NL1003012C2 - Cyclopentadiene compound substituted with aralkyl groups. - Google Patents

Description

- 1 -

CYCLOPENTADIENE COMPOUND SUBSTITUTED WITH ARALKYL GROUPS

The invention relates to a substituted cyclopentadiene compound.

Cyclopentadiene compounds, both substituted and unsubstituted, are widely used as starting materials for the production of ligands in metal complexes with catalytic activity. In the vast majority of cases, either unsubstituted or one to five methyl groups substituted cyclopentadiene is used. In addition to transition metals and lanthanides in particular, the metals in these complexes are used.

15 In the J. of Organomet. Chem, 479 (1994), 1-29, has reviewed the influence of the substituents on cyclopentadiene as a ligand in metal complexes. It establishes on the one hand that the chemical and physical properties of metal complexes can be varied over a wide range by adapting the substituents to the cyclopentadiene ring. On the other hand, it is noted that no predictions can be made about the expected effect of specific substituents.

In the following, cyclopentadiene will be abbreviated as "Cp". The same abbreviation will be used for a cyclopentadienyl group if it is clear from the context whether cyclopentadiene itself or its anion is meant.

A drawback of the known substituted Cp compounds is that, when used as a ligand, they form a metal complex which, as a catalyst component used for polymerizing olefins, requires a considerable amount of cocatalyst, in particular of the frequently and favorably used methylaluminoxane compounds, to obtain a sufficient active catalyst.

1003012 - 2 -

Olefins here and hereafter designate α-olefins, diolefins and other ethylenically unsaturated monomers. When speaking of polymerizing olefins, this means both polymerizing a single type of olefinic monomer and copolymerizing two or more olefins.

The object of the invention is to provide substituted Cp compounds, in the presence of which as a ligand in a metal complex this complex as catalyst component requires the addition of a smaller amount of cocatalyst, in particular a methylaluminoxane compound (MAO), than in the presence of a known Substituted Cp compound to still obtain a catalyst system with the same activity.

This object is achieved according to the invention in that at least one of the substituents is an aralkyl group.

The presence of a Cp ligand with at least one aralkyl group in place of methyl groups in a metal complex appears to lead to a more favorable ratio between activity and added amount of cocatalyst, in particular MAO, than the known Cp compounds. Single and quaternary benzyl-substituted cyclopentadiene is known in the art. Not known or suggested is its beneficial effect when used in metal complexes or the amount of cocatalyst required to make these metal complexes have good catalytic activity.

The substituted Cp compound may also contain multiple aralkyl groups as substituents.

Preferably, the Cp compound contains at least two aralkyl groups as substituents. It has been found that as the number of aralkyl substituents on 1003012-3 - the Cp compound increases, the activity as a catalyst component of a metal complex to which the Cp compound is present as a ligand also increases.

These can then be the same or different.

In addition to the aralkyl group required for the compound according to the invention as a substituent, other groups may be substituted at the other positions of the Cp. These can be selected from, for example, alkyl groups, both linear and branched and cyclic and alkylene and aralkyl groups. It may also contain one or more heteroatoms from groups 14-17 of the Periodic System, in addition to carbon and hydrogen, for example O, N, Si or F, in which a heteroatom is not directly bound to the Cp. Examples of suitable other groups are methyl, ethyl, (iso) propyl, secondary butyl, pentyl, hexyl and octyl, (tertiary) butyl and higher homologues, cyclohexyl, benzyl.

The Cp compound can also be a heterocyclopentadiene compound. Here and hereafter, a heterocyclopentadiene compound is understood to mean a compound derived from cyclopentadiene, but in which at least one of the C atoms in its 5-ring is replaced by a heteroatom, wherein 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 in the 5-ring, these heteroatoms can be the same or different. More preferably, the heteroatom 30 is selected from the group 15, even more preferably the heteroatom is phosphorus.

