MXPA00001026A - Catalysts based on fulvene metal complexes - Google Patents

Abstract

The invention concerns a catalyst system based on fulvene metal complexes (metallocene), which have been activated with a Lewis acid free from aluminoxan and boron, and its use for polymerising unsaturated compounds, in particular for polymerising and copolymerising olefins and/or dienes. An example for a catalyst system is:(CP*)(C5(CH3)4=CH2)ZRPH. Said complex has been activated with triisobutylaluminium (TIBA).

Description

CATALYSTS BASED ON FULVENO METALLIC COMPLEXES. FIELD OF THE INVENTION The present invention relates to a catalytic system based on fulvene metal complexes as well as to its use for the polymerization of unsaturated compounds, especially for the polymerization and copolymerization of olefins and / or dienes. Description of the prior art. The use of metal cyclopentadienyl complexes has been known for a long time, especially the use of metallocene complexes in admixture with activating co-catalysts, preferably alumoxanes (MAO) for the polymerization of olefins and diolefins (for example EP-A) 129 368., 347 128, 347 129, 69 951, 351 392, 485 821, 485 823). The metallocenes have been revealed as specific catalysts, highly effective, in the polymerization of olefins especially. In order to increase the activity, the selectivity, the control of the microstructure, the molecular weights and the molecular weight distribution, a plurality of new metallocene catalysts or metallocene catalyst systems has been developed in recent years. for the polymerization of olefinic compounds. The catalyst systems described above based on MAO have, however, serious drawbacks, as will be explained below in greater detail. For REF .: 32479 on the side can not prepare the aluminoxanes, especially MAO, neither in situ nor in the previous formation with high capacity of reproduction. MAOs are a mixture of various alkylaluminum-containing species that are in mutual equilibrium. The number and structure of the aluminum compounds present in the MAO can not be defined exactly. Therefore, the polymerization of olefins with catalytic systems containing MAO can not always be reproduced. In addition MAOs are not stable to storage and modify their composition when thermal stresses occur. A serious drawback consists in the large excess in MAO, which is required for the activation of the metallocenes. The large MAO / metallocene ratio is a mandatory precondition for obtaining high catalytic activity. This results in a fundamental disadvantage of the process, since the aluminum compound must be separated from the polymer during processing. The MAO is also a determining factor for costs. Large excesses in MAO are uneconomical for industrial application. To avoid these drawbacks, polymerization catalysts free of alumoxane have been developed in the past years. In an exemplary way, it is described by Jordán et al. in J. Am. Chem. Soc., Vol. 108 (1986), 7410 a cationic complex of methyl zirconocene, which has as counter-ion tetraphenyl borate and which polymerizes ethylene in methylene chloride. EP-A 227 003 and EP-A 277 004 describe ionic metallocenes, which are obtained by reaction of metallocenes with ionizing reagents. EP-A-468 537 discloses catalysts with an ionic structure which are formed by the reaction of di-alkyl methalocene compounds with tetrakis (pentafluoro-n-nyl) boron compounds. Ionic metallocenes are suitable as catalysts for the polymerization of olefins. However, the sensitivity of the catalysts to impurities, such as, for example, humidity and oxygen, is a disadvantage. Thus, in carrying out the polymerizations, measures have to be taken to ensure the highest possible purity of the monomers used and of the solvents. This is very cumbersome and expensive from the industrial point of view. In order to eliminate these drawbacks, EP-A 427 697 and WO 92/01723 describe processes for the polymerization of olefins, in which the combination of metallocene dichlorides with aluminum alkyls and tetrakis (pentafluorophenyl) boron compounds is used. Catalytic system mode. Alkylaluminum compounds serve, on the one hand, as agents for alkylating the metallocene components and acting, on the other hand, as cleansers to protect the active species of the catalyst against impurities. The processes, corresponding to the state of the art, for obtaining cationic metallocenes have, however, the disadvantage that the cationizing reagents, for example tetrakis (penta-fluorophenyl) boron compounds, are partly cumbersome for their synthesis and its use causes high costs. According to the authors Bercaw et