NL1003013C2 - Cyclopentadiene compound substituted with cyclic groups. - Google Patents

Description

- 1 -

CYCLOPENTADIENE COMPOUND SUBSTITUTED WITH CYCLIC GROUPS

The invention relates to a multi-5-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, lanthanides are also used as metals in these complexes.

15 In the J. of Organomet. Chem, 479 (1994), 1-29 has been reviewed on 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 20 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 in a metal complex, they do give them a certain stability, but that at higher temperatures the stability of these complexes decreases faster than desired.

It is an object of the invention to provide substituted Cp compounds which, when used as a ligand in a metal complex, impart to them better resistance to higher temperatures than the known Cp compounds.

The olefins are referred to herein and hereinafter as α-olefins, diolefins and other ethylenically unsaturated monomers. When speaking of olefin polymerization, this includes both polymerizing a single type of olefinic monomer and copolymerizing two or more olefins.

This object is achieved according to the invention in that at least two of the substituents are cyclic alkyl groups.

The presence of at least two cyclic alkyl groups in place of hydrogen or methyl groups appears to lead to better resistance to higher temperatures than with other Cp compounds used as ligand.

The cyclic alkyl groups can be the same or different. In addition to the substituent required for the compound of the invention as a substituent, at least two cyclic alkyl groups may be substituted at the other positions of the Cp. These other substituents can be selected from, for example, alkyl groups, both linear and branched, alkenyl and aralkyl groups. It may also contain, in addition to carbon and hydrogen, one or more heteroatoms from groups 14-17 of the periodic Table, for example O, N, Si or F, where a heteroatom is not directly bound to the Cp. Examples of suitable groups are methyl, ethyl, (iso) propyl, secondary butyl, pentyl, hexyl and octyl, (tertiary) butyl and higher homologs, benzyl, phenyl, paratolyl.

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 1003013-3 is replaced by a heteroatom, 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 hot 5 atoms can be the same or different. More preferably the heteroatom is selected from the group 15, even more preferably the heteroatom is phosphorus.

Substituted Cp compounds can be prepared by reacting a halide of the substituent 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 understood to mean Cp itself and Cp already substituted at 1 to 3 positions, whereby two substituents can form a closed ring. With the method according to the invention, unsubstituted compounds can thus be converted into mono- or poly-substituted, but it is also possible to further substitute one or several-substituted Cp-derived compounds, whereby 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 associated steric hindrance of the compounds to be substituted, up to three to five-substituted Cp compounds can be obtained. When reacting with tertiary halides, as a rule only three-substituted Cp compounds can be obtained, with primary and secondary halides generally being substituted four and often even five-fold. Cyclic groups which are suitable as substituents are, for example, cyclopro- 10 0 3 0 1 3 - 4 -. , pyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclododecyl, cyclopent-2-enyl, cyclopent-3-enyl, cyclohex-2-enyl, cyclohex-3-enyl, cyclohexa- 2,4-dienyl, cyclohept-2 -enyl, cyclohept-3-enyl, cyclo-5-hept-4-enyl, cyclohepta-2-6-dienyl, cyclohepta-2,4,6-trienyl, cycloocta-2-enyl, cycloocta-4-enyl, cycloocta- 2,7-dienyl, cycloocta-2,6-dienyl, cyclonon-2-enyl, cyclonona-2,8-dienyl and cyclonona-2,4,68-tetraenyl. Preferably 2, 3 or 4 cyclic alkyl groups are substituted on the Cp compound according to the invention. In addition to these cyclic alkyls, any other groups mentioned above can then also be substituted on the Cp compound.