Metal complexes that are catalytically active when one of their ligands is a compound of the invention are complexes of metals from groups 4-10 of the Periodic System and rare earths. Group 4 and 5 metal complexes are preferably used as catalyst component 1003012-4 for the polymerization of olefins, metal complexes of groups 6 and 7, in addition also for metathesis and ring-opening metathesis polymerizations and group metal complexes 8-10 for olefin 5 copolymerizations with polar comonomers, hydrogenations and carbonylations. Particularly suitable for the polymerization of polyolefins are such metal complexes in which the metal is selected from the group consisting of Ti, Zr, Hf, v, and Cr.

Substituted Cp compounds can be prepared by reacting a halide of the substituting compound in a mixture of the Cp compound and an aqueous solution of a base in the presence of a phase transfer catalyst. Cp compounds are here understood to mean Cp itself and Cp already substituted in at least 1 to 3 positions, whereby two substituents can form a closed ring. The method to be described in more detail below can thus be converted into unsubstituted compounds into mono- or polysubstituted, but also one or several times substituted Cp-derived compounds can be further substituted, after which ring closure is also possible.

Virtually equivalent amounts of the halogenated substituents can be used. An equivalent amount is understood to mean an amount in moles corresponding to the desired substitution rate, for example 2 moles per mole of Cp compound if two-fold substitution with the respective substituent is intended.

Depending on the size and the associated steric hindrance of the compounds to be substituted, a maximum of three to five times substituted Cp compounds can be obtained. When reacting with tertiary halides, as a rule, only triply substituted Cp compounds can be obtained, with primary and secondary halides being generally substituted with four and often even five-fold.

Suitable substituent aralkyl groups 5 are, for example, benzyl, di-, tri- and tetrabenzyl, 2-phenylethyl, diphenylmethyl, triphenylmethyl, naphthalene-methyl, 3-phenylpropyl, 1-phenyl-2-propyl, 4-tertiarybutylbenzyl, 2- and 3-Paratolypropyl, but others can also be used. Preferably 1, 2 or 3 aralkyl groups are substituted on the Cp compound according to the invention. The substituents are preferably used in the process in the form of their halides, more preferably in the form of their bromides. When using bromides, a smaller amount of phase transfer catalyst appears to suffice and a higher yield of the target compound is found to be obtained.

It is also possible with this method to obtain Cp compounds which are substituted with specific combinations of substituents without intermediate separation or purification. For example, a two-fold substitution can first be carried out using a certain halide and a third substitution with another substituent in the same reaction mixture by adding a second, different halide to the mixture after some time. This can be repeated so that it is also possible to manufacture Cp derivatives with three or more different substituents.

The substitution takes place in a mixture of the Cp compound and an aqueous solution of a base. The concentration of the base in the solution is between 20 and 80%. Hydroxides of an alkali metal, for example K or Na, are very suitable. The base is present in an amount of 5-60 moles, preferably 6-30 moles per mole of Cp compound. It has been found that a significant shortening of the reaction time can be 1003012 - 6 -.

are achieved when the caustic solution is used in portions, for example by initially mixing only a portion of the solution with the other components of the reaction mixture and after some time separating the aqueous phase and replacing it with a fresh amount of the lye solution.

The substitution takes place at atmospheric or elevated pressure, for example up to 100 Mpa, the latter especially when volatile components are present. The temperature at which the reaction takes place can vary between wide limits, for example from -20 to 120 ° C, preferably between 10 and 50 ° C. Starting the reaction at room temperature is generally a suitable step, after which the temperature of the reaction mixture can rise due to the heat released during the reaction.