al., JACS (1972), 94, 1219, is the fulvene complex formed? -2, 3, 4, 5-tetramethylcyclopentadienyl-1-methylene) (77 -pentamethylethylpentadi-enyl) titanmethyl by thermolysis of bis (77-pentamethyl-cyclopentadienyl) titanedimethyl. Nothing is known about the activity for the polymerization of this complex. Described in T. J. Marks et al., JACS (1988), 110, 7701, the thermolysis of pentamethyl-cyclopentadienyl complexes of zirconium and hafnium. By thermolysis of bis (77-pen-tamethylcyclopentadienyl) zir-coniodiphenyl, the complex of fulvene (77 -2, 3,4,5-te-tramethylcyclopentadienyl-1-methylene) (77 -penta-methylcyclopentadiene) zirconiofenyl is formed. This compound itself has no activity for polymerization. Detailed description of the invention. So there was the task of finding a catalyst system that avoided the aforementioned drawbacks. In addition, procedures based on metallocene systems free of aluminoxane should be developed. It has now surprisingly been found that catalyst systems based on fulvene metal complexes are suitable in a particularly good manner for the task envisaged. The object of the present invention is therefore a catalyst system consisting of a) a fulvene metal complex of the formula wherein M means a metal of groups IIIb, IVb, Vb, VIb or of the lanthanides or of the actinides of the Periodic System of the Elements [N.N. Greenwood, A.Enshaw, Chemie der Element, VCH 1990], A means an anionic ligand bridged if necessary one or several times, R1, R2, R3, R4, R5, R6, R7 are the same or different and mean hydrogen, halogen, a cyano group, an alkyl group with 1 to 20 carbon atoms, a fluoroalkyl group with 1 to 10 carbon atoms, a fluoroaryl group with 6 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, an aryl group with 6 to 20 carbon atoms carbon atoms, an aryloxy group with 6 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, an arylalkyl group with 7 to 40 carbon atoms, an alkylaryl group with 7 to 40 carbon atoms, a - arylalkenyl with 8 to 40 carbon atoms, an alkynyl group with 2 to 10 carbon atoms, a silyl group optionally substituted by hydrocarbon radicals with 1 to 10 carbon atoms, or R, R, R, R, R , R, R form respectively together with the linking atoms, one or more aliphatic or aromatic ring systems s, which may contain one or more heteroatoms (O, N, S) and having from 5 to 10 carbon atoms, m means 0, 1, 2 or 3 as well as k means 1, 2 or 3 and the sum of m + k is, depending on the degree of oxidation of M, from 1 to 5 and b) a Lewis acid free of aluminoxane and of boron, suitable for the activation of the metal complex a), the molar proportion being found between the component a ) and component b) in the range from 1: 0.1 to 1: 10,000, preferably from 1: 1 to 1: 1,000. The synthesis of the fulvene metal complexes of the formula (I) is known and has been described for example in T. J. Marks et al., Organometallics 1987, 6, 232-241. Another object of the present invention is a process for obtaining a catalyst system, characterized in that a mixture consisting of a Lewis acid free of aluminoxane and boron, suitable for activation, is heat-treated in a suitable reaction medium, and a metal complex of the formula (II) in which M, A, R 1 to R 7 have the meaning indicated in claim 1) and X means hydrogen, halogen, an alkyl group with 1 to 30 carbon atoms, aryl group with 6 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, an arylalkyl group with 7 to 40 carbon atoms, an alkylaryl group with 7 to 40 carbon atoms, an arylalkyl group with 8 to 40 carbon atoms, an alkynyl group with 2 to 10 carbon atoms, a substituted silyl group, if appropriate. The heat treatment is carried out in the temperature range of 60 ° C to 250 ° C, preferably 90 ° C to 150 ° C. The duration of the heat treatment is in the range of 1 minute to 20 hours, preferably in the range of 15 minutes to 120 minutes. Suitable reaction media are, for example, aromatic hydrocarbons, such as benzene or toluene, or aliphatic hydrocarbons, such as hexane, heptane, octane, cyclohexane or mixtures of various hydrocarbons. The heat treatment is carried out in the presence of an olefin or a diolefin. The molar ratio between the Lewis acid and the metal complex of the formula (II) is in the range from 1: 0.1 to 1: 10,000, preferably from 1: 1 to 1: 1,000. Suitable metal complexes of the fulvene of the formula (I) are especially those in which M means a metal of groups IVb, Vb or of the lanthanides of the Periodic Table of the Elements. A means an allyl group of the formula C3R 5, where R6 has the same meaning as R up to R in. the formula (I), a halide F, Cl, Br, I, a sulfonate of