The substituents are preferably used in the process in the form of their halides, 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 20 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 be carried out first with the aid of a certain halide and, in the same reaction mixture, a third substitution with a different substituent by adding a second, different halide to the mixture after some time. This can be repeated so that it is also possible to produce 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 language, for example K or Na, are very suitable. The base is present in an amount of 5-60 mol, preferably 6-30 mol, per mol Cp compound. It has been found that a significant reduction of the reaction time can be achieved when the caustic solution is used in parts, for example by initially mixing only a part of the solution with the other components of the reaction mixture and after some time removing the aqueous phase. and replace 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 usually a suitable step, after which the temperature of the reaction mixture may rise due to the heat released in the reaction. The substitution takes place in the presence of a phase transfer catalyst capable of transferring OH-20 ions from the aqueous phase to the Cp and halide-containing organic phase, which react there with a cleavable from the Cp compound H atom. As a 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, 30 Switzerland; General Mills Co., USA) and Adogen 464 (Aldrich Chemical Co., USA). Compounds such as benzyl triethylammonium chloride (TEBA) or bromide (TEBA-Br), benzyl trimethyl ammonium chloride, bromide, or hydroxide (Triton B), tetra-n-butylammonium chloride, bromide, 35-iodide, hydrogen sulfate or hydroxide and cetyltrime thylammonium bromide or chloride, benzyl tributyl, tetra-n-pentyl, tetra-n-hexyl and trioctylpropyl ammonium 1003013-6 -nium chlorides and bromides are also suitable. Useful phosphonium salts are, for example, tributyl-hexadecylphosphonium bromide, ethyltriphenylphosphonium bromide, tetraphenylphosphonium chloride, benzyltriphenyl-5phosphonium iodide and tetrabutylphosphonium chloride. Crown ethers and crypt teeth can also be used as a phase transfer catalyst, for example 15-crown-5, 18-crown-6, dibenzo-18-crown-6, dicyclohexano-18-crown-4, 4,7,13,16,21 -pentaoxa-1,10-diazabicy-10 clo [8.8.5] tricosane (Kryptofix 221), 4,7,13,18-tetra-oxa-1,1,10-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 may also be used as a 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 geer oss-1 inked polystyrene or other polymer. The phase transfer catalysts are used in an amount of 0.01-2, preferably 0.05-1, equivalent 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 is then recovered from the organic phase by fractional distillation.

By this process, Cp compounds substituted singly, two-, three-, four- and five-fold with the desired cyclic alkyl groups and any other groups.

The Cp compounds of the invention substituted with one or more cyclic groups are particularly suitable for incorporation as a ligand in 1003013-7:> a metal coroplex which, when used as a catalyst component, results in the presence of this ligand as a catalyst with improved activity compared to the metal complexes with the known Cp-5 compounds as ligand. The invention therefore also relates to a metal complex in which at least one cyclopentadiene compound substituted with two cyclic alkyl groups is present as a ligand.

Furthermore, it was found that the presence of at least one substituent on the Cp compound of the form -RDR'n, where R is a linking group between the Cp and the DR '' group, D is a heteroatom, selected from group 15 or 16 of the Periodic Table of Elements R 'is a substituent and n is the number of R' groups attached to D ', in a substituted Cp compound in which at least one of the further substituents is a cyclic alkyl group, using that Cp compound as a ligand in a metal complex, giving a complex which, as a catalyst component used in the polymerization of α-olefins, exhibits better temperature resistance than the presence of a single Cp-compound substituted with cyclic groups.

Corresponding complexes in which the Cp compound is not substituted in the manner indicated are found to be unstable or, if otherwise stabilized, to yield less active catalysts than the substituted Cp compound complexes of the invention, in especially in the polymerization of α-olefins.

Furthermore, the Cp compounds according to the invention appear to be able to stabilize highly reactive intermediates such as organo-metal hydrides, borohydrides, alkyls and cations. In addition, they appear to be suitable as stable and volatile precursors for use in Metal Chemical Vapor Deposition.

The invention therefore also relates to Cp compounds thus substituted.

1003013 - 8 -

From Synthesis, 1993, 684-686, tetramethyl cyclopentadiene is known with the fifth substituent being eth-yldimethylamine. In no way can the stabilizing effect be deduced from this publication or the presumption of the presence of the further substituted Cp compounds according to the invention as ligands in metal complexes giving a complex which is used as a catalyst component in the polymerization of α-olefines exhibit better temperature resistance than the presence of a known Cp compound.

The R group forms the link between the Cp and the DR group. The length of the shortest connection between the Cp and D is critical in that it determines the accessibility of the metal by the DR group when the Cp compound is used as a ligand in a metal complex. obtain desired intramolecular coordination. Too short a length of the R group (or bridge) may 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, contains one or more heteroatoms from group 14-16 of the Periodic Table of the Elements. Thus, a substituent can be an N, O 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.

100301c - 9 -

Preferably, the R group has the following structure: (-ER22-) p 5 with p = 1-4 and E an atom from group 14 of the periodic table. 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 tetraalkylsilethylene (-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 of Elements and one or more substituent (s) R 'attached to D. The number of R 'groups (n) is linked to the nature of the heteroatom D, in the sense that n = 2 if D is from group 15 and n = 1 if D is from group 16. Preferably, the heteroatom D is selected from the group of nitrogen (N), oxygen (0), phosphorus (P) or sulfur (S); more preferably, the heteroatom is nitrogen (N). Also preferably preferred, 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 C atoms. Another possibility is that two R 'groups in the DR' 'group are linked together to form an annular structure (so that the DR' 'group can be a pyrrolidinyl group).