The substitution takes place in the presence of a phase transfer catalyst capable of transferring OH ions from the aqueous phase to the Cp- and halide-containing organic phase, which react there with an H atom which can be separated from the Cp compound. As the phase transfer catalyst, quaternary ammonium, phosphonium, arsonium, antimony, bismuthonium, and tertiary sulfonium salts can be used. More preferably, ammonium and phosphonium salts are used, for example, tricaprylmethyl ammonium chloride, commercially available under the name Aliquat 336 (Fluka AG, Switzerland; General Mills Co., USA) and Adogen 464 (Aldrich Chemical Co., USA). Compounds such as benzyl triethyl ammonium chloride (TEBA) or bromide (TEBA-Br), benzyl trimethyl ammonium chloride, bromide, or hydroxide (Triton B), tetra-n-butylammonium chloride, bromide, iodide, hydrogen sulfate or -35 hydroxide and cetyl trimethyl or - chloride, benzyltributyl, tetra-n-pentyl, tetra-n-hexyl and trioctylpropyl ammonium chlorides and bromides 1003012-7x are also suitable. Useful phosphonium salts are, for example, tributylhexadecylphosphonium bromide, ethyltriphenylphosphonium bromide, tetraphenylphosphonium chloride, benzyltriphenylphosphonium iodide and tetrabutylphosphonium chloride. Crown ethers and crypt teeth can also be used as phase transfer catalyst, for example 15-crown-5, 18-crown-6, dibenzo-18-crown-6, dicyclohexano-18-kion-6, 4,7,13,16,21-pentaoxa -1,10-diazabicyclo [8.8.5] tricosane 10 (Kryptofix 221), 4,7,13,18-tetraoxa-1,10-diazabicyclo [8.5.5] eicosane (Kryptofix 211) and 4,7,13, 16,21,24-hexaoxa-1,1-diazabicyclo [8.8.8] hexacosane (“[2.2.2] *) and its benzo derivative Kryptofix 222 B. Polyethers such as ethers of ethylene glycols can also be used as phase transfer catalyst. Quaternary ammonium salts, phosphonium salts, phosphoric acid triamides, crown ethers, polyethers and crypt teeth can also be used on a support such as, for example, on a geeross-inked polystyrene or other polymer. The phase transfer catalysts are used in an amount of 0.01-2 equivalents to the amount of Cp.

When performing the process, the components can be added to the reactor 25 in different sequences.

After the reaction has ended, the aqueous phase and the Cp compound-containing organic phase are separated. The Cp compound 30 is then recovered from the organic phase by fractional distillation.

The substituted Cp compounds of the invention are particularly suitable for incorporation as a ligand into a metal complex and then produce the beneficial effect described above that less cocatalyst is required to form a catalyst with a certain degree of complexity. activity. The invention therefore also relates to a metal complex in which at least one cyclopendadiene compound substituted with at least one aralkyl group is present as a ligand.

It was further found that the presence of a group of the form -RDR'n, where R is a linking group between the Cp and the DR'n group, D is a heteroatom, selected from group 15 or 16 of the Periodic Table of the Elements, R 'is a substituent and n is the number of D-linked R' groups as a further substituent on a two or multiply substituted Cp compound in which at least one of the substituents is an aralkyl group when used as a ligand in a metal complex a catalyst component with increased activity in polyolefin 15 polymerization. In addition to the advantage of the aralkyl-substituted Cp compound as described above, an increased activity in the polymerization of olefins appears when such a multi-substituted Cp compound is present as the only Cp ligand in a metal complex in which the metal is not in highest valency state. Transition metal complexes, in which the metal is not in the highest valence state, but in which the Cp ligand does not contain a group of the form RDR'n, as a rule, are not active at all in olefin polymerizations. In the review article mentioned in the J. of Organomet. Chem. from 1994 it is even noted that "An important feature of these catalyst systems is that tetravalent Ti centers are 30 required for catalytic activity". It should be remembered that Ti is exemplary of the metals suitable as metal in the conventional cyclopentadienyl-substituted metal complexes.

Corresponding complexes in which the Cp-35 compound is not substituted in the manner indicated appear to be unstable or, if otherwise stabilized, to provide less active 1003012-9 catalysts than the complexes of substituted Cp compounds of the invention , especially in the polymerization of α-olefins.

Furthermore, the Cp compounds according to the invention have been found to be able to stabilize highly reactive intermediates such as organomethal hydrides, borohydrides, alkyls and cations. In addition, they have been found to be suitable as stable and volatile precursors for use in Metal Chemical Deposition.

The invention therefore also relates to thus multiply substituted Cp compounds.