the formula 03R, an amide of the formula NR 2 > a pyrazolate of the formula N2C3R 73 where R7 means hydrogen or an alkyl group with 1 to 10 carbon atoms, a pyrazolyl borate of the formula R ° B (N2C3R73) 3 an alcoholate or phenolate of the formula OR, a siloxane of the OSiR 3 formula, a thiolate of the formula SR, an acetylacetonate of the formula (R- ^ O ^ R6, a diimine of the formula (RN = CR) 2, a cyclopentadienyl of the formula C5H R65_ where q means 0, 1, 2, 3, 4, 5, an indenyl of the formula C 9QHp7-rr where r means 0, 1, 2, 3, 4, 5, 6, 7, a fluorenyl of the formula C 13 Hg_sR q where s means O, 1, 2, 3, 4, 5, 6, 7, 8, 9 as well as an alkyl moiety with 1 at 30 carbon atoms, an aryl radical with 6 to 10 carbon atoms, as well as an alkylaryl radical having 7 to 40 carbon atoms, R 1 to R 5 and R 6 mean an alkyl group with 1 to 30 carbon atoms, an aryl group with 6 to 10 carbon atoms, an alkylaryl group with 7 to 40 carbon atoms, especially hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertbutyl, phenyl, methylphenyl, cyclohexyl and benzyl, myk they have the meaning indicated above. Especially preferred are fulvene metal complexes of the formula (I), in which M means titanium, zirconium, hafnium, vanadium, niobium and tantalum, A means bis (trimethylsilyl) amide, dimethylamide, diethyl amide, diisopropylamide, , 6-di-tert. -butyl-methylphenolone, cyclopentadienyl, methylcyclopentadienyl, benzylcyclopentadienyl, n-butylcyclopentadienyl, pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, 2,4,7-trimethylcyclopentadienyl, dimethylcyclopentadienyl, indigo, 2-methylindenyl, 2-methyl-4,5. -benzoindenyl, 2-methyl-4-phenylindenyl, fluorenyl or 9-methyl-fluorenyl.

The formula (I) indicated for fulvene metal complexes should be considered as a formal representation of the relations of the bonds and represents an example of a structural variant. As is known to the person skilled in the art, the relationships of the metal complex bonds depend, among other things, on the central atom, the oxidation level as well as the substituents of the fulvene ligands. Suitable Lewis acids are co-catalysts known in the field of Ziegler-Natta catalysts, such as, for example, aluminum, magnesium or zinc compounds. Particularly suitable Lewis acids are trialkylaluminium compounds, such as trimethylaluminum, triethylaluminum, triisobutylaluminum, triisooctylaluminum, dialkylaluminum compounds such as diisobutylaluminum, diisobutylaluminum fluoride and diethylaluminum chloride, and substituted triarylaluminum compounds, such as tris (pentafluorophenyl) aluminum as well as ionic compounds containing tetrakis (pentafluorophenyl) aluminum, such as triphenylmethyl-tetrakis aluminate (pentafluoro-nyl), as well as N, N-dimethylanilinium-tetrahydrate aluminate (pentafluorophenyl) lo). Other examples of suitable Lewis acids are dialkyl-zinc or magnesium compounds, such as dimethyl-zinc, diethyl-zinc, di-isobutyl-zinc, butyl-ethylmagnesium, dibutylmagnesium, as well as diethylmagnesium. It is obviously possible to use the co-catalysts mixed together. Another object of the present invention is the use of the new catalyst system for the polymerization of unsaturated compounds, especially olefins and dienes. Polymerization is understood here as both the homopolymerization and also the copolymerization of the above-mentioned unsaturated compounds. Especially, alkenes with 2 to 10 carbon atoms, such as ethylene, propylene, butene-1, pentene-1 and hexene-1, octene-1, isobutylene and arylalkenes, such as styrene, will be used in the polymerization. As dienes, conjugated dienes, such as 1,3-butadiene, isoprene, 1,3-penta-diene, and non-conjugated dienes, such as 1,4-hexa-diene, 1,5-heptadiene, are especially used. , 7-dimethyl-l, 6-octadiene, 4-vinyl-1-cyclohexene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene and dicyclopentadiene. The catalysts according to the invention are suitable for obtaining rubbers based on copolymers of ethylene with one or more of the cited α-olefins and the aforementioned dienes. Furthermore, the catalyst system according to the invention is suitable for the polymerization of cyclo-olefins such as norbornene, cyclopentene, cyclohexene, cyclo-octane, and for the copolymerization of cycloolefins with ethylene or with α-olefins. The polymerization can be carried out in the liquid phase, in the presence or absence of an inert solvent, or in the gas phase. Suitable solvents are aromatic hydrocarbons, such as benzene and / or toluene, or aliphatic hydrocarbons, such as propane, hexane, heptane, octane, isobutane, cyclohexane or mixtures of the various hydrocarbons.

