NL1003019C2 - Multiply substituted cyclopentadiene. - Google Patents

Description

- 1 - MULTIPLY SUBSTITUTED CYCLOPENTADIAS 5

The invention relates to a multi-substituted cyclopentadiene compound. Cyclopentadiene compounds are widely used as a ligand in metal complexes.

Cyclopentadiene compounds are widely used as a ligand in metal complexes, which act as catalyst components, especially for the polymerization of olefins. Depending on the metal, its valence state and the ligands used, the complexes appear to be more or less suitable for certain applications.

In the J. of Organomet. Chem, 479 (1994), 1-29, reviews 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.

The most commonly used cyclopentadiene compounds are unsubstituted or cyclopentadiene substituted with one to five methyl groups. However, these appear when used as a ligand in metal complexes, in which the metal is not in the highest valence state, so that the metal is, for example, Ti (III), Hf (III), Zr (III) or V (IV) to provide catalyst components of low to very low activity, especially in olefin polymerization.

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 10 o 3 o 1 s - 2 - that tetravalent Ti centers are required for catalytic activity". It should be remembered here that Ti is exemplary of the metals which are suitable as metal in the conventional cyclopentadienyl-substituted metal complexes.

Also Cp compounds with a substituent of the form - (ER2) pD (R ') nH, in which E is an atom selected from group 14 of the Periodic Table of the Elements, D a heteroatom is selected from group 15 or 16 of the 10 Periodic Table of the Elements, R and R 'are substituents and n is the number of D-linked R' groups and p = 1-4 are known. These compounds are described, inter alia, in EP-A-0.420.236 and WO-A-93/08221. These compounds are very suitable as a ligand in olefin polymerization catalysts.

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.

Olefins here and hereafter designate α-olefins, diolefins and other ethylenically unsaturated monomers. When speaking of polymerizing olefins, this includes 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 containing a substituent of the form - (ER2) pD (R ') „H, in which E is a 30 atom selected from group 14 of the Periodic Table of the Elements, D is a heteroatom from group 15 or 16 of the Periodic Table of the Elements, R and R 'are substituents, n is the number of D-linked R' groups and p = 4, which, when used as a ligand in a metal complex, wherein the metal not in the highest valency state is catalyst components with activity higher than 1003018-3 which yields with the usual Cp-containing ligands.

This object is achieved according to the invention in that at least two other substituents are linear alkyl groups with at least two C atoms.

Surprisingly, when substituted as a ligand in the above-described metal complexes, thus substituted Cp compounds appear to yield catalyst components with a higher activity in the polymerization of olefins, especially of ethylene, than the known Cp compounds.

The linear alkyl groups with at least two C atoms can be the same or different. preferably the substituted Cp compound contains 2,3 or 4 linear alkyl groups as a substituent. These linear alkyl groups do not contain a heteroatom. In addition to these alkyl groups and the substituent of the form - (ER2) pD (R ') nH, the presence of which is required in the context of the invention, other substituents may also be present.

The poly-substituted Cp compound of the invention contains at least two linear alkyl groups, not containing a heteroatom, as substituents, H being not considered a substituent. In addition to the two required substituents and the substituent of the form - (ER2) pD (R ') nH, the poly-substituted Cp compound may also contain other substituents, optionally containing a heteroatom.

Particularly suitable linear alkyl groups are ethyl, propyl, butyl, pentyl, hexyl and octyl groups, but higher homologs can also be used. Cp compounds substituted four-fold with ethyl and / or propyl groups are preferred. Substituents, which may be present in addition, are, for example, alkyl groups, both linear and branched and cyclic, aryl and aralkyl groups. Also, in addition to carbon and hydrogen, one or more heteroatoms 1003018-4 from groups 14-17 of the periodic table may exist, for example, 0, N, Si or F. Examples of suitable groups are methyl, ethyl, (iso) propyl, secondary butyl, pentyl, hexyl and octyl, (tertiary-5) butyl and higher homologues, cyclohexyl, benzyl, phenyl, paratolyl.

Substituted Cp compounds can be prepared by reacting a halide of the substituting compound in a mixture of the Cp-10 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 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, after which ring closure is also possible.

Almost 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 generally being able to be substituted four and often even five-fold.