From Synthesis, 1993, 684-686, tetramethylcyclopentadiene is known with the fifth substituent being ethyldimethylamine. In no way can the stabilizing action be deduced from this publication or the presence of the further substituted Cp compounds according to the invention to be presumed as ligands in metal complexes.

The R group forms the link between the Cp 20 and the DR group. The length of the shortest connection between the Cp and D is critical in that it uses the Cp compound as a ligand in a metal complex to determine the accessibility of the metal by the DR group to thereby achieve the desired intramolecular coordination. Too short a length of the R group (or bridge) can prevent the DR group from coordinating properly due to ring tension. R is at least one atom long.

The R 'groups can each individually be a hydrocarbon radical of 1-20 carbon atoms (such as alkyl, aryl, aralkyl, etc.). Examples of such hydrocarbon radicals are methyl, ethyl, propyl, butyl, hexyl, decyl, phenyl, benzyl and p-tolyl. R 'may also be a substituent which, in addition to or instead of carbon and / or hydrogen, is one or more

heteroatoms from group 14-16 of the Periodic Table of the Elements. For example, a substituent can have an N, O

1003012-10 and / or Si-containing group. R 'should not be a cyclopentadienyl or derivative group.

The R group can be a hydrocarbon group of 1-20 carbon atoms (such as alkylidene, arylidene, arylalkylidene, etc.). Examples of such groups are methylene, ethylene, propylene, butylene, phenylene, with or without a substituted side chain. Preferably, the R group has the following structure; 10 (-ER22-) p with p = 1-4 and E an atom from group 14 of the Periodic System. The R2 groups can each be H or a group as defined for R '.

The main chain of the R group can therefore contain, in addition to carbon, silicon or germanium. Examples of such R groups are: dialkylsilylene, dialkylgermylene, tetraalkyldisilylene or tetraalkylsilaethylene (-SiR22CR22-). The alkyl groups in such a group preferably have 1-4 C atoms and are more preferably a methyl or ethyl group.

The DR '' group consists of a heteroatom D selected from group 15 or 16 of the Periodic Table 25 of the Elements and one or more substituent (s) R 'bound to D'. The number of R 'groups (n) is linked to the nature of the heteroatom D, in that n = 2 if D is from group 15 and n = 1 if D is from group 16. With The heteroatom D is preferably selected from the group nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S); more preferably, the heteroatom is nitrogen (N). Also preferably the R 'group is an alkyl, more preferably an n-alkyl group with 1-20 C atoms. More preferably, the R 'group is an n-alkyl of 1-10 carbon atoms. Another possibility is that two R 'groups in the DR' 'group are linked together to form a 1003012 - 11 - ring structure (so that the DR' 'group can be a pyrrolidinyl group). The DR group can coordinate bonding with a metal.

A Cp compound to which so many a group of the form RDR '' is substituted as at least one aralkyl group can be prepared by subsequently substituting a group of the aforementioned substituted Cp compound for the above-described synthesis route, for example, according to the following synthetic route .

In a first step of this route, a substituted Cp compound is deprotonated by reaction with a base, sodium or potassium.

As base, for example, organolithium compounds (R3Li) or organomagnesium compounds (R3MgX) can be used, wherein R3 is an alkyl, aryl or aralkyl group and X is a halide, for example n-butyl lithium or i-propyl magnesium chloride. Potassium hydride, sodium hydride, inorganic bases, for example NaOH and KOH, and alcoholates of Li, K and Na can also be used as base. Mixtures of the above compounds are also applicable.

This reaction can be performed in a polar dispersant such as an ether.

Examples of suitable ethers are tetrahydrofuran (THF) or dibutyl ether. Non-polar solvents, such as, for example, toluene, can also be used.

