q + e) would be 5. A preferred embodiment of the The catalyst composition according to the present invention comprises a complex of transition metal in which a bidentate / manoanionic 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 M (III) (V) where the symbols have the same meaning as that described above for the formula (I), and where M (III) is a transition metal selected from group 4 of the periodic table of the elements and is in a state of oxidation 3+. Said transition metal complex does not have K anionic ligands (for an anionic, -O in case of M3->.

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-93/19104 have the general formula? Cpß (ZY) bMLe (VI) The group Y in this formula (VI) is a heteroatom, such as phosphorus, oxygen, sulfur or nitrogen, cavly attached to the transition metal M (see page 2 of WO-A-93/19104). This means that the group Cp ^ íZY) ,, is of dianióica nature and has the ammonic charges residing previously on the groups Cp and Y. Consequently, the group Cp ^ íZY ^ of formula (VI) contains two covalent bonds? the first between the 5-member ring of the croup Cp and the transition metal M, and the second between the group Y and the transition metal. In contrast, the group X in the complex according to the present invention is monoanionic in nature, whereby a covalent bond between the group Y i v is present. gr. , the group Cp) and the transition metal, and a coordinated link may be present between the transition metal M and one to more of the groups (Ar-Rt ~) and (-Rt-DR '"> This changes the nature of the transition metal complex and consequently the nature of the catalyst that is active in the polymerization As referred to herein, a coordinate bond is a bond (e.g., H3N-BH--.) that when breaks, produces either (i) doe species with no net charge and no unpaired electrons (eg, H3N? and BH3) or (xi) two species with net charge and with unpaired electrons (eg, Hj) - * and EH3--) On the other hand, as referred to herein, a cavalent bond is a bond (eg, CH3-CH3) that when broken produces either (i) two species with no net charge and with unpaired electrons (e.g.? CH -; - and CH3-) or (ii> two species with net charges and without unpaired electrons (v. < r. t CH3 * and CH3? - A description of coordinated and covalent links s is exposed in Haaland and others (Angew. Chem Int. Ed. Eng. Vol. 28, 1989, p. 992), the complete description of which is hereby incorporated by reference. The following explanation is proposed, although it is made clear that the present invention is by no means limited to this theory. In reference now more particularly to Fig. 2, the transition metal complexes described in WO-A-93/19104 are ionic after interaction with the co-catalyst. However, the transition metal complex according to WO-3/19104 which is active in the polymerization, contains a neutral total charge (based on the assumption that the polymerization transition metal complex comprises a metal of transition M (III>, a dianionic ligand and a growing monoanionic polymer chain ΔP0D) In 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 formula (V) - comprises a transition metal M (ISI), a bidentate mannionic ligand and a polymer chain Increasing manaani (POL).) The transition metal complexes in which the transition metal is in a state of reduced oxidation, but which have the following structure? Cp - MÍIII) - L-, (VID are generally not active in copal reactions imerization.) It is precisely the presence, in the transition metal complex of the present invention, of the group DR'_, or Ar (the donor), apitially attached to the rump AND middle pair of the R group, which gives a stable transition metal complex suitable for polymerization, said intramolecular donor is preferred over an external (intermolecular) donor, taking into account the fact that the former shows 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 solvent or diluent is used , including liquid manomer, in said polymerization reactor.The catalyst composition of the present invention also contains a co-catalyst., the co-catalyst can 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, magnesium and aluminum, with aluminum being preferred. At least one hydrocarbon radical is attached directly to the metal to provide a carbon-metal bond. The hydrocarbon group used in said compounds preferably contains 1-30, most preferably I-10 carbon atoms. Examples of suitable compounds include, without limitation, ilsadium, butyllithium, diethylzinc, chlorobute Imagnesium, and dibutyl I agnesia. Preference is given to organoalumium compounds, including, for example and without limitation, the following? composed of trialqui lauminum, such co-triumiumiumium and triisobutylaluminium? aluminum alkyl hydrides, such as di-isobutyl aluminum hydride? compounds of alkalcoxy-organaal minia? and halogen-containing arganaluminum compounds, such as diethyl aluminum chloride, diisobutyl aluminum chloride and ethyl aluminum loride. Preferably, linear or cyclic stainless solids are selected as the organoaluminum compound.

