NL1003017C2 - Fluorene substituted with a heteroatom-containing group. - Google Patents

Description

- 1 - GESTTBST TTTTF.FRΓ) CONTAINING A HETEROATOM-CONTAINING GROUP

FLUORENE

The invention relates to a substituted fluorene compound containing at least one substituent of the form -RDR '', wherein R is a linking group between the fluorene and the DR '' group, D a heteroatom selected from group 15 or 16 of the Periodic Table of the Elements, R 'is a 10 substituent and n is the number of R' groups attached to D.

In the following, fluorene will be abbreviated as 'Flu'. The same abbreviation will also be used for a fluorenyl group if it is clear from the context whether fluorene itself or its anion is meant.

Metal complexes in which cyclopentadiene compounds exist as ligands are generally used as catalyst components in the polymerization of, in particular, α-olefins.

It is often stated that compounds such as fluorene derived from cyclopentadiene can also be used as ligands. To date, fluorene compounds have only been used in so-called sandwich compounds. These are metal complexes in which two cyclopentadienyl derivatives are bound to the metal, of which in this case at least one is a fluorene compound. It is not known whether and, if so, in what other form, for instance substituted or unsubstituted, and in which metal complexes fluorene built up and suitable as catalyst component, could be a useful ligand.

Surprisingly, it has now been found that very useful catalyst components for olefin polymerization can be obtained when the Flu-35 compounds of the invention are used singly as a ligand on a metal that is not in its highest valency state. Thus is a 100301? - 2 - mono-Flu-substituted metal complex obtained from metals in a valency state lower than the highest possible, in which the Flu-containing ligand exerts a strong stabilizing effect without blocking the 5 active sites of the complex so that the complexes in a cationic state have excellent catalytic performance.

Corresponding complexes in which the Flu compound is not substituted in the manner indicated are found to be unstable or, if otherwise stabilized, to have poorer catalytic properties than the complexes of substituted Flu compounds of the invention.

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

20 From J. Org. Chem., 1989, 54, 4302-13 discloses 9-methyldimethylamine fluorene. The special suitability of these and such compounds as a ligand to a metal that is not in its highest valency state cannot be inferred or suspected in any way from this publication.

A substituted Flu compound is understood to mean a fluorene substituted at least with a group of the form RDR'n. In addition, other groups of the form R2 to be defined below may also be present at 30 positions on both 6-rings of the fluorene. Preferably, the RDR'n group is at the 9 position of the fluorene.

The Flu compound can also be a heterofluorene compound. Here and hereafter, a heterofluorene group is understood to mean a group derived from fluorene, but in which at least one of its 1003017 - 3 - C atoms has been replaced by a heteroatom, wherein the heteroatom can be selected from group 14, 15 or 16 of the Periodic Table of the Elements. If more than one heteroatom is present, these heteroatoms can be the same or different. More preferably, the heteroatom is selected from the group 15, even more preferably, the heteroatom is nitrogen.

The R2 groups can each be separately hydrogen or 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. Two adjacent hydrocarbon radicals may also be linked together in a ring system. R2 may also be a substituent containing, in addition to or instead of carbon and / or hydrogen, one or more heteroatoms from Group 14-17 of the Periodic Table of the Elements. For example, a substituent can be an N, O, F 20 and / or Si-containing group. R2 should not be a cyclopentadienyl or derivative group.

In the substituent of the form RDR'n, the R group forms the link between the Flu and the DR 'group. The length of the shortest connection between the Flu and 25 D, hereinafter referred to as the main chain of R, is critical in that it determines the accessibility of the metal atom by the DR group to obtain 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. The R group is at least 1 atom long. 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: 1003017-4.

(-ER32-) p with p = 1-4 and E is an element of group 14 of the Periodic System. The R3 groups are as defined for R2.

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, tetra-10-alkyl disilylene or tetraalkylsilaethylene (-SiR32CR32-). 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, 15 selected from group 15 or 16 of the Periodic Table 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, and sheet in that n = 2 if D is from group 15 and 20 that n - 1 if D is from group 16. Preferred is the heteroatom D selected from the group nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S); more preferably, the heteroatom is nitrogen (N). The R 'groups can be the same or different and can be selected from the same groups as defined for R2 with the exception of hydrogen. 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 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, for example, a pyrrolidinyl group).