1003019 - 5 -

With this method, two-, three-, four-fold with the desired linear alkyl and optionally in free positions still with other groups of substituted Cp-compounds can be obtained. The substituents are preferably used in the process in the form of their halides and 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 by this method to obtain Cp-bonds which are substituted with specific combinations of substituents without intermediate separation or purification. For example, a two-fold substitution using a certain alkyl halide can be performed first, 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 per 30 moles of Cp compound and preferably in an amount of 7-15 moles per mole of Cp compound. These amounts are significantly lower than the 40 moles per mole of Cp compound customary in the art. The substitution takes place at atmospheric or elevated pressure, for example up to 100 Mpa, the latter mainly in connection with the presence of volatile components. The temperature at which the reaction takes place can be 1003019-6. - varying 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 as a result of the heat released in the reactions occurring or by external heating.

The substitution takes place in the presence of a phase transfer catalyst, which is capable of transferring OH ions from the aqueous phase to the organic phase containing Cp and halide 10, which react there with an H-cleavable from the Cp compound. atom. 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 in various sequences.

After the reaction is complete, 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.

Depending on the size and the associated steric hindrance of the compounds to be substituted, three to five times substituted Cp compounds can be obtained.

Furthermore, the substituted Cp compound of the invention contains at least one substituent of the form - (ER2) pD (R ') „H, wherein p = 1-4.

E is selected from group 14 of the Periodic Table of the Elements and can therefore be C, Si, Ge and Sn. Preferably E is Si or Ge.

D is selected from group 15 or 16 of the Periodic Table of the Elements. When D is selected from group 15, the element has a coordination number 3 and when D is selected from group 16, the element has a coordination number 2. Preferably DN, 10030 is:-:, Ρ, S. Particularly preferred is D N.

R and R 'are substituents and can each separately be a hydrocarbon radical of 1-20 carbon atoms (such as alkyl, aryl, arylalkyl, etc.). Examples of such hydrocarbon radicals are methyl, ethyl, propyl, butyl, hexyl, decyl, phenyl, benzyl and p-tolyl.

R 'may also be a substituent containing, in addition to or instead of carbon and / or hydrogen, one or more hetero atoms from Group 14-16 of the Periodic Table 10 of the Elements. For example, a substituent can be an N, O and / or Si-containing group. R 'should not be a cyclopentadienyl or derivative group. n represents the number of substituents bound to D. n is 1 when D is selected from the group of 15 elements and n is 0 when D is selected from the group of 16 elements.

A Cp compound containing a substituent of the form - (ER2) pD (R ') nH can be synthesized starting from a Cp compound substituted with at least two linear alkyl substituents with at least two C atoms.

This substituted Cp compound is deptotonated to the anion with a base, sodium or potassium.

As base can be used, for example, organolithium compounds (R3Li) or organomagnesium compounds (R3MgX) in which R3 'is an alkyl, aryl or aralkyl group and X ^ halide, such as, for example, n-butyl lithium or i-30 propyl magnesium chloride.

Potassium hydride, sodium hydride, inorganic bases, such as NaOH and KOH, and alcoholates of Li, K and Na can also be used as the base.

Mixtures of the above compounds can also be used.

The anion is then reacted with a compound of the form (R2E) pX2 and the resulting reaction product is reacted with a compound of the form LiD (R ') nH or with a compound of the form DR'nH2, wherein D, R ', n and P are as defined above.

This method is described more specifically in EP-A-0.420.236.

Metal complexes that are catalytically active when one of their ligands is a compound of the invention are metal complexes from groups 10-10 of the Periodic System and rare earths.

Group 4 and 5 metal complexes are preferably used as a catalyst component for polymerizing olefins, metal complexes of groups 6 and 7, in addition also for metathesis and ring-opening metathesis polymerisations and metal complexes of group 8-10. 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. If the metals are not in their highest valency state, the Cp compounds appear to provide excellent stability of the complex formed without blocking the active sites, thus catalytic activity is greater than when using other Cp compounds.

In the review article mentioned in the J. of Organomet. Chem. from 1994 it is even noted that 30 "An important feature of these catalyst systems is that tetravalent Ti centers are required for catalytic activity". It should be borne in mind here that Ti is exemplary of the metals which are suitable as metal in the usual cyclopentadienyl-35 substituted metal complexes.