Then, during a second step of the synthesis route, the cyclopentadienyl-30 anion formed reacts with a compound of the formula (DR '- - R-Y) or (X-R-Sul), wherein D, R, R's and n are as defined above. Y is a halogen atom (X) or a sulfonyl group (Sul). Chlorine, bromine and iodine can be mentioned as halogen atom X. Preferably, the halogen atom X is a chlorine or bromine atom. The sulfonyl group has the form -SO2R6, wherein R6 is a hydrocarbon radical of 1-20 carbon atoms, for example, 1003012-12, alkyl, aryl, aralkyl. Examples of such hydrocarbon radicals are butane, pentane, hexane, benzene, naphthalene. R6 may also contain, in addition to or instead of carbon and / or hydrogen, one or more 5 heteroatoms from group 14-17 of the Periodic Table of the Elements, such as N, 0, Si or F.

Examples of sulfonyl groups are: phenylmethanesulfonyl, benzenesulfonyl, 1-butanesulfonyl, 2,5-dichlorobenzenesulfonyl, 5-10 dimethylamino-1-naphthalenesulfonyl, pentafluorobenzenesulfonyl, p-toluenesulfonyl, trichloromethanesulfonyl, trifluoromethanesulfonethanesulfonylsulfonylsulfonyl 2,4,6-trimethylbenzenesulfonyl, 2-mesitylenesulfonyl, 15-methanesulfonyl, 4-methoxybenzenesulfonyl, 1-naphthalenesulfonyl, 2-naphthalenesulfonyl, ethanesulfonyl, 4-fluorobenzenesulfonyl and 1-hexadecan sulfonyl.

Preferably, the sulfonyl group is p-toluenesulfonyl or trifluoromethanesulfonyl.

When D is a nitrogen atom and Y is a sulfonyl group, the compound of the formula (DR '- - RY) is formed in situ by reaction of an amino alcohol compound (R'2NR-0H) with a base (as defined above), potassium or sodium, followed by a reaction with a sulfonyl halide (Sul-X).

The second reaction step can also be performed in a polar dispersant, as described for the first step.

The temperature at which the reactions are carried out is between -60 and 80 ° C. Reactions with X-R-Sul and with DR 'n-R-Y, in which Y is Br or I are usually carried out at a temperature between -20 and 20 ° C.

Reactions with DR, -R-Y, wherein Y is Cl, are usually carried out at a higher temperature (10 to 80 ° C). The upper limit for the temperature at which the reactions are carried out is partly determined by the boiling point of the compound DR'n-R-Y and that of the 1003012-13 used solvent.

After the reaction with a compound of the formula (X-R-Sul), a further reaction with LiDR'n or HDR'n is carried out to replace X with a DR'n-5 functionality. For this purpose, optionally in the same dispersing agent as mentioned above, a reaction is carried out at 20 to 80 ° C.

During the synthesis process according to the invention partly geminal products can be formed. A geminal substitution is a substitution in which the number of substituents increases by 1, but the number of substituted carbon atoms does not increase. The amount of geminal products formed is low when the synthesis is carried out from a substituted Cp compound having 1 substituent and increases as the substituted Cp compound contains more substituents. In the presence of sterically large substituents on the substituted Cp compound, little or no geminal products are formed.

Examples of sterically large substituents are secondary or tertiary alkyl substituents.

The amount of the mineral product that is formed is also low when the second step of the reaction is carried out under the influence of a Lewis base, the conjugated acid of which has a dissociation constant, for which pKe is less than or equal to -2.5. The pKm values are based on D.D. Perrin: Dissociation Constants of Organic Bases in Agueous Solution, International Union of Pure and Applied Chemistry, 30 Butterworths, London 1965. Values were determined in aqueous H 2 SO 4 solution.

Ethers can be mentioned as an example of suitable weak Lewis bases.

When geminal products have been formed during the process of the invention, these products can be easily separated from the non-geminal products by converting the mixture of geminally 1003012-14 and non-geminally substituted products into a salt by reaction with potassium, sodium or a base, after which the salt is washed with a dispersing agent in which the salt of the non-geminal products does not dissolve or dissolves poorly. The compounds as mentioned above can be used as base.

Suitable dispersing agents are non-polar dispersing agents, such as alkanes. Examples of suitable alkanes are heptane and hexane.