The DR group can bind coordinatively with a metal.

The optionally poly-substituted flu compounds according to the invention are found if 1003017-5. Used as the only ligand in a metal complex in which the metal is not in its highest valence state to provide compounds with good stability and good catalytic activity. The invention therefore also relates to this application. Incidentally, the substituted Flu compounds can also be used singly or multiply as ligands on metals, which are in their highest valency state, with good results. In this case, too, active catalysts are obtained, which in many cases give better results in a specific application than the known Flu-containing ligands.

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 and rare earths. Group 4 and 5 metal complexes are preferably used as catalyst component 20 for the polymerization of 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.

Olefins here and hereinafter denote 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 invention therefore also relates to the metal complexes thus composed and their use as catalysts in particular for the polymerization of olefins, both linear and branched and cyclic olefins and whether or not conjugated dienes and mixtures thereof.

The group of the form RDR'n can be substituted at the 9-position on any Flu-compound already substituted at one or more positions of the six-rings. Methods for substituting Flu with groups other than RDR '' are known, for example, from Bull. Chem. Soc. of Japan, 59, 97-103 (1986) and Liebigs Am. Chem. 1976, 74-88. For example, the RDR 'group can be applied according to the following synthetic route, provided that the 9-position of the fluorene is not substituted.

In a first step of this route, a substituted Flu 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, eg 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 fluorenyl anion formed reacts with a compound of the formula (DR '- - RY) or (XR-Sul), wherein D, R, R' and n are as above 10 0 3 0 t 7 - 7 - 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 -SO2R6, wherein R6 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 heteroatoms from group 14-17 of the Periodic Table of the Elements, such as N, O, Si or F.

Examples of sulfonyl groups are: phenylmethanesulfonyl, benzenesulfonyl, 1-15 butanesulfonyl, 2,5-dichlorobenzenesulfonyl, 5-dimethylamino-1-naphthalenesulfonyl, pentafluoro-benzenesulfonyl, p-toluenesulfonyl, trichloromethanesulfonyl, trifluoromethanesulfon-2-sulfanes isopropylbenzenesulfony1, 2,4,6-trimethylbenzene-20 sulfonyl, 2-mesitylene sulfonyl, methanesulfonyl, 4-methoxybenzenesulfonyl, 1-naphthalenesulfonyl, 2-naphthalenesulfonyl, ethanesulfonyl, 4-fluorobenzenesulfonyl and 1-hexadecane 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'a-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.

The synthesis of metal complexes with the above-described specific Flu compounds as 1003017-8 ligand can take place according to the methods known per se for this purpose. The use of these Flu compounds does not require modifications of these known methods. Here, the substituted 5-Flu compound is converted into an anion using, for example, a lithium alkyl or a Grignard compound, and then this anion is reacted with a metal halide. Also, the Li-Flu compound or corresponding Flu compound obtained with the Grignard compound can be converted into a Si or Sn-Flu compound, which is then reacted with the metal halide.

The polymerization of α-olefins, for example 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 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. An organometallic compound is usually used as the co-catalyst, 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) borane, 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, optionally perfluorinated hydrocarbons are eligible. The monomer to be used in the polymerization can also be used as a dispersion or solvent.

The following 15 methods of analysis were used in the characterization.

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

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

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

Experiment I

Preparation of 2- (NN-dimethylaminoethyl) toss in situ In a three-necked round bottom flask equipped with magnetic stirrer and dropping funnel, a solution of 2-dimethylaminoethanol was added under dry nitrogen to 10 0 3 c 1 7 -ιοί 1 equivalent in dry THF at - 10 ° C a solution of n-butyl lithium in hexane (1 equivalent) was added (dosing time: 60 minutes). After adding all butyl lithium, the mixture was brought to room temperature and stirred for 2 hours. The mixture was then cooled (-10 ° C) and paratoluenesulfonyl chloride (1 equivalent) was added. It was then stirred at this temperature for 15 minutes before the solution was added to a fluorenyl anion. Similar tosylates can be prepared in an analogous manner.