The synthesis of metal complexes with the above-described specific Cp compounds as 1 0 0 '- 9 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, for example ethylene, propylene, butene, hexene, octene and mixtures thereof and with should 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 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.

For example, mention may be made 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 particularly between 25 and 250 ° C. 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. Also aromatic

10 0 3 0 1 S

- 10, possibly perfluorinated hydrocarbons, are eligible. The monomer to be used in the polymerization can also be used as a dispersion 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.

10

Example I; the preparation of (N-t-butvlaminol (dimethyl) f2,3.4.5-tetraethyloclopentadienyl Isilane titanium dichlotide) Example 1A: the preparation of tetra (ethylcylcloentadiene)

A 1 L double-walled reactor equipped with a baffles, cooler, overhead stirrer, thermometer and dropping funnel was charged with 1050 g of 20 clear 50% NaOH (13.1 mol) and cooled to 10 ° C. Then 32 g of Aliquat 336 (79 mmol) and 51 g (0.77 mol) of freshly cracked cyclopentadiene were added. The reaction mixture was stirred turbulently for several minutes. Then 344 g of ethyl bromide 25 (3.19 mol) was added in one hour. It was cooled with water. After stirring at room temperature for 1 hour, the reaction mixture was heated to 35 ° C, followed by stirring for another 6 hours. Stirring was stopped and phase separation was awaited. The water layer was drained and 1050 g (13.1 mol) of fresh 50% NaOH were added. Stirring was then continued for 5 hours at room temperature. GC showed that 15% tri-, 78% tetra- and 7% penta (ethyl) cyclopentadiene was present in the mixture at that time. The product 35 was distilled at 11 mbar and 91 ° C. After distillation, 74.8 g of tetra (ethyl) cyclopentadiene were obtained.

The product was characterized by GC, 100501ft-11 GC-MS (13C and 1H-NRR.

Example IB: the preparation of (N-t-butvlamino) (dimethyl) (2.3.4.5-5 tetraethyloclopentadienyl) silane

In a 2 liter glass flask, with stirring, 17.8 grams of tetra (ethyl cyclopentadiene (0.1 mol) were dissolved in 1 liter of dry THF. This solution was cooled with an ice bath to 0 ° C. solution, 62.5 ml of a 1.6 molar butyllithium in hexane solution (0.1 mol) was slowly added A light yellow solution was formed, which was stirred at room temperature for two hours This solution was added in about 4 hours to a solution of 42.4 ml of dimethyldichlorosilane (0.35 mol) in 300 ml of dry THF in a 2 liter flask A light yellow solution was formed, which was stirred for another three hours at room temperature, after which the solvent and the excess dimethyldichlorosilane 20 evaporated at 50 ° C and 10 mm mercury pressure The residue, a clear yellow liquid with some solid (LiCl), was added in about 1 hour to a solution of 54 ml of tertiarbutylamine (0.5 mol) in 250 ml of dry THF in a 1 liter glass flask, g cooled using an ice bath. The ice bath was then removed and the resulting reaction mixture was stirred for about 10 hours. The resulting precipitate was filtered through a Buchner funnel. The yellow filtrate was evaporated at 50 ° C and 10 mm of mercury pressure.

Vacuum distillation of the residue ultimately yielded 15 g of pure (N-t-butylamino) (dimethyl) (2,3,4,5-tetraethylcyclopentadienyl) silane.

Example IC: The preparation of (Nt-35 butvlamino) (dimethyl) (2.3.4.5-tetraethyloclopentadienvl) silane titanium dichloride Under an inert atmosphere (dried 1003019 - 12 - nitrogen) in a 200 ml flask (Nt) -butylamino) (dimethyl) (2,3,4,5-tetraethylcyclopentadienyl) silane (9.8 mmol) dissolved in 75 ml diethyl ether. This solution was cooled to 0 ° C with stirring using an ice bath. To this was added 12.2 ml of a 1.6 molar butyl lithium solution in hexane for about 5 minutes. The ice bath was then removed and the solution was stirred at room temperature for two hours. A slight cloudiness (white) in a yellow solution was visible. This reaction mixture was cooled to -78 degrees Celsius (dry ice bath; at this low temperature there was clearly a lot of white precipitate) and was added via a bend or coupling to a blue slurry of 3.6 grams of titanium trichloride (also cooled to -78 15 degrees Celsius) ( complexed with 3 equivalents of THF: "TiCl3.3THF"; 9.8 mmol). The reaction mixture turned dark, and after removing the dry ice bath and allowing the reaction mixture to rise to room temperature, the color became much darker (purple / brown / black). After stirring for about 14 hours, 1.4 grams of silver chloride AgCl was added (9.8 mmol).