In addition to, or as an alternative to, the organometallic compound, the catalyst, the catalyst composition of the present invention may include a compound containing to produce, in a reaction with the transition metal of the present invention, a non-coordinating or low coordination anion. Such compounds have been described, for example, in EP-426, 63, the complete disclosure of which is incorporated herein by reference. Said anion is bound in a manner that is sufficiently unstable to be replaced by an unsaturated monomer during the copolymerization. Such compounds are also mentioned in EP-A-277,003 and EP-A-277,004, the complete descriptions of which are incorporated herein by reference. Said compound preferably contains an Ibarane triaryl to a tetraborate Iborata or an aluminum equivalent thereof. Examples of suitable co-catalyst compounds include, but are not limited to, the following? - tetrakis (entafl uorofeni 1) borate di dimeti lani l inio tC¿, Hs.N l CH-s) s, Hl ~ tBíC ^ F .-,).,: --- bis (7,? - dicarbaundecaborate) - cobal tatoí II I) di dimeti lani linio? - tr (n-bu il) ammonium tetra and iborate? - tetrakis (pentafl uarofeni 1) triphenyl-carbenium borate? - tetrafe i Iborato de dimet i lani linio? - tris (entaflusrafeni l) borane? and - raquis (entafluarofeni l) borate. If the noncoordinating or low coordination anion 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, the full disclosure of which is incorporated herein by reference, the reaction product of a halogenated transition metal complex and an organometallic compound, such as for example triethyluminum ( TORCH). The molar ratio of the co-catalyst 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 ?! And preferably it is on a scale of about 1? 1 to about 2,500? 1. If a component containing or producing a noncoordinating anion or low coordination anion is selected as the co-ca to the hoist, the molar ratio is usually found in a range of about 100 to about 10000? , and preferably on a scale of about 1? 2 to about 250? 1. As would be appreciated by a person skilled in the art, the transition metal complex, as well as the ca-catalyst may be present in the catalyst composition as a single component or as a mixture of several components. For example, mixing may be required when there is a need to affect the molecular properties of the polymer, such as molecular weight, and in particular the molecular weight distribution. The present invention relates to a process for the co-polymerization of one or more oc-olefins and one or more aromatic vinyl monomers. As referred to herein, the term "onomeric" encompasses digests, trimers, and oligomers. The "-alephine is preferably at least one member selected from the group consisting of ethylene, propylene, butene, pentene, heptene and octene, and any combination thereof. Preferably, at least one member selected from the group consisting of ethylene and propylene is selected as the α-olefin. Suitable aromatic vinyl monomers that can be polymerized in the process of the present invention include, without limitation, those represented by the formula? wherein each R13 in the formula () is selected, for example, independently as one of the following? hydrogen? an aliphatic, cycloaliphatic or aromatic hydrocarbon group having from 1 to 10 carbon atoms, conveniently from 1 to 6 carbon atoms, very .6 conveniently from i to 4 carbon atom? and a halogen atom. Exemplary aromatic vinyl onomers include, without limitation, styrene, chlorostyrene, n-butylstyrene, and p-vini l toluene. Styrene is especially preferred. The amount of the aromatic vinylic manomer incorporated in the pitches of the present invention is 0.1 milligrams per minute. Additional olefin anomer may be copolymerized in the same process to thereby produce terpolymers and higher polymers ( which are also referred to herein as included by the term "copal eras" and made by the "co-polymerization process.") Other olefin monomers include, by way of example and without limitation, ethylene, prapylene, butene , pentene, hexene, heptene, octene, and dienes such as 1,4-hexadiene, 1,7-octadiene, dicyclopentadiene (DCPD), 5-methylene-2-norbornene, and polyenes such as the ibutadiene cone. The invention is also suitable for the preparation of rubber copalimers based on an α-olefin, an aromatic vinyl monomer and a third monomer, it is preferred to use a diene as the third monomer. Suitable for preparing rubber copolymers include those specified above. The catalyst can be run as ee, or optionally the catalyst can be supported on a suitable support or carrier, such as alumina, MgCls or silica, to provide a heterogeneous supported catalyst. The transition metal complex or the co-catalyst may be supported on the carrier. It is also possible to support both the transition metal complex and the co-catalyst, in the same carrier or in different carriers. When more than one carrier is provided, the carriers may be the same or different from each other. The supported catalyst systems of the invention can be prepared separately before they are introduced into the co-polymerisation reaction, they can be formed in itself, for example, before starting the co-polymerization reaction. By way of example, the co-reaction may be carried out under conditions of solution to suspension, in a suspension using a perfluorinated hydrocarbon, or similar liquid, in the gas phase (for example, using a fluidized bed reactor), or in a Solid phase powder polymerization. A catalytically effective amount of the present catalyst and co-catalyst is any amount that correctly results in the formation of copal. These amounts can be determined easily by the skilled artisan by routine experimentation. For example, when the co-polymerization is carried out in a liquid reaction medium, by solution or suspension polymerization, which are preferred for the process of the invention, the amount of transition metal complex to be used can generally be such that the The concentration of the transition metal in the solution or the dispersing agent is approximately 10"" or the approximately 10-3 moles / l, and preferably from 10 ~ "mols / the approximately 10 - ** moles / l. It is understood that the transition metal complex described herein undergoes several transformations or forms intermediate species prior to, and during, the course of co-polymerization.Thus, other catalytically active species or intermediates formed therein are contemplated herein. of the metal complexes described herein and other metal complexes (precursors) different from those described herein that result in the same catalytic species as the of the present invention, without departing from the scope of the present invention. Any liquid that is inert relative to the catalyst system can be used as a dispersing agent in the co-polymerization process. What suitable inert liquids that can be selected as the dispersing agent include, without limitation, the following? one or more aliphatic hydrocarbons oe saturated straight or branched chain, including without limitation, butane, pentane, hexane, heptane, pentamet and Ihep tana, and any combination thereof? and / or one or more fractions of mineral oil, including without limitation, light or regular gasoline, naphtha, erasin, gas oil, and any combination thereof. Aromatic hydrocarbons can also be used, for example benzene, ethylbenzene and toluene? however, due to the high caste associated with aromatic hydrocarbons, as well as for safety considerations, it is generally preferred not to use these solvents for production on a technical (or commercial) scale. In the polymerization process on a technical (or commercial) scale, therefore, it is preferred to use as a solvent the low-priced aliphatic hydrocarbons or mixtures thereof, marketed by the petrochemical industry. Excess aromatic vinyl or olefin manomers, including liquid vinyl aromatic or olefin manomers, may also be applied in the so-called bulk polymerization process. If an aliphatic hydrocarbon is used as the solvent, it may still contain minor amounts of aromatic hydrocarbons such as, for example, toluene. In this way, if, for example, methylaluminoxane is selected (MAO >; As the co-catalyzed, toluene can be used as the solvent for the MAO to dissolve the MAO in solution and supply the solution to the polymerization reactor. Is it convenient to dry or purify the solvents, if they are used? this can be done by the person skilled in the art without undue experimentation. If solution or bulk polymerization is used, it is preferably carried out at temperatures well above the melting point of the polymer to be produced. Suitable temperatures generally include, without limitation, temperatures on a scale from about 120 ° C to about 260 ° C.