Metal complexes, in which at least one cyclopentadiene compound as defined above are present, are found to exhibit improved stability compared to such complexes in which other Cp compounds are present as ligand, especially when the metal in the complex is not in its highest valency state is wrong. Also, such complexes require less cocatalyst as described above. The invention therefore also relates to said metal complexes and their use as a catalyst component for polymerizing olefins.

Metal complexes that are catalytically active when one of their ligands is a compound of the invention have already been specified above.

The synthesis of metal complexes with the above-described specific Cp compounds as a ligand can take place according to the methods known per se. The use of these Cp-30 compounds does not require modifications of these known methods.

The polymerization of α-olefins, for example ethylene, propylene, butene, hexene, octene and mixtures thereof and with dienes can be carried out in the presence of the metal complexes with the cyclopentadienyl compounds of the invention as a ligand. Particularly suitable for this are the 1003012-15 complexes of transition metals, not in their highest valency state, in which just one of the cyclopentadienyl compounds according to the invention is present as a ligand and in which the metal is cationic during the polymerization. These polymerizations can be carried out in the known manner and the use of the metal complexes as a catalyst component does not necessitate any substantial adaptation of these processes. The known polymerizations are carried out in suspension, solution, emulsion, gas phase or as bulk polymerization. As the co-catalyst, an organometallic compound is usually used, the metal being selected from Group 1, 2, 12 or 13 of the Periodic Table of the Elements. Mention may be made, for example, of trialkylaluminum, alkylaluminum halides, alkylaluminoxanes (such as methylaluminoxanes), tris (pentafluorophenyl] borate, dimethylanilinium tetra (pentafluorophenyl) borate or mixtures thereof. The polymerizations are carried out at temperatures between -50 ° C and + 350 ° C, more in particular between 25 and 250 ° C. Applied pressures are between generally between atmospheric pressure and 250 MPa for bulk polymerizations more in particular between 50 and 250 Mpa, for the other polymerization processes between 0.5 and 25 MPa. and solvents, for example, hydrocarbons can be used as pentane, heptane and mixtures thereof Also aromatic, optionally perfluorinated hydrocarbons can be used, and the monomer to be used in the polymerization can also be used as a dispersing or solvent.

The invention will be elucidated on the basis of the following examples without, however, being limited thereto.

The following analysis methods are used in the characterization of the products obtained.

1003012 - 16 -: - '

Gas chromatography (GC) was performed on a Hewlett-Packard 5890 Series II with an HP Crosslinked Methyl Silicon Gum (25mx0.32mmx1.05μπι) column. Combined Gas Chromatography / Mass Spectrometry (GC-5 MS) was performed with a Fisons MD800 equipped with a guadrupole mass detector, autoinjector Fisons AS800 and CPSil8 column (30mx0.25mmxlpm, low bleed).

NMR was performed on a Bruker ACP200 (1H = 200MHz; 13C = 50MHz) or Bruker ARX400 (1H = 400MHz; 13C = 100MHz).

For the characterization of metal complexes, a Kratos MS80 or a Finnigan Mat 4610 mass spectrometer was used.

Example I

Preparation of di (2-phenyl-propyl) cyclopentadiene

A 1 L double-walled reactor equipped with a baffles, cooler, overhead stirrer, thermometer and dropping funnel was charged with 600 g of clear 50% NaOH (7.5 mol) and cooled to 8 ° C. Then 20 g of Aliquat 336 (49 mmol) and 33 g (0.5 mol) of freshly cracked cyclopentadiene were added. The reaction mixture was stirred turbulently for several minutes. Then 219 g of 1-bromo-2-phenylpropane (1.1 mol) were added all at once. It was cooled with water. After stirring at room temperature for 2 hours, the reaction mixture was heated to 70 ° C and stirred for another 6 hours. GC showed that at that time 89% di (2-phenyl- (propyl) cyclopentadiene) was present. The product was distilled at low pressure and high temperature, after which 95.34 g (0.4 mol; 80%) di (2 phenyl-propyl) cyclopentadiene.

The product was characterized by GC, GC-MS, 13C and 1 H NMR.