The reaction mixture was stirred at room temperature for 15 hours, during which time the mixture turned to red while clear silver precipitate formed. The reaction mixture was filtered through a tilt filter and the residue was evaporated to dryness. Then 50 ml of hexane was added to the residue and this mixture was filtered. The precipitate on the filter was washed with 20 ml of hexane and the collected hexane fractions were evaporated until slight turbidity (approx. 45 ml). This cloudy mixture was heated very slightly (35 degrees Celsius) and placed in a -20 degrees Celsius refrigerator. After 17 hours, 35 crystals were formed. The whole was kept at -80 degrees Celsius for 20 hours after which the solid was filtered off and washed with two times 15 ml of 100301? - 13 - cold (-20 degrees Celsius) hexane. Yield: 1.54 grams of (N-t-butylamino) (dimethyl) (2,3,4,5-tetraethylcyclopentadienyl) silane titanium dichloride.

Example II; the preparation of (N-t-butvlamino) (dimethylH2.3.4.5-tetrapropyl-cyclopentadienvebermane titanium dichloride

Example IIA: the preparation of 10 tetra (propyl) cycloentadiene

A 1 L double-walled reactor equipped with a baffles, cooler, overhead stirrer, thermometer and dropping funnel was charged with 1000 g of clear 50% NaOH (12.5 mol) and cooled to 10 ° C. Then 30 g of Aliquat 336 (74 mmol) and 50 g (0.75 mol) of freshly cracked cyclopentadiene were added. The reaction mixture was stirred turbulently for several minutes. Then 373 g of propyl bromide (3.03 mol) was added over an hour. It was cooled with water. After stirring at room temperature for 1 hour, the reaction mixture was heated to 35 ° C, followed by stirring for another 6 hours. Stirring was stopped and phase separation was awaited. The water layer was drained and 990 g (12.4 mol) of fresh 50% NaOH 25 was added. Stirring was then continued for 5 hours at room temperature. GC showed that at that time 14% tri-, 80% tetra- and 6% penta (propyl) cyclopentadiene was present in the mixture. The product was distilled under reduced pressure. After vacuum distillation, 103.14 g of tetra (propyl) cyclopentadiene were obtained.

The product was characterized by GC, GC-MS, 13C and 1 H NMR. 1 1003019

Example IIB: Preparation of (N-t-butyl-aminol (dimethyl) (2,3,4,5-tetrapropyl-cyclopentadienyl) proton - 14 -

In a 2 liter glass flask, with stirring, 18.8 grams of tetra (propyl) cyclopentadiene (0.08 mol) was dissolved in 1 liter of dry THF. This solution was cooled to 0 ° C using an ice bath. To the cooled solution, 50 ml of a 1.6 molar butyl lithium in hexane solution (0.08 mol) was slowly added. A light yellow solution was formed, which was stirred at room temperature for two hours. This solution was added in about 4 hours to a solution of 48.6 grams of dimethyldichloromerman (0.28 mol) in 250 ml of dry THF in a 2 liter flask. A light yellow solution was formed, which was stirred for another three hours at room temperature. After this, the solvent and the excess dimethyldichloro-germ 15 were evaporated at 80 degrees centigrade and 5 mm mercury pressure. The residue, a clear yellow liquid with some solid (LiCl), was added in about 1 hour to a solution of 43 ml of tertiarbutylamine (0.4 mol) in 250 ml of dry THF in a 1 liter glass flask, which was Cooled using an ice bath. The ice bath was then removed and the resulting reaction mixture was stirred for about 10 hours. The resulting precipitate was filtered through a Buchner funnel. The yellow filtrate was evaporated at 50 ° C and 10 mm mercury pressure. Vacuum distillation of the residue eventually yielded 14 g of pure (N-t-butylamino) (dimethyl) (2,3,4,5-tetrapropylcyclopentadienyl) germane 1 2 3 4 5 6 1003019