It is possible to use the catalyst system according to the invention arranged on a support. Suitable support materials include, for example, inorganic or organic polymeric supports, such as silica gel, zeolites, soot, activated carbons, aluminum oxide, polystyrene and polypropylene. In this case, the catalyst system according to the invention can be applied in a conventional manner to the carrier materials. The methods for the arrangement on supports of catalyst systems have been described, for example, in the US 4 808 561, 4 912 075, 5 008 228 and 4 914 253. The polymerization is carried out in general at pressures from 1 to 1,000, preferably from 1 to 100 bar, and at temperatures from -100 to + 250 ° C, preferably at 0 to + 150 ° C. The polymerization can be carried out in conventional reactors, continuously or discontinuously. The invention will be explained in more detail by means of the following examples. General indications: The preparation and handling of the organometallic compounds was carried out with the exclusion of air and humidity under argon protection (Schlenk technique). All necessary solvents were made absolute before use by boiling for several hours by means of a suitable drying agent and subsequent distillation under argon. The synthesis of the compounds of the formula (I) and of the formula (II) was carried out according to T. J. Marks et al., Organometallies (1987) 232-241. The compounds were characterized with -NMR, C-NMR and by mass spectroscopy. Abbreviations: CP *: C5 (CH3> 5 Cp "": C5 (CH3) 4H Ind: CgE- Fv: C5 (CH3) 4 = CH2 Fv "": C5 (CH3) 3H = CH2 Ph: 6H5 PhLi : Phenillithium HV: High vacuum RT: Room temperature A. Synthesis of the compounds of the formula (II) Example 1. Bis (β-pentamethylcyclopentadienyl) zirconiodiphenyl, [Cp 2 ZrPll2- '"3.62 g (8.37 g) are suspended. mmoles) of bis { β-pentamethylcyclopentadienyl) -zirconium dichloride in 60 ml of diethyl ether, the yellow-white suspension obtained is cooled to 78 ° C and 13.90 ml (25.0 mmol) are added dropwise. ) Finally, it is left to warm to RT and stirred overnight.The beige suspension was concentrated in HV to dryness and the residue was taken up in 40 ml of hexane.This suspension was filtered and the resulting red solution was concentrated by evaporation half of the suspension, which required a white solid product.For the additional crystallization, the suspension was cooled to -20 ° C. The solution was decanted and the The remnant was dried in HV. 2.94 g (68%) were obtained. Example 2. Bis (77 -tetramethylcyclopentadienyl) zirconiodiphenyl, [(Cp »») 2ZrPh23. 2.06 g (5.05 mmol) of bis (77-tetramethylcyclopentadienyl) zirconium dichloride were suspended in 60 ml of ether, the yellow-white suspension obtained was cooled to -78 ° C and added, slowly, dropwise , 8.48 ml (15.27 mmoles) of PhLi. It was then heated to RT and stirred overnight. The orange suspension formed was concentrated by evaporation to dryness in HV and the residue was taken up in 40 ml of hexane. It was filtered and the filtrate was concentrated by evaporation to the middle, whereby a solid orange-yellow product was precipitated. For the additional crystallization, the solution was cooled to -20 ° C. The orange crystals, in the form of needles, were isolated and dried in HV. 1.38 g (56%) were obtained. Example 3. { ? -Pentamethylcyclopentadienyl) (77 -indenyl) zirconium-difnyl, [(Cp *) (Ind) ZrPh2]. 640 mg (1.55 mmol) of (77-pentamethylcyclopentadienyl) (77-indenyl) zirconium dichloride was suspended in 40 ml of ether. At -78 ° C, 2.41 ml (4.34 mmoles) of PhLi were added dropwise, allowed to warm to RT and stirred overnight. The yellow-brown suspension was concentrated by evaporation in HV, the residue was taken up in n-hexane and the resulting light yellow-brown solution was filtered by evaporation to half in HV and refrigerated at -20 ° C for crystallization. . The light beige solid product, precipitated in this case, was isolated and dried in HV. 345 mg (45%) were obtained. B. Synthesis of the compounds of the formula). Example 4.? - (2, 3, 4, 5-Tetramethylcyclopentadienyl-1-methylene) (77-pen-tamethylcyclopentadienyl) zirconiofenyl, [(CP) (Fv) ZrPh].