In general, the suspension or gaseous phase polymerization takes place at lower temperatures, that is, temperatures well below the melting temperature of the polymer to be produced. Generally, temperatures suitable for suspension or gaseous phase polymerization are less than about 1050C. The polymer solution originating from the polymerization can be treated by a known method ' per se . In general, the catalyst is deactivated to a certain extent during the polymer treatment. Deactivation is also effected in a manner known per se, for example, by means of water or an alcohol. Removal of the catalyst residues can generally be omitted, since the amount of catalyst in the copolymer, in particular the content of halogen and transition metal in the polymer, is very low due to the use of the catalyst ethemate according to the invention. The copolymerization can be carried out at subatmospheric, atmospheric and elevated pressure, and under conditions in which at least one of the monomers is a liquid, which can be accomplished by applying suitable combinations of temperature and pressure, continuously discontinuous way. If the coating is carried out under pressure, the polymer yield can be substantially increased, resulting in a still lower catalyst residue content. Preferably, the copolymerization is carried out at pressures in the range from about 0.1 MPa to about 25 MPa. Higher pressures may be applied, typically, but not limited, to 100 MPa and more, if the polymerization is carried out in so-called high-pressure reactors. In said high pressure process, the catalyst according to the present invention can also be used with good results. The magnetization can also be carried out in several steps, in series, as well as in parallel. If required, the catalyst composition, temperature, hydrogen concentration, pressure, residence time, etc., or any combination thereof, can be varied step by step. In this way, products having a wider distribution of molecular weights can be obtained.

EXAMPLES The method according to the invention will be explained below with reference to the following examples, which serve to explain the present invention in more detail. It will be appreciated that the invention is not restricted to these examples and methods. All tests in which organometallic compounds were included were carried out in an inert nitrogen atmosphere, using standard Schlenk equipment. A method for the synthesis of (di eti la inoet i l) -tetrameti Ici ciopentadienyl is published in P. Jutzi et al., Synthesis 1993, 684, the full disclosure of which is incorporated herein by reference. TiCl 3, esters, lithium reagents, 2-bromate-2-butene and 1-chlorocyclohexene were supplied by Aldrich Chemical Company. TiCl.g »3THHF was obtained by heating TiCl3 for 24 in THF with reflux. In the following example, THF refers to tetrahydrofuran, "Me" refers to methyl, "(t) Bu" refers to tertiary butyl, "Ind" refers to indenyl, "Flu" refers to fluorenyl, and "iPr" refers to "refers to ieopropyl.