Example IIC: the preparation of (N-t-2-butvlamino) (dimethyl) (2.3.4.5-3-tetrapropylcopentadienvylbermane titanium dichloride 4

Synthesis as of (Nt-5-butylamino) (dimethyl) (2,3,4,5-6-tetraethylcyclopentadienyl) silane titanium dichloride, now containing: 3.3 grams (Nt-butylamino) (dimethyl) (2,3,4, 5--15 tetrapropylcyclopentadienyl) germane (8.08 nunol) 10.1 ml 1.6 molar butyl lithium in hexane solution (16.16 mmol); cooling the dilithium compound to -78 degrees Celsius gives only a slight turbidity of 5 to 2.99 grams of titanium trichloride. 3 THF (8.08 mmol) 1.16 grams of silver chloride (8.1 mmol) recrystallization from approximately 30 ml of hexane instead of 45 ml yield: 1.23 g (Nt-butylamino) (dimethyl) (2,3,4,5-10 tetrapropylcyclopentadienyl) germane titanium dichloride.

Note: according to NMR there was still some product in the last £traate (after recrystallization); that has not been worked up.

15

Example III: Preparation of (N-t-butvlamino) (dimethyl-2,3,4,5-tetraoctyl-cyclopentadiene-silane titanium dichloride 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 1 0 0 3 0 1 δ

Example UIA: the preparation of 2 tetra (octyl) cyclopentadiene 3

A 4 1.5 L double-walled reactor equipped with a baffles, cooler, overhead stirrer, 5 thermometer and dropping funnel was charged with 900 g of 6 clear 50% NaOH (11.3 mol) and cooled to 7 10 ° C. Then 30 g of Aliquat 336 (74 mmol) and 48 g (0.72 mol) of freshly cracked cyclopentadiene 9 were added. The reaction mixture was stirred turbulently for several minutes. Then 577 g of octyl bromide 11 (2.99 mol) was added in an hour. This was cooled with water. After stirring at room temperature for 1 hour, the reaction mixture was heated to 35 ° C, followed by stirring for another 14 hours. Stirring was stopped and phase separation was awaited. The water layer was drained 16 and 920 g (11.5 mol) of fresh 50% NaOH was added. Stirring was then continued for 5 hours at room temperature. GC showed that at that time 10% tri-, 83% tetra- and 7% penta (octyl) cyclopentadiene was present in the mixture. The product was distilled under reduced pressure. After vacuum distillation, 226.6 g of tetra (octyl) cyclopentadiene 5 were obtained.

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

Example IIIB: Preparation of (N-t-10 butvlamino) (dimethylW2.3.4.5-tetraoctyl] cyclopentadienyl) silane

In a 2 liter glass flask, 25.7 grams of tetra (octyl) cyclopentadiene (0.05 mol) was dissolved in 1 liter of dry THF, with good stirring. This solution was cooled to 0 ° C using an ice bath. To the cooled solution, 31 ml of a 1.6 molar butyl lithium in hexane solution (0.05 mol) was slowly added. A light yellow solution was formed, which was stirred at room temperature for two hours. This solution was added in about 4 hours to a solution of 21.8 ml of dimethyldichlorosilane (0.18 mol) in 250 ml of dry THF in a 2 liter flask. A light yellow solution was formed, which was stirred for another five hours at room temperature. After this, the solvent and excess dimethyldichlorosilane were evaporated at 50 ° C and 10 mm mercury pressure. The residue, a clear yellow liquid with some solid (LiCl), was added in about 1 hour to a solution of 26.8 ml t-butyl amine (0.25 mol) in 250 ml dry THF in a 1 30 liter glass flask, which was cooled using an ice bath. The ice bath was then removed and the resulting reaction mixture was stirred for about 10 hours. The resulting precipitate was filtered through a Buchner funnel. The yellow filtrate was evaporated at 50 ° C and 10 mm of mercury pressure. Distillation using a mercury diffusion pump (10-6 mbar) of the residue ultimately yielded 14.5 grams of pure (Nt-10 0 3 0 1 0 - 17-butylamino) (dimethyl) (2,3,4,5-tetraoctylcyclopentadienylsilane) .