The DR group can coordinate bonding with a metal.

To the Cp compound substituted with at least two cyclic groups and any other groups, a group of the form -RDR'n can be substituted, for example, by the following synthetic route.

In a first step of this route, a substituted Cp compound is deprotonated by 1003015-10 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-mentioned compounds can also be used.

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 anion formed is reacted with a compound of the formula (DR'n-RY) or (XR-Sul), wherein D, R, R's are n as previously 20 defined. 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 is in the form -SO 2 R 5, wherein R 6 is a hydrocarbon radical of 1-20 carbon atoms, for example, 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 hetero atoms from group 30 14-17 of the Periodic Table of the Elements, such as N, O, Si or F.

Examples of sulfonyl groups are: phenylmethanesulfonyl, benzenesulfonyl, 1-butanesulfonyl, 2,5-dichlorobenzenesulfonyl, 5-dimethylamino-1-naphthal-35sulfonyl, pentafluorobenzenesulfonyl, p-toluenesulfonyl, trichloromethanesulfonyl, 2,4-trifluoro-sulfonyl, trifluoronyl triisopropylbenzenesulfonyl, 2,4,6-trimethylbenzenes 1003013-11 -sulfonyl, 2-mesitylene sulfonyl, methanesulfonyl, 4-methoxybenzenesulfonyl, 1-naphthalenesulfonyl, 2-naphthalenesulfonyl, ethanesulfonyl, 4-fluorobenzenesulfonyl and 1-fluorobenzenesulfonyl. Preferably the sulfonyl group is 5-toluenesulfonyl or trifluoromethanesulfonyl.

When D is a nitrogen atom and Y is a sulphonyl group, the compound of the formula (DR'-RRY) is formed in situ by reaction of an amino alcohol compound (R'2NR-OH) with a base (as shown here - 10 described 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, where Y is Br or I are usually carried out at a temperature between -20 and 20 ° C. Reactions with DR '- R-Y, where 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'-R-Y and that of the solvent used.

After the reaction with a compound of the formula (X-R-Sul), another reaction with LiDR '' or HDR 'is performed to replace X with a DR' 'functionality. For this purpose, optionally in the same dispersant 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 35 in which the number of substituted carbon atoms does not increase. The amount of geminal products formed is low when the synthesis is performed starting from 100301-12 - 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 5 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: pK, less than or equal to -2.5. The pKa values are based on D.D. Perrin: Dissociation Constants of Organic Bases in Aqueous Solution, Inter-15 National Union of Pure and Applied Chemistry, Butter-worths, 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 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 is present, are found to exhibit improved stability and activity compared to such complexes in which other Cp compounds are present as a ligand. The invention therefore also relates to such metal complexes and their use as a catalyst component for the polymerization of olefins. In these metal complexes, one or more Cp compounds according to the invention may be present as a ligand. Two of these ligands can be linked by a bridge. 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 Table 10 and rare earths. Group 4 and 5 metal complexes are preferably used as a catalyst component for the polymerization of olefins, group 6 and 7 metal complexes, in addition also for metathesis and ring-opening metathesis polymerizations and group 8-10 metal complexes for olefin copolymerizations with polar comonomers, hydrogenations and carbonylations. Particularly suitable for the polymerization of olefins are such metal complexes in which the metal is selected from the group consisting of Ti, Zr, Hf, V and Cr.

The synthesis of metal complexes including lanthanide 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 compounds does not require modifications of these known methods.

The polymerization of α-olefins, eg ethylene, propylene, butene, hexene, octene and mixtures thereof and combinations 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 complexes of transition metals, not in their highest fall state, in which just one of the cyclopentadienyl compounds of 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 manner previously known, 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 organo-metal 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 tri-alkyl aluminum, alkyl aluminum halides, alkyl aluminum oxanes (such as methyl aluminum oxanes), tris (pentafluorophenyl) borate, dimethyl anilinium tetra (pentafluorophenyl) borate or mixtures thereof. The polymerizations are carried out at temperatures between -50 ° C and + 350 ° C, more particularly between 25 and 250 ° C. The pressures used are between generally between atmospheric pressure and 250 MPa for bulk polymerizations, more particularly between 50 and 250 Mpa, for the other polymerization processes between 0.5 and 25 MPa. As dispersants and solvents, for example, hydrocarbons can be used as pentane, heptane and mixtures thereof. Aromatic, optionally perfluorinated hydrocarbons are also eligible. 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.