Synthesis of transition metal complexes of bidentate monocyclopentadiene. Examples I-IV indicate non-limiting methods for preparing embodiments of the transition metal complexes of the present invention.

EXAMPLE I Synthesis of di (2-di-methylaminoethyl) tetramethyl-1-chloroethylene chloride (III) (CwMe.t (CH?)) NMe ^ TiCl) (a) Preparation of 4-hydroxy-4- (imeti ino-ethyl) -, 5-dimethyl-2,5-heptadiene. 2-Bromo-2-butene (108 g? 0.800 mol) was added at 10. g of lithium (1.43 moles) in ethyl ether (300 ml) in the tranecureo for about 30 minutes under reflux. Deepuée of shaking during the night (17 hours), ee added to the reaction mixture 3- (N, N-di-ethylamino) -ethyl propionate (52.0 g, 0.359 mol) over the course of about 15 minutes. After stirring for 30 minutes at room temperature, 2O0 ml of water was added dropwise. After separation, the water phase was extracted twice with 50 ml of CH .-. CI.- ,. The organic phase was concentrated by boiling and the residue was distilled under reduced pressure. The yield was 51.0 g (657.). (b) Preparation of (dimethylenol) tetramethyl cyclopentadiene The compound (21.1 g? 0.10 oles) prepared as described above in Example I (a) was added in one portion to p-oluenesulfonic acid-Ha0 ( 28.5 g? 0.15 moles) 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 aj-jCO-j1"lOH ^ O in 250 ml of water.After separation, the water phase was extracted from the The combined ether layer was dried (Na 2 SO 4), filtered and concentrated by boiling, then the residue was distilled under reduced pressure, the yield was 11.6 g. 60%). (c) Preparation of (dimethylaminoet yl) tetramethyl cyclopentadienyl tiylium (III) diclators 1.0 n-BuLi equivalent (1.43 ml? 1.6 M> (after cooling to -60 ° C) was added. a solution of Ct5Me ^ H (CH2)? 2NMes-: from Example Kb) (0.442 g? 2.29 mmoles) in THF (50 ml>, after which the cooling bath was removed.After heating to room temperature, the solution was cooled to -100 ° C and then TiCl3"3THF (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. addition of special boiling point gasoline (ie, a C ^ hydrocarbon action with a boiling scale of 65-70 ° C, which is obtained from Shell or Exxon), the complex was purified (green colored solid ) by repeated washing of the solid, followed by filtration and retro-distillation of the solvent. pure eja by sublimation.

EXAMPLE II Synthesis of dichloride of < dibutylaminoeti 1 < tetramethyl iclopentadienyl titanium (III). < CwMe ^ (CHa¡) aNBu8TiCla¡) (a) Preparation of ethyl 3- (N, N-di-n-butylamino) ropionate. Ethyl 3-bromopropyanate (18.0 g.O.10 mol) was carefully added to di-n-butylamine (25.8 g? 0.20 males).

Followed by agitation for doe hours. Then, diethyl ether (200 ml) and pentane (200 ml) were added, the precipitate was filtered off, the filtrate was concentrated by boiling and the residue was distilled off under high pressure, the yield was 7.0 g (31T). . (b) Preparation of bis (2-buteni l) (di-n-but i laminoeti l) methanol 2-li thio-2-butene was prepared from 2-bromo-2-butene (16.5 g? 0.122 moles) ) and lithium (2.8 g 0.4 mole), as in Example I. To this, the ester of Example II (a) (7. g? 0.31 mole) was added with reflux in the course of about 5 minutes, followed by stirring for approximately 30 minutes. Then, water (200 ml) was added carefully, dropwise. The water layer was separated and extracted twice with 50 ml of CH.-Cl.-,., The combined organic layer was washed once with 50 ml of water, dried with '-gCO- .., it was filtered and concentrated by boiling. The yield was 9.0 g (1007.).

() Preparation of (di-n-but i laminoeti 1) tetramet and cyclopentadiene 4.5 g (0.015 mole) of the compound of example II (b) were added dropwise to 40 ml of 0 ° concentrated sulfuric acid. C, followed by stirring for another 30 minutes at 0 ° C. Then, the reaction mixture was poured into a mixture of 400 ml of water and 200 ml of hexane. The mixture was made alkaline with NaOH (60 g) while cooling in an ice bath. The water layer was separated and extracted with hexane. The combined hexane layer was dried with K- »C0-, filtered and concentrated by boiling. The residue was distilled at subathemical pressure. The yield was 2.3 g (55%). (d) Preparation of (di-n-butylaminoetyl) tetramethyl 1-cyclopentadiethylthio (III) dichloride. 1.0 equivalent of n-BuLi (0.75 ml? 1.6 M) was added (after cooling to -60 ° to a solution of the CβMe ^ H (CH 2) E! IMBu 5 -i from Example II (c) (0.332 g, 1.20 mmolee) in THF (50 ml), after which the cooling bath was removed. At room temperature, the solution was cooled to -100 ° C and then TiCL3 »THF (0.45 g? 1.20 mmoles) was added, after stirring for 2 hours at room temperature, the THF was removed at subatmospheric pressure. as in example I.