35 Experiment II

Preparation of 2- (N, N-dimethvlaminoethyl) toss leaf in situ 10 0? 0 1 2 - 17 -

In a three-necked round bottom flask equipped with a magnetic stirrer and dropping funnel, a solution of 5 n-butyl lithium in hexane (1 equivalent) was added to a solution of 2-dimethylaminoethanol (1 equivalent) in dry THF at -10 ° C under dry nitrogen (dosing time: 60 minutes). After adding all butyl lithium, the mixture was brought to room temperature and stirred for 2 hours. Then the mixture was cooled (-10 ° C) after which paratoluenesulfonyl chloride (1 equivalent) was added. It was then stirred at this temperature for 15 minutes before the solution was added to a cyclopentadienyl anion.

Similar tosylates can be prepared in an analogous manner. In some of the 15 following examples, a tosylate is always coupled to alkylated Cp compounds. In addition to the desired substitution reaction, this coupling also involves geminal coupling. In almost all cases, the geminal isomers could be separated from the non-geminal isomers by converting the non-geminal isomers into their sparingly soluble potassium salt, followed by washing this salt with a solvent in which this salt does not or poorly dissolve. 1 2 3 4 5 6 7 8 9 10 11 1003012

Example III

2

Preparation of (dimethvlaminoethvUdi (2-phenyl-3-propyl-cyclodadiene 4)

In a 250 ml three-necked round bottom flask equipped with a magnetic stirrer and dropping funnel, 6 was added under nitrogen atmosphere to a cooled (0 ° C) solution 7 of di (2-phenyl-propyl) cyclopentadiene (6.05 g; 20 8 mmol) in dry tetrahydrofuran (100 ml) 12.5 mL of 9 added a 1.6 molar solution of n-butyl lithium in hexane 10 dropwise. After stirring at room temperature for 24 hours, a solution of the 2- (dimethylaminoethyl) tosylate (20 mmol) in THF / hexane (see Example 1B) was added. After stirring for 18 hours, the conversion was found to be 90% and water (100 ml) was carefully added dropwise to the reaction mixture, after which the tetrahydrofuran was distilled off. The crude product was extracted with ether, then the combined organic phase was dried (over sodium sulfate) and evaporated. The residue was purified on a column with silica gel, resulting in 5.98 grams (80%) (dimethylaminoethyl) di (2-phenyl-propyl) cyclopentadiene.

Example IV

Preparation of ((dimethvlaminoethyl ^ di (2-phenyl-propyl-cyclo-tadienyl-titanium-dichloride)

To (dimethylaminoethyl) di (2-phenyl-propyl) cyclopentadiene (1.12 grams, 3 mmol) dissolved in 15 mL of tetrahydrofuran, 1.87 mL at 0 ° C (ice bath)

of a 1.6 molar butyl lithium in hexane solution. After stirring for 15 minutes, this mixture was further cooled to -78 degrees Celsius and a slurry of 20 Ti (III) Cl3.3THF (1.11 g, 3 mmol) in 20 mL THF, also cooled to -78 degrees Celsius, was added.

added. The cooling bath was removed and the resulting dark green solution was stirred at room temperature for 72 hours. After evaporation, 30 mL of petroleum ether (40-60) was added. After complete evaporation again, a green powder (1.65 g) was obtained containing ((dimethylaminoethyl) di (2-phenyl-propyl) cyclopentadienyl) titanium dichloride.

Comparative Experiment A

30 Preparation of ((dimethvlaminoethvlclyclooenta-dienvl) t itaniumdichlor ide

The synthesis was carried out as in Example IV, however, it was now started with: 1.37 grams of (dimethylaminoethyl) cyclopentadiene (10 mmol) 6.2 mL of a 1.6 molar butyl lithium solution in hexane 3.7 grams of TiCl3.3THF ( 10 mmol) 2.60 g of powder containing (dimethylaminoethyl) cyclopentadienyl) titaniumdichloride 1003012-19 - was obtained.

Examples V-VIII and Comparative Experiments B and C Batch ethylene / octene copolymerization experiments The copolymerizations of ethylene with octene were carried out in the following manner.