Example II

a. Preparation (dimethvlaminoethylvluorene

In a 250 ml three-necked round bottom flask equipped with magnetic stirrer and dropping funnel, 30 ml of a solution of fluorene (8 g; 48.1 mmol) in dry tetrahydrofuran (125 ml) of a 1.6 molar solution of n-butyl lithium in hexane is added dropwise. After stirring at room temperature for 24 hours, a solution of 2- (dimethylaminoethyl) tosylate (48 mmol) prepared in situ was added in THF / hexane. 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 tetrahydro uranium was distilled off. The crude product was extracted with ether and the combined organic phase was dried (over sodium sulfate) and evaporated. The residue was purified on a silica gel column, resulting in 9.1 grams (80%) (dimethylaminoethyl) fluorene.

b. Synthesis of ((dimethylaminoethyl] fluorenyl titanium dichloride 35 In a 200 mL Schlenk flask, (dimethylaminoethyl) fluorene (2.37 grams, 10 mmol) was dissolved in 30 mL of tetrahydrofuran, at 0 * C (ice bath) 1003017 - 11 -

6.2 mL of a 1.6 molar butyl lithium in hexane solution was added. After stirring for 15 minutes, this mixture was further cooled to -78 degrees Celsius and a slurry of 5 Ti (III) Cl3.3THF (3.71 g, 10 mmol) in 30 mL THF, also cooled to -78 degrees Celsius, was added.

added. The cooling bath was removed and the resulting dark green / brown solution was stirred at room temperature for 80 hours. After evaporation, 45 mL of petroleum ether (40-60) was added. After complete evaporation again, a greenish / brownish powder (4 g) containing ((dimethylaminoethyl) fluorenyl) titanium dichloride was obtained.

Nurturing Experiment A

Preparation of (Fluorine Titanium Dichloride 15 The preparation was carried out as Synthesis as in Example I but now with 1.7 grams of fluorene (10.2 mmol), 6.4 mL of 1.6 molar butyl lithium in hexane solution and 3.78 grams of TiCl3.3THF (10.2 mmol).

2.95 grams of material were obtained in which the target compound could not be characterized positively.

Examples III-IV and Comparative Experiments B and C Ethylene / octene copolmerization

The copolymerizations of ethylene with octene 25 were carried out in the following manner.

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

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

In a 100 ml catalyst metering vessel, 25 ml of the alkane mixture was dosed as a solvent. Herein, the desired amount of an Al-containing cocatalyst 1003017-12 - ~ 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 guenched 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. Then an antioxidant (Irganox 1076, TM) was added to the organic fraction to stabilize the polymer. The polymer was dried under vacuum at 70 ° C for 24 hours.

The following can be varied: - metal complex 20 - type and amount of scavenger - type and amount of cocatalyst - temperature

The catalyst obtained in Example II was used at two different temperatures in the polymerization experiments III and IV. For comparison, the catalyst obtained in Example A at the same two temperatures was used in polymerization experiments B and C.

30 The current conditions are shown in Table 1.

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Claims (11)

A substituted fluorene compound containing at least one substituent of the form -RDR '', wherein R is a linking group between the fluorene and the DR '' group, D a heteroatom selected from group 15 or 16 of the Periodic System of Elements, R 'are a substituent and n is the number of R' groups bound to D, with the exception of 9-methyldimethylamine-fluorene. The compound of claim 1, wherein the RDR'n group is substituted at the 9 position. A compound according to claim 1 or 2, wherein the R group has the structure 15 (-ER32-) p wherein p = 1-4, E is an element from group 14 of the Periodic Table and wherein the R3 groups are each 20 H or a hydrocarbon radical. A compound according to any one of claims 1-3, wherein D is selected from the group consisting of N, O, P and S. A compound according to any one of claims 1-3, wherein 25. is nitrogen. Metal complex in which a fluorene compound according to any one of claims 1 to 5 is present as a ligand. Metal complex in which the metal is present in a state other than the highest valency and in which a compound according to any one of claims 1 to 5 is present as a ligand. A metal complex according to claim 6 or 7, wherein the metal is a Group 5 or 6 transition metal of the Periodic Table or a lanthanide. The metal complex of claim 8, wherein the transition metal is selected from the group consisting of 1003017-15 from Ti, Hf, Zr, and V. Use of a metal complex according to any one of claims 6-9 as a catalyst component. 11. Use according to claim 10 for polymerizing olefins. 