EXAMPLE III Another catalyst component was prepared, dichloride of < dideci laminoeti 1) tetramet i 1-cyclopentadieni l-titania (ISS (CsSMe ^ (CH = ¡) -, N (C10H21) 2TiClz>, in a manner analogous to that described in example I, the difference being that applied the corresponding di-deci l-amino-propionate in place of ethyl 3- (N, N-dimethylamino) ropionate.

EXAMPLE IV Synthesis of the > 2 > 4-triisp? RoPil-3- (ditnetyl-aminoe il) cyclopentadieni 13-i tanjo < II) dimeti what (a) Reaction of cyclopentadiene with isopropyl bromide. Aqueous KOH (50%? 1950 g, approximately 31.5 moles in 2.483 l of water) was placed and as a phase transfer agent, Adogen 464 (31.5 g) in a three-necked flask. 3 1 necks equipped with a condenser, mechanical stirrer, heating mantilla, thermometer and an input adapter. Freshly fractionated cyclopentadiene (55.3 g, 0.79 mole) and isopropyl bromide (364 g, 2.94 mole) was added and stirring was started. The mixture turned brown and its temperature rose (50 ° C). The mixture was 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 (with MgSO 4) the solvent was evaporated, leaving a brown yellow oil. GC and GC-MS analysis showed that the product mixture contains diisopropyl cyclopentadiene (iPr.--Cp, 40%) and tri-isopropylcyclopentadiene (iPr-j-Cp, 60%). IPr2-Cp and iPr3-Cp were isolated by distillation under reduced pressure (20 mHg). The yield depended on the accuracy of the distillation (approximately 0.2 moles of iPr-2-Cp (25%) and 0.3 moles of iPr3-Cp (40%)). (b) Reaction of 1, 2,4-tri-isopropy-cyclopentadiene with lithium chloride and dimethyl chloride In a 500 ml dry flask containing a magnetic stirrer, under dry nitrogen, a solution of 62.5 ml of n-1 was added. butyllithium (1.6 M in n-hexane? 100 mmol), to a solution of 19.2 g (100 mmoles) of iPr3-Cp in 250 ml of THF at -60 ° C. The solution was allowed to come to room temperature, after which the solution was stirred overnight. After cooling to -60 ° C, dimethyl laminoeti chloride (11.3 g, 105 moles) was added, free of HCl (by the method of Rees, WS Jr. &Dippel .A., In 0PPI BRSEFS vol. 24, No. 5, 1992, which is incorporated herein by reference) by means of a dropping funnel over the course of 5 minutes. The solution was allowed to come to room temperature, after which it was stirred overnight. The progress of the reaction was monitored by means of GC. After the addition of water and a mixture of alkanes, the organic layer was separated, dried and evaporated under reduced pressure. After the iPr3-Cp starting material (30%), 5 isomers of the product (di eti laminoeti l) -triisoprspi Iciclapentad ene (LH? 70%) are visible in GC. Two isomers are geminal (together 30%). The removal of the geminal isomers was made feasible by precipitation of the potassium salt of the IPr3-Cp anion and filtration and washing with a mixture of scopes (3x). The overall yield (in relation to iPr3-Cp) was 30 mM (30%). (c) Reaction sequence applied at 1, 2,4-tri-iso-propyl 1-3- (dimethylaminoeti I) - iclopentadeni l 3-ti-tanium (III dimethyl) TiCl 3 »3THF (18.53 g, 50.0 mmol) solid was added to a solution of K iPr3-Cp in 160 ml of THF at -60 ° C immediately, after which the solution was allowed to come to room temperature.The color changed from blue to green.After all the TiCl3 disappeared, the The reaction mixture was again cooled to -60 ° C, after which 2.0 equivalents of MeLi (62.5 ml of a 1.6 M solution in Ets0) were added. After heating to room temperature again, the black solution was stirred for 30 minutes. more, after which the THF was removed under reduced pressure.

Polymerization experiments Examples V to XVII indicate non-limiting procedures for preparing ca-palmers with the transition metal complexes of the present invention. The polymerization experiments were carried out in accoce with the procedure which is described in general terms below. Unless indicated otherwise, the conditions specified in example V were applied in each of the individual examples.