Gas chromatography (GC) was performed on a Hewlett-Packard 5890 Series II with an HP Crossi inked Methyl Silicon Gum (25mx0.32mmx1.05 / m) column. Combined Gas Chromatography / Mass Spectrometry (GC-MS) 35 was performed with a Fisons MD800 equipped with a quadrupole mass detector, autoinjector Fisons AS800 and CPSil8 column (30mx0.25mmxlpm, low bleed).

1003013-15 NMR was performed on a Bruker ACP200 (1H = 200MHz; 13C = 50MHz) or Bruker ARX400 (1H = 400MHz; 13C = 100MHz). A Kratos MS80 or a Finnigan 5 Mat 4610 mass spectrometer was used to characterize metal complexes.

Experiment I

Preparation of 2- (NN-dimethylaminoethylethosylate in situ). In a three-necked round bottom flask equipped with magnetic stirrer and dropping funnel, a solution of n-butyl lithium was added under dry nitrogen to a solution of 2-dimethylaminoethanol (1 equivalent) in dry THF at -10 ° C. in hexane (1 equivalent) added (do-15 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) and then paratoluenesulfonyl chloride (1 equivalent) 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 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.

Example II

A. Preparation of di (cvlohexyl) cyclopentadiene

A 1 L double-walled reactor equipped with baffles, cooler, overhead stirrer, thermometer 1003013 - 16 - meter 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 172 g of cyclohexyl bromide (1.05 mol) was added. 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 79% di (cyclohexyl) cyclopentadiene was present. The product was distilled at 0.04 mbar and 110-120 ° C. After distillation, 73.6 g of di (cyclohexyl) cyclopentadiene were obtained. The characterization was done by GC, 15 GC-MS, 13C and 1 H NMR.

b. Preparation of (dimethvlaminoethvl) di (cvclohexvl) cv-clopentadiene

In a 250 ml three-necked round bottom flask equipped with magnetic stirrer and dropping funnel, a solution of n was added under a nitrogen atmosphere to a cooled (0 ° C) solution of dicyclohexyl cyclopentadiene (6.90 g; 30.0 mmol) in dry tetrahydrofuran (125 ml). butyl lithium in hexane (18.7 µm 1.6 mol / L; 30 mmol) was added dropwise. After stirring at room temperature for 24 hours, 2- (dimethylaminoethyl) tosylate (30.0 mmol) prepared in situ was added. After stirring for 18 hours, the conversion was found to be 88% and water (100 ml) was carefully added dropwise to the reaction mixture, after which the te-trahydro uranium was distilled off. The crude product was extracted with ether and the combined organic phase was dried (sodium sulfate) and evaporated. The residue was purified on a column with silica gel, resulting in 7.4 g of (dimethylamino-35 ethyl) dicyclohexylcyclopentadiene.

c. Synthesis of 1- (dimethvlaminoethyl) -2,4-dicvclo- 1003013 - 17 - hexyl-cyclopentadienyl titanium-dichloride and fl-fdime-thvlaminoethyl) -2,4-dicvclohexyl-clopentadienyl dimethyl (III) rCJMc, TiCNMc (Ti), CHCiMc (Ti) .1 and IC .H, (cr.CtH ,, 1, (CH,), ΝΜ, Τ i (111) Me? 1 5 1.37 g (4.54 nunol) (dimethylaminoethyl) dicyclohexylcyclopentadiene were dissolved in a Schlenk vessel in 30 ml diethyl ether, after which the solution was cooled to -60 ° C. Then 2.84 ml n-butyl lithium (1.6M in hexane; 4.54 mmol) was added dropwise. The reaction mixture was slowly brought to room temperature and then Stirred for 2 hours After evaporation of the solvent, a yellow powder remained, to which 30 mL of petroleum ether was added.

In a second Schlenk vessel, 40 mL of tetrahydrofuran was added to 1.68 g of Ti (Ills I) C13.3THF (4.53 mmol). Both Schlenk vessels were cooled to -60 ° C, after which the organolithium compound was added to the Ti (III) Cl3 suspension. The reaction mixture was then stirred at room temperature for 18 hours after which the solvent was evaporated. 50 mL of petroleum ether was added to the residue, which was then evaporated again. A green solid containing 1- (dimethylaminoethyl) -2,4-dicyclohexyl cyclopopenadienyl titanium (III) dichloride remained.