They were dissolved in 20 ml of toluene, 4.20 g (8.14 mmoles) of Cp 2 ZrPh2 prepared according to example 1. The yellow solution was heated for 6 hours at 110 ° C, whereupon it was colored dark red . After refining, the solvent in HV was removed. The light red residue was taken up in a little hexane and crystallized at -20 ° C. The mother liquors were decanted and the light red crystals were dried in HV. 2.56 g (72%) of a crystalline solid product were obtained. Example 5. (17-Trimethylcyclopentadienyl-methylene) (77-tetramethylcyclopentadienyl) zirconiofenyl, [(Cp "") (Fv "") ZrPh]. They were dissolved in 20 ml of toluene, 900 mg (1.85 mmoles) of Cp "" 2ZrPh2 prepared according to example 2. The orange solution was heated for 2 hours at 100 ° C, whereupon it was colored dark red. After cooling, the solvent was removed in HV. The residue was taken up in a little n-hexane and crystallized at -20 ° C. The mother liquors of the red crystals were decanted and, after drying, a brown red solid was obtained, which was constituted, according to the NMR data, by two isomers in the proportion of 92: 8. 363 mg (48%) were obtained. Example 6. (77 -2,3,4,5-Tetramethyl-cyclopentadienyl-1-methylene) (77 -indenyl) zirconiofenyl, [(Fv) (Ind) ZrPh]. The mixture was heated in toluene for 1 hour at 100 ° C, a solution of 120 g (0.24 mmole) of Cp IndZrPh2, prepared according to example 3, resulting in a color change from yellow to red. After cooling, the solvent was removed in HV. The residue was taken up in a little hexane and crystallized at -20 ° C. The mother liquor of the red crystals is decanted and dried in HV. 68 mg (67%) are obtained. C. Examples of polymerization. Example 7. Obtaining the catalyst solution. 20.5 mg (40 μmoles) of [Cp 2 ZrPh2) were dissolved in 16 ml of toluene. Then 4 ml of a 1 molar solution of triisobutylaluminum (TIBA) in toluene was added and heated for 60 minutes at 100 ° C, whereby the initially colorless solution was colored light yellow. Polymerization of ethylene. 250 ml, 100 ml of toluene and 0.5 ml of a 1 molar solution of TIBA in toluene were placed in a reactor and stirred for 10 minutes. Next, ethylene was introduced into the solution with a tube for the introduction of gases, continuously, at a pressure of 1.1 bar. Polymerization was initiated by the addition of 1 ml of catalyst solution. After 15 minutes of polymerization time, at a temperature of 40 ° C and with an ethylene pressure of 1.1 bar, the reaction was stopped by the addition of 10 ml of methanol, the polymer was filtered off. formed, washed with acetone and dried in the vacuum drying cabinet. 2.02 g of polyethylene were obtained. Comparative example. Example 7 was repeated with the difference that 1 ml of a solution of 17.7 mg (34 μmol) of [Cp 2 ZrPh2] in 6/6 ml of toluene was used instead of the catalyst solution. previous thermal treatment. No polymer was obtained. Example 8. Obtaining the catalyst solution. 23.7 mg of toluene 23.7 mg (54 μmol) of [(Cp *) (Fv) ZrPh] from example 4 was dissolved. Polymerization of ethylene. The polymerization of Example 7 was repeated with the difference that 0.5 mmole of tris (2,4,4-trimethyl-pentyl) aluminum (TIOA) was placed in place of TIBA, and the polymerization was initiated by the addition 0.5 ml of the catalyst solution. 2.59 g of polyethylene were obtained.