EXAMPLE V Styrene was distilled from CaH.- »low vacuum. 600 ml of a mixture of alkanes was introduced as a solvent in a stainless steel reactor with a volume of 1.5 liters under a dry N- atmosphere. Then, the required amount of dry styrene was introduced into the reactor. The reactor was heated to S0 ° C, with stirring, at an absolute ethylene pressure of 800 kPa. 25 ml of a mixture of alkanes was dosed as a solvent in a catalyst premix vessel having a volume of 100 ml. The required amount of the etioluminoxane co-catalyst (MAO, from Witco, 10 wt% solution in toluene) was pre-mixed for one minute with the required amount of transition metal compound. Subsequently, this mixture was dosed to the reactor, after which the polymerization began. The polymerization reaction was carried out isothermally. An absolute constant ethylene pressure of 8 bar was maintained. After the desired time, the ethyl supply was stopped and the reaction mixture was drained and quenched with the help of methanol. The reaction mixture containing methanol was washed with water and HCl to remove the residual catalyst. Then, the mixture was neutralized with the help of NaHCO.- ,. Then, an antioxidant (Irganox 1076, TM) was added to the organic fraction to stabilize the polymer. The polymer was dried under vacuum for 24 hours at 70 ° C.

EXAMPLE VI The reactor was filled with 600 ml of alkane mixture and 45 g of styrene according to the procedure indicated above in example V. The reactor was brought to a temperature of 80 ° C and saturated with 8 bar of ethylene, with stirring . 10 micromoles of EtCp (iPr) 3NMe: -? TiCls were previously mixed. (Example IV) with 20 myole of MAO (Al / Ti = 2000) for 1 minute in a catalyst dosing vessel. After 6 minutes of polymerization, the reaction mixture was drained and quenched with the help of methanol. After being stabilized, the polymer was dried in vacuo. The polymer yield reached 15.8 kg / o Ti-hour »The product was analyzed by means of SEC-DV, -« - H-NMR and CED. The polymer formed was a co-polymer with an Mw of 250,000 g / mol and a maximum melting temperature (determined by CED) of 93 ° C.

COMPARATIVE EXPERIMENT A With the aid of the transition metal compound MeCi-Jf-NtBuTiCl2, known from EP-A-416,815, a polymerization area was carried out under the conditions described in Example VI, using MAO as the co-catalyst (proportion Al? Ti =? O>, for 7 minutes) The yield was 14.6 kg / mol Ti-hour The product had an Mw.de 145,000 g / mol, and a maximum temperature of 114 ° C.

EXAMPLE VII Example VI was repeated, but 75 g of styrene was added to the contents of the reactor. 10 micromoles of the transition metal compound (CßMe4H (O -,), - N- (* -? Or * ^ 2i sTiCla (Example III), were mixed with 10 millimoles of MAO (Al? Ti = 1000? 1) during 1 minute in the catalyst dosing vessel The reaction mixture was subjected to co-polymerization The yield was 6.7 g The styrene content determined by "-H-NMR reached 7.5 wt%" The Mw, determined by of SEC-DV, was 180,000 g / mol.

EXAMPLE VII Example VII was repeated, but 10 micromoles of the transition metal compound (Ca5Me4 (CHz) zNBuaTiClz (Example II) were mixed together for 1 minute.The copolymer formed had an Mw (determined by means of SEC-DV) of 180,000. g / mol The styrene content was determined by H-RMI and 6.3 mole% was found.

EXAMPLE IX A co-polymerization process was carried out using the transition metal compound (Ce5ME.sub.4 (CH.sub.1 -?): -? NMei-tClCl- (Example I), under the conditions described in Example VII. The copolymer formed contained 8.6 mol% styrene, determined by means of * H NMR The polymer had an Mw of 130,000 g / mol (SEC-DV).

Comparative Experiment B The co-poling of ethylene and styrene was carried out as described in Example VII, with the exception that the catalyst composition included 10 μM MessSiCp * NtBuTiCls8 micromoles and 20 mmolee MAO ( Al? Ti = 2000? 1), which were mixed for 1 minute in the catalyst dosing vessel.The polymer formed (6.2 g) was found to have an Mw of 82,000 g / mol (determined by means of SEC-DV) and contained 4.2 mol% styrene.