In a Schlenk vessel, 0.31 g (0.671 mmol) of the 1- (dimethylaminoethyl) -2,4-dicyclohexylcyclopentadienyl-titanium (III) di-chloride described above was dissolved in 30 mL diethyl ether. The solution was cooled to -60 ° C and 0.73 mL (1.84M in diethyl ether; 1.34mmol) of methyl lithium was added dropwise. The solution was slowly brought to room temperature and stirred for an additional 1 hour. The solvent was then evaporated and the residue extracted with 40 mL of petroleum ether. The filtrate was evaporated for 35 and dried under vacuum for 18 hours. 0.14 g of a black / brown oil containing [1- (dimethylaminoethyl) -2,4-dicyclohexylcyclopentadienyl] dimethyltit-10- (18) left (III).

Example III

a. Preparation of tri (cvlohexvl) cvclopentadiene 5 A 1 L double-walled reactor equipped with a baffle, cooler, overhead stirrer, thermometer and dropping funnel was charged with 600 g of clear 50% NaOH (7.5 mol) and then cooled to 8 ° C. Then 20 g Aliquat 336 (49 mmol) and 33 10 g (0.5 mol) freshly cracked cyclopentadiene were added. The reaction mixture was stirred turbulently for several minutes. Then 256 g cyclohexyl bromide (1.57 mol) was added. It was cooled with water. After stirring at room temperature for 1 hour, the reaction mixture was heated to 70 ° C and stirred for another 2 hours. After 2 hours, stirring was stopped and phase separation was awaited. The water layer was drained and 600 g (7.5 mol) of fresh 50% NaOH were added. Stirring was then continued at 70 ° C for 4 hours. GC showed that at that time 10% di- and 90% tri- (cyclohexyl) cyclopentadiene was present in the mixture. The product was distilled at 0.04 mbar and 130 ° C. After distillation, 87.4 g of tri (cyclohexyl) cyclopentadiene were obtained. The characterization was done by GC, GC-MS, 13C and 1 H-NMR.

b. Preparation of (dimethvlaminoethvl) tri (cvclohexvl) cv clopentadiene

The reaction was carried out identically as for (dimethylaminoethyl) dicyclohexylcyclopentadiene. The conversion was 91%. The product was obtained by preparative column purification on silica gel with successively petroleum ether (40-60 ° C) and THF as eluent in a yield of 80%.

C. Synthesis of 1- (dimethvlaminoethyl) -2,3.5-tricvclo-hexyl-cyclopentadienyl titanium dichloride and fl- (di-1003015 - 19-methvlaminoethyl) -2,3,5-tr icvclohexylclopentadiene-nvl 1 dimethyl t it on fill) f C, H f c-Hex), f CH?) 7NMe7T i (111) Cl ΐ \ and fCeH (c-HexU (CH, KNMe.Ti (III1Me..1

Chilled slurry (-70 * C) of Ti (III) Cl3.3THF (2.11 g) at -70 ° C was added to lithium (dimethylaminoethyl) tricyclo-5 hexylcyclopenradiene (2.11 g, 5.70 mmol) dissolved in 20 mL of tetrahydrofuran. , 5.70 mmol) in 20 mL of THF. The resulting dark green solution was stirred at room temperature for 72 hours. After 10 evaporation, 30 mL of petroleum ether (40-60) was added. After complete evaporation again, a mint green powder (2.80 g) was obtained containing 1- (dimethylaminoethyl) -2,3,5-tricyclohexylcyclopentadienyl titanium (III) dichloride. Slurry of 0.50 g (0.922 mmol) of the above obtained [1- (dimethylaminoethyl) -2,3,5-tricyclohexylcyclopentadienyl titanium (III) dichloride) cooled to -70 ° C. [Lithium chloride] in 30 mL of diethyl ether was added dropwise 1.15 mL of methyl lithium (1.6 M in diethyl ether, 1.84 mmol). The green-brown slurry immediately turned dark. The mixture was then stirred at room temperature for 1 hour, completely evaporated and dissolved in 40 mL of petroleum ether. After filtration and complete evaporation of the solvent, a black powder (0.40 g, 0.87 mmol) containing tri-cycloxexylcyclopentadienyl-dimethylaminoethylTi (III) dimethyl was obtained.

Polymerization experiments IV-VI

A. The copolymerization of ethylene with oropene was carried out on the following phase.

A 1 liter stainless steel reactor was charged under dry N2 with 400 ml of pentamethyl heptane (PMH) and 30 µl triethyl aluminum (TEA) or trioctyl aluminum (TOA) as a scavenger. The reactor was pressurized to 0.9 MPa with purified monomers and conditioned so that the propylene: ethylene ratio in the gas was 1: 1 above the PMH. The reactor contents were brought to the desired temperature with stirring 1003013-20.