600 ml of an alkane mixture (pentamethyl heptane or boiling point gasoline) was placed under dry N2 as reaction medium in a 1.5 liter stainless steel reactor.

Then the target amount of dry octene was charged to the reactor. The reactor was then heated with stirring to the desired temperature under a desired ethylene pressure.

In a 100 ml catalyst dosing vessel, 25 ml of the alkane mixture was dosed as a solvent. Herein, the desired amount of an Al-containing cocatalyst was premixed with the desired amount of metal complex for 1 minute.

This mixture was then metered into the reactor and polymerization started. The polymerization reaction thus started was carried out isothermally. The ethylene pressure was kept constant at the set pressure. After the desired reaction time, the ethylene feed was stopped and the reaction mixture was drained and quenched with methanol.

The reaction mixture with methanol was washed with water and HCl to remove catalyst residues.

The mixture was then neutralized with NaHCO 3. An antioxidant (Irganox 1076, TM) was then added to the organic fraction to stabilize the polymer. The polymer was dried under vacuum at 70 ° C for 24 hours.

35

Can be varied: - metal complex 10030) 2 - 20 - - type and amount of scavenger - type and amount of cocatalyst - temperature 5 The catalyst obtained in example 4 was used at two different temperatures and MAO / Ti ratios in polymerization experiments 5 to 8. For comparison the catalyst obtained in Example A at the same two temperatures was used in 10 polymerization experiments B and C.

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- »W W Δ 5? β α je> * · • u e u * [

o · c> >>> S

* »> - w__j__H__H__j__H B

| -O “

K Η HO

O β Η M 3 O β Η Η H * 1> 1 "I> => lo l>.

In o in 1003012

Claims (6)

1. Substituted cyclopentadiene compound, characterized in that at least one substituent is an aralkyl group with the exception of mono- and pentabenzyl-cyclopentadiene. 2. Metal complex in which at least one cyclopentadiene compound substituted with at least one aralkyl group is present as a ligand. 3. Two or multiply substituted cyclopentadiene compound of which at least one substituent has the form -RDR'n, wherein R is a linking group between the cyclopentadiene and the DR 'group, D a heteroatom selected from group 15 or 16 of the Periodic Table of the Elements, R 'is a substituent and n is the number of R' groups attached to D, and wherein at least one of the remaining substituents is an aralkyl group. Metal complex, in which at least one cyclopentadiene compound according to claim 3 is present as a ligand. Use of the metal complex according to claim 2 or 4 as a catalyst component for polymerizing α-olefins. Use of the metal complex according to claim 4 as catalyst components for polymerizing o-olefins, the complex containing a metal which is not in its highest valency state. 30 1003012 J ^ r »J IJ J w C> _ M> <^ f. W * /......- - ... REPORT ON THE NEW INTERNATIONAL TYPE OF LOENTIF CATALOGUE OF THE NATIONAL APPLICATION Characteristic of the applicant or of the faculty 8669NL Neo-Tananose application no. NV Oaum of wet request for onoarzoait of mtamaionaai type By ao Instants voor Internaten eal Onoerzoek (ISA) tai wet request for investigation of mtemaoonaai type eega ka na nr. SN 27499 NL I. CLASSIFICATION OF THE SUBJECT (at eepessmg of shipping country · autdaDet.all dassificaoesymEwo statements) - - ------ - ---------— * Including mum Donate eassiDcaaa (IPC) Int. Cl. 6: C 07 C 13/15, C 08 F 10/00, C 07 F 17/00 II. RESEARCHED FIELDS OF OE TECHNOLOGY Onoerzocrne minimum documentation I Classification system I Classification symbols' * 1 Int. Cl.6 C 07 C, C 07 F, C 08 F Onoerzocrne anoere ooeumentaoe ao mnrnum documentation insofar as dargeiike doeumanan in oe research geoieoan qn o pgenoman III.! X NO EXAMINATION FOR CERTAIN CONCLUSIONS (remarks on supplement payload) j IV. LACK OF UNIT OF INVENTION (comments including supplemental tax) ./ = orm PCT.1SA.ro t; ai CS / 6