EXAMPLE X A catalyst was synthesized on a carrier by adding 10 ml of dry toluene to 1453 g of SiO - »(Grace / Davidson W952, drying for 4 hours at 4000C under dry N2). Then, 16 ml of MAO (Witco, 30% by weight, in toluene) was added over the course of 10 minutes with stirring at 300. The sample was dried for 2 hours under vacuum with stirring, after which 25 ml of a mixture of alkanes was added and the resulting mixture was stirred for 12 hours at 300 K. Then a suspension of 10-* moles was added. (C 2 Me) (CH 2) a: NMes »TiCls- (Example I) with stirring After drying, it was encased that the catalyst contained 25.9 mole% Al and had an Al / Ti ratio of 328. It was carried out a co-polymerization experiment using the sustained catalyst described above under conditions comparable to those of Example VI 45 g of styrene was added to the reactor, then 20 micromoles (based on Ti) of the sustained catalyst were introduced into the reactor. The co-polymerization reaction was carried out at a barium ethylene pressure at 80 ° C. The polymer formed (1450 kg / Ti-hour mal) was analyzed by means of SEC-DV. of 490,000 g / mol, at a styrene content of 3.1 mol% (deter mined by * H NMR).

EXAMPLE XI A 1.5 liter volume stainless steel reactor was filled with 600 l of a mixed high boiling range solvent (with a boiling scale starting at 180 ° C) for a solution polymerization. The temperature rose to 1500C while stirring. Afterwards, the reactor was saturated with ethylene and the ethylene pressure was brought to 21 bar. 45 g of dry styrene was introduced into the reactor. Then, 0.4 mmol alkylaluminum (triethyl aluminum) was introduced into the reactor as a scavenger. The transition metal complex (CßMe ^ (CHz) s? NMessTi ea ,, obtained by labeling the compound of example I by means of a method similar to that described in example IV (c), was previously mixed with tetrakis (pentafluoropheni 1). ) borate of dimethy lani 1 ina (DMAHBFja., -,) in 25 ml of high boiling point alkane solvent (ratio B / Ti • * = 2) for 1 minute in a 100 ml catalyst dosing container. The co-pal reaction began by introducing the reaction mixture from the catalyst premix vessel into the reactor.A constant ethylene pressure of 21 bar was maintained and the co-polymerization was carried out isothermally at 150 ° C. After 10 minutes, the reaction mixture was drained from the reactor, quenched with methanol and stabilized with anti-oxidant (Irganox 1076 (TM)) After vacuum drying, the product was analyzed by means of SEC-DV. that the product had a molecular pee 82, OOO g / mol The product also contained 2.7 mol% styrene, determined by means of 1 H NMR, and the CED curve indicated a maximum melting temperature of 127 ° C.

EXAMPLE XII A co-polymerization reaction was carried out as described in Example VII, with the exception that the transition metal complex was (CasMei - (CHsa> -2NBus, TiMej2, obtained by mixing the compound of Example II according to the method described in Example IV (c) The polymer formed was analyzed by means of SEC-DV (Mw = 80,000 g / mal > and 4H NMR (4.0 mole% styrene content).

EXAMPLE XIII A co-polymerization reaction was carried out as described in Example VI, except that the transition metal complex was EtCp1 iPr) 3NMe¡BTiMe2, obtained by methylating the compound of Example IV. The polymer formed was analyzed by means of SEC-DV (Mw = 105,000 g / mol) and H NMR (content of tinno 3.8 mol%).

EXAMPLE XIV A co-polymerization reaction was carried out as described in Example VI, with the difference that 3.0 ml of dry 1,7-octadiena were further introduced into the reactor, camo a third monomer after having introduced the styrene ( terpol imer ization).

After that, the co-pollication was carried out in exactly the same way as described in the example.

SAW. The polymer formed contained 1.6 mol% styrene and 0.6% octadiene, both determined by means of * - ^ C-R N and * H NMR, at a polymer yield of 12,000 kg / mol Ti-hour.

EXAMPLE XV A procedure for co-operating the ethylene / styrene was carried out as described in Example VI, copolying now only 225 g of styrene at an ethylene pressure of 600 KPa. The co-pal imerization was carried out at 80 ° C using (CsMe ^) (CHas) s, NMe = iTiCls, (example I) and MAO (Al / Ti-1000). The formed product was purified and analyzed by means of SEC-DV. It was found that the Mw was 100 kg / mol, and the Mn was 53,000 g / mol. The iH NMR analysis showed that the polymer contained 19.9 mol% styrene.

EXAMPLE XVI A co-polymerization experiment was carried out as described in Example XII, with the exception that the transition metal compound was EtCp (iPr) 3NMe2TiClβ (Example IV), which was used in combination with MAO (Al / Ti = 1000) and 135 g of styrene was added as the second monomer. The SEC-DV analysis of the formed polymer revealed an Mw of 150,000 g / mol. The Mn was 47,000 g / mol. The copolymer contained 12.3 mol% styrene determined by means of * H NMR.