Example 9. Polymerization of ethylene. They were placed in a 6 liter autoclave, 2 liters of toluene and 20 ml of TIBA and stirred for 10 minutes. Then 1 ml of the catalyst solution of example 8 was added. The polymerization was carried out at 40 ° C with an ethylene pressure of 10 bar. After 30 minutes of polymerization time the autoclave was decompressed, the charge was stopped with 1 liter of methanol, the precipitated polymer formed was filtered off, washed with acetone and dried in the vacuum drying cabinet. 27 were obtained, 9 g of highly crystalline polyethylene with a melting point of 150 ° C according to the measurement made by DSC. Example 10. Obtaining the catalyst solution. In 10 ml of toluene, 11.9 mg (24.4 μmol) of [(Cp "") 2ZrPh2 from example 2 were dissolved. Then 2.5 ml of a 1 molar solution of triisobutylalu-minium (TIBA) were added in toluene and heated for 60 minutes at 100 ° C, whereby the initially colorless solution was colored light yellow. Copolymerization of ethylene and 1-hexene. 250 ml of glass, 100 ml of toluene, 0.5 ml of a 1 molar solution of TIBA in toluene and 2.5 ml of 1-hexene were added and stirred for 10 minutes. Next, ethylene was introduced into the solution with a tube for the introduction of gases, continuously, at a pressure of 1.1 bar. Polymerization was initiated by the addition of 1 ml of the catalyst solution. After 15 minutes of polymerization time at a temperature of 40 ° C and with an ethylene pressure of 1.1 bar, the reaction was stopped by the addition of 10 ml of methanol, the polymer formed was filtered off, washed with acetone and dried in the vacuum drying cabinet. 1.6 g of an ethylene / l-hexene copolymer were obtained. Example 11. Obtaining the catalyst solution. 36.6 ml of toluene 15 mg (36.6 μmol) of [(Cp "") (Fv "") ZrpH] of example 5 were dissolved. Copolymerization of ethylene and propylene. They were placed in a 1.4-liter steel autoclave, which is equipped with a mechanical stirrer, pressure gauge, temperature sensor, a device for temperature control, a lock for the catalyst and devices for dosing the monomers for ethylene and propylene, 500 ml of toluene and 1 ml of triisobutylaluminum and stirred for 10 minutes. Then 58 g of propylene were metered in. The internal temperature was adjusted to 40 ° C with a thermostat. Ethylene was then metered in until the internal pressure of the reactor rose to 4 hours. By adding 2 ml of the catalyst solution, the polymerization was started and ethylene was dosed continuously so that the internal pressure was constantly 4 bar at 40 ° C. After a polymerization time of 1 hour, the polymerization was stopped with a 1% solution of HCl in methanol, stirred for 10 minutes and then the polymer was precipitated with methanol. The polymer obtained in this way was washed with methanol, isolated and dried for 20 hours at 60 ° C under vacuum, whereby 22.7 g of copolymer was obtained. The determination by IR spectroscopy of the composition of the copolymer indicated an incorporation of 86.4% of ethylene and 13.6% of pro-pylene. A Tg of -29 ° C was determined according to the DSC method. Example 13. Obtaining the catalyst solution. 32.6 ml of toluene were dissolved in 13.6 mg (32.6 μmol) of [(Fv) (Ind) ZrPh] of example 6. Terpolymerized ethylene, propylene and 5-ethylidene-2-nor-bornene. 500 ml of toluene and 1 ml of TIBA were placed in a 1.4 liter steel autoclave, which is equipped with a mechanical stirrer, pressure gauge, temperature sensor, with a device for temperature control, a lock for the catalyst and devices for the monomer dosing for ethylene and propylene. Then 54 g of propylene and 5 ml of 5-ethylidene-2-norborne-no were metered in. The internal temperature was adjusted with a thermostat at 40 ° C. Ethylene was then metered in until the internal pressure of the reactor increased to 4 bar. Polymerization was initiated by the addition of 5 ml of catalyst solution and ethylene was dosed continuously so that the internal pressure was constant at 4 bar at 40 ° C. After 1 hour of polymerization time the autoclave was decompressed and the polymer solution was combined with a 0.1% by weight hexane solution of Vulkanox BKF, stirred for 10 minutes and then the polymer was precipitated with methanol. The polymer obtained in this way was isolated and dried under vacuum for 20 hours at 60 ° C., whereby 89.7 g of terpolymer were obtained. The determination by IR spectroscopy of the composition of the terpolymer indicated an incorporation of 75.2% of ethylene, 24.3% of propylene and 0.5% of ENB. With the DSC method a Tg of -37 ° C was determined. It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (9)