Example IIIC: Preparation of (Nt-5-butylamino) (dimethyl) (2,3,4,5-tetraoctyl-cyclopentadienyl Isilane titanium dichloride Synthesis as of (Nt-butylamino) (dimethyl) (2,3,4,5-tetraethyl-cyclopentadienyl) silane titanium dichloride, 10 now with: 3.22 grams (Nt-butylamino) (dimethyl) (2,3,4,5-tetraoctylcyclopentadienyl) silane (5 mmol) 6.2 ml 1.6 mol butyl lithium in hexane solution (9, 9 15 mmol) j cooling the dilithium compound to -78 degrees centigrade provides hardly any turbidity on 1.83 grams of titanium trichloride. 3 THF (4.95 mmol) 0.72 grams of silver chloride (5 mmol) cold storage (-100 ° C) in approximately 15 ml pentane instead of 20 45 ml hexane for 72 hours yielded a viscous dark red oil yield: 0.49 gram (Nt-butylamino) (dimethyl) (2,3,4,5-tetraoctylcyclopentadienyl) silane titanium dichloride. : According to NMR, the last filtrate (after recrystallization) still contained a lot of product, which has not been reprocessed.

Experiment a: the preparation of (N-t-30-butyl-amino (dimethyl-H 2.3.4.5-tetramethyl-cyclopentadiene-silane) titanium dichloride. The synthesis of metal complexes was carried out in the manner described for Examples 1-4 of WO-A-93/08221.

Polymerization Examples IV-VI and Polymerization Experiment A.

35 1003019 - 18 - a ..

The copolymerization of ethylene with octene was carried out in the following manner.

600 ml of an alkane mixture 5 (pentamethyl heptane or boiling point gasoline) was placed under dry N 2 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 warmed to the desired temperature under a desired ethylene pressure with stirring.

25 ml of the alkane mixture as a solvent was dosed into a 100 ml catalyst dosing vessel. Herein, the desired amount of methylaluminoxane (MAO) was premixed with the desired amount of metal complex for 1 minute such that the Al / Ti ratio in the reaction mixture is equal to 2000.

This mixture was then dosed to the reactor after which the 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 guenched with methanol.

An anti-oxidant (Irganox 1076r) was then added to the organic fraction to stabilize the polymer. The polymer was dried under vacuum at 70 0 for 24 hours. The following condition was varied: metal complex

The current condition is always stated in the tables with polymerization conditions.

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Claims (3)

1. Poly-substituted cyclopentadiene compound containing at least one substituent of the form ~ (ER2) pD (R ') nH, wherein E is an atom selected from group 14 of the Periodic Table of the Elements, D is a heteroatom from group 15 or 16 of the Periodic Table of Elements, R and R 'are substituents, n is the number of D-linked R' groups and p = 1-4, characterized in that at least two other substituents are linear alkyl groups with at least two C atoms. A metal complex containing a cyclopentadiene compound according to claim 1 as a ligand. Use of a metal complex according to claim 2 as a catalyst component in the polymerization of olefins. 1003013 cooperation treaty (pctj -....... REPORT ON NEWNESS RESEARCH OF INTERNATIONAL TYPE 1DENT1FIKAT1E OF OE NATIONAL APPLICATION Characteristic of * applicant ef vin de gemacnogd 8679 NL Nedenanose application no. Mdianngseatim 1003019 for 9th edition urn Applicant (Neem) DSM NV Daum van nel request for a survey * of n lem ai on aai type By oe tneanee for In temet onaai Research (ISA) granted to the request for a research of «Mtnaaoneal type nr. _ - __ SN 27506 GB_ I. CLASSIFICATION OF THE SUBJECT (for the preparation of a dassieaeate. Please indicate all the dasificate symbols) Follow ao MMmaaonaw Oattiheat »(1PC) Int. Cl.6: C 07 F 7/10, C 07 F 7/30, C 07 F 17/00, C 08 F 10/00 II. RESEARCHED FIELDS OF TECHNIQUE _Onoarzocftte minimum documentation Classification system ClastificationsvmDoten Int. Cl.6 C 07 F, C 08 F Survey of other ooeoeoeoeoeoe than the minimum docu me wet »insofar as such documents n the areas examined are included III. I i NO EXAMINATION FOR CERTAIN CONCLUSIONS (comments on supplementary sheet) IV. LACK OF UNIT OF INVENTION (comments on supplement totad) I 1 = drm PC ”-lSA, 23i; a'ce ts & i iL