Comparative Experiment C A co-pal imerization experiment was carried out as described in Example XIII, except that the catalyst composition included the transition metal compound Mes-: SiCp * NtBuTiCl? », In combination with MAO (Al / Ti = 1000). At a styrene content comparable to that obtained in Example XII, it was found that Mw and Mn were only 24,000 g / mol and 9,000 g / mol, respectively.

TABLE 1 Axis of complexes of transitional aetal according to the invention (see formulas I and V) SW In this way, it will be noted that the objectives and principles of this invention have been fully and effectively realized. However, it will be considered that the above specific preferred embodiments have been shown and described for the purposes of this invention, and are subject to change without departing from said principles.

Claims (15)

NOVELTY OF THE INVENTION CLAIMS

1. A process comprising co-polymerizing at least one olefin and at least one aromatic vinyl monomer in the presence of a catalyst comprising a complex of reduced transition metal and a co-catalyst, wherein said reduced traneition metal complex has the following structure? X

I M - L "I where? M? is a reduced traneition 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? (rR ^ -J ^ YÍ-R ^ -DR7">, and is a member selected from the group consisting of a cyclopentadienyl group, amido (-NRr-), and phosphide (-PR'-)? R is at least one member selected from the group that you connected of (i) a connecting group between the rump Y and the DR'nt group and (ii) a connecting group between the group Y and the Ar group, where the ligand X contains more than one group R, the R groups can be identical or different from each other? D ee an electron donor heteroatom selected from group 15 or 16 of the periodic table of the elements? R 'is a substituent selected from the group consists of a hydrogen, a hydrocarbon radical and a heteroatom-containing portion, except that R 'can not be hydrogen when Rt is directly attached to the electron donating hetero atom D, where if the monoanionic ligand r toothed X contains more than one substituent R ', can the substituents R' be identical or different from each other? Ar e Is an electron donor aryl group? L is a monoanionic ligand bonded to the reduced transition metal M, wherein the monoanionic ligand L is not a ligand comprising a cyclopentadienyl group, amide (-NR-> or phosphido (-PR '-) Í and wherein the ligands monoanionics L can be identical or different from each other? K is a neutral or anionic ligand bound to the reduced transition metal M, where if the transition metal complex contains more than one K-ligand, the K-ligands can be identical or different one of the other? m is the number of li adas, where if the ligand K is an anionic ligand, it is 0 for M3 +, m is 1 for M *** and m is 2 for s *, and if K is a neutral ligand , m is increased by one for each neutral K ligand? n is the number of Rr groups attached to electron donative heteroatom D, where if D is selected from group 15 of the periodic table of ele ents, n is 2, and if D is selected from group 16 of the periodic table of the elements, n is 1? qys are the number of groups (-R * -DR '") and groups (Ar-Rt_) attached to the group Y, respectively, where q + s is an integer not less than 1? and t is the number of R groups that connect each of (i) the groups Y and Ar, and (ii) the groups Y and DR'nr where t is independently selected as O or i. 2. A method according to claim 1, characterized in that the group Y is a cyclopentadienyl group.

3. A process according to claim 2, characterized in that the cyclapentadienyl group is an indenyl group, benzaindeni the fluorenyl not substitued or substituted.

4. A method according to claim 2, characterized in that said reduced transition metal complex has the following structure? X I M (III) - L, I in which i M (III) is a transition metal of group 4 of the periodic table of the elements in oxidation state 3+.

5. A process according to claim 2, characterized in that said reduced transition metal is titanium.

6. A process according to claim 2, characterized in that said heteatoma D electron donor is nitrogen.

7. A method according to claim 2, characterized park said group R has the following structure; (-CR * sß-> | p, * 'where p is 1, 2, 3 or 4.

8. - A method according to claim 2, characterized in that said monoanionic ligand L is selected from the group consisting of a halide, an alkyl group, and a benzyl group.

9. A process according to claim 2, characterized in that said co-catalyst comprises a linear or cyclic aluminoxane or a tricarium Iborane or tetraari Iborate.

10. A method according to claim 2, characterized in that at least one member selected from the group consisting of said reduced transition metal complex and said co-catalyst is supported on at least one carrier.

11. A process according to claim 2, characterized in that said "-alephine is at least one member selected from the group consisting of ethylene, prapylene, butene, hexene, octene, and any combination thereof.

12. A process according to claim 2, characterized in that said aromatic vinyl monomer is at least one member of the group consisting of styrene, chloro-irene, n-butyleneterene, p-vini l toluene, and any combination thereof.

13. A method according to claim 2, further characterized in that. said process comprises co-erecting a diene.

14. - A method according to claim 2, further characterized in that said procedure comprises a step for obtaining a rubber-type cappolymer.

15. A method according to claim 13, further characterized in that said method comprises a step of obtaining a rubber-type copolymer.