1. CLAIMS Having described the invention as above, the content of the following claims is claimed as property: 1. Catalyst system, characterized in that it is constituted by a) a metallic complex of fulvene of the formula (I) wherein M means a metal of groups IIIb, IVb, Vb, VIb or of the lanthanides or of the actinides of the Periodic System of the Elements [N.N. Greenwood, A.Enshaw, Chemie der Elemente, VCH 1990], A means a bridged anionic ligand, if appropriate, one or more times, R1, R2, R3, R4, R5, R6, R7 are the same or different and mean hydrogen, halogen , a cyano group, an alkyl group with 1 to 20 carbon atoms, a fluoroalkyl group with 1 to 10 carbon atoms, a fluoroaryl group with 6 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms , an aryl group with 6 to 20 carbon atoms, an aryloxy group with 6 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, an arylalkyl group with 7 to 40 carbon atoms, an alkylaryl group with 7 at 40 carbon atoms, an arylalkenyl group with 8 to 40 carbon atoms, an alkynyl group with 2 to 10 carbon atoms, a silyl group optionally substituted by hydrocarbon radicals having 1 to 10 carbon atoms, or RJ R, R, R, R, R, R form respectively together with the linking atoms, one or several systems to aliphatic or aromatic rings, which may contain one or more heteroatoms (O, N, S) and having from 5 to 10 carbon atoms, m means 0, 1, 2 or 3 as well as k means 1, 2 or 3 and the sum of m + k is, depending on the degree of oxidation of M, from 1 to 5 and b) a Lewis acid free of aluminoxane and boron, suitable for the activation of the metal complex a), finding the molar proportion between the component a) and component b) in the range from 1: 0.1 to 1: 10,000, preferably from 1: 1 to 1: 1,000. 2. Catalyst system according to claim 1,
2. C3ra_ * eriza b perqué is used as a Lewis acid txi oarpuesto of pl -minium, zinc or magnesium.
3. 3. Catalyst system according to claim 1, wherein the acrylate is acylated with Lewis acid or a trial-quilaluminum mixture.
4. 4. - Process for obtaining a catalyst system according to one of claims 1 to 3, characterized in that a mixture consisting of a Lewis acid free of aluminoxane and boron is heat-treated in a suitable reaction medium, suitable for activation , and of a metal complex of the formula (II) wherein -in M, A, R to R have the meaning indicated in claim 1) and X means hydrogen, halogen, an alkyl group with 1 to 30 carbon atoms, an aryl group with 6 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, an arylalkyl group with 7 to 40 carbon atoms, an alkylaryl group with 7 to 40 carbon atoms, an arylalkyl group with 8 to 40 carbon atoms, an alkynyl group with 2 to 10 carbon atoms, a substituted silyl group, if appropriate.
5. 5. Process according to claim 4, characterized in that the heat treatment is carried out in the temperature range from 60 ° C to 250 ° C, preferably from 90 ° C to 150 ° C.
6. 6. Method according to claims 4 or 5, characterized in that the duration of the heat treatment is in the range of 1 minute to 20 hours, preferably 15 minutes to 6 hours.
7. 7. Process according to one of claims 4 to 6, characterized in that the heat treatment is carried out in an aliphatic or aromatic solvent.
8. 8. Process according to one of claims 4 to 7, characterized in that the heat treatment is not carried out in the presence of an olefin or a diolefin.
9. 9. Use of the catalyst system according to one of claims 1 to 3, for the polymerization of olefins and / or dienes.