After conditioning the reactor, the metal complex (5 μταοί) to be used as the catalyst component and the cocatalyst (30 μπιοί BF20) were premixed for 15 minutes and fed to the reactor by means of a pump. The mixture was premixed in ± 25 ml PMH in a catalyst dosing vessel and rinsed with ± 75 ml PMH all under dry N2 flow.

During the polymerization, the monomer concentrations were kept as constant as possible by adding propylene (125 normal liters / hour) and ethylene (125 normal liters / hour) to the reactor. The reaction was monitored according to the temperature course and the course of the monomer feed.

After 10 minutes of polymerization, the monomer feed was stopped and the solution was tapped under pressure and collected. The polymer was dried under vacuum at about 120 ° C for 16 hours. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 1003013 B. The homopolymerization of ethylene and the copolymerization of ethylene with octene were carried out on the next 3 steps.

4 600 ml of an alkane mixture (pentamethyl-heptane or boiling point petrol) was placed under dry N 2 as 6 reaction medium in a stainless steel reactor with a capacity of 1.5 liters. Then the intended amount of dry octene was introduced into the reactor 9 (this amount can also be zero.) The reactor 10 was then heated to the desired temperature under stirring under a desired ethylene pressure with stirring.

12

In a 100 ml catalyst dosing vessel with a volume of 13 ml, 25 ml of the alkane mixture as solvent 14 were dosed. Herein, the desired amount of an Al-containing co-catalyst was premixed with the desired amount of metal complex for 1 minute 16 such that the ratio Al / (metal in the complex) in the reaction mixture is 2000.

- 21 -

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.

Then the mixture was neutralized with NaHCO 3. An anti-oxidant (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.

15 In both cases the following conditions were varied: - metal complex - type and amount of scavenger 20 - type and amount of cocatalyst - temperature

The current conditions are shown in Table I.

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Claims (5)

1. Poly-substituted cyclopentadiene compound, characterized in that at least two substituents are cyclic alkyl groups with the exception of di- and tricyclohexylcyclopentadiene. 2. Metal complex in which at least one cyclopentadiene compound substituted by two cyclic alkyl groups is present as a ligand. 3. Tri- or multiply substituted cyclopentadiene compound, of which at least one substituent is -RDR'n, wherein R is a linking group between the cyclopentadiene and the DR'n 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 D-linked R' groups, and wherein at least one of the remaining substituents is a cyclic alkyl groups. Metal complex, in which at least one cyclopentadiene compound according to claim 2 or 3 is present as a ligand. Use of the metal complex according to claim 4 as a catalyst component for polymerizing α-olefins. 100301? MMlItbi · Μ ·. <II \ «» «· ·· .¼. v. - t REPORT ON NEW HEIOSON RESEARCH OF INTERNATIONAL TYPE II0ENT1FICATION OF THE NATIONAL APPLICATION KtnrmrK of, among others, applicant ol van da gamacnogoa 8670 NL Neoenanase application no. Inoienngsaaum 1003013. May 3, 1996 Priority invoked Applicant (Name) DSM NV Date of wet request for onη onaerzoea from mtemaicnaai typ # Ooor aa mstanoe for tntamaaonaai Research (ISA) on wet varzoaK for underneath of awamaaonal type eegeMono nr. SN 27500 NL, CLASSIFICATION OF THE SUBJECT (at eepassmg van verccndlenae daaxJieaoaa, alia daasifeaaesymboien opga van) 'oigans ao mtamaoonaie aamheaaa (IPC) Int. Cl. 6: C 07 C 13/15, C 08 F 10/00, C 07 F 17/00. FIELDS OF OE TECHNIQUE RESEARCHED _i_Onaarzocma mmimum documentation I Classification system | Classificationsvmootan '| Int. Cl. 6 C 07 C, C 07 F, C 08 F Unsourced anoara aocumentaoe to, among others, minimum documentation insofar as very good documents m aa unoerzocnta gaöaaan sentence o pg and om an III.! X: NO RESEARCH OPPORTUNITIES FOR CERTAIN CONCLUSIONS (remarks on supplement totad) IV. "; LACK OF UNIT OF INVENTION (listing on replenishment payload) i, / rorm PCT.ISA / tOliaiCS f9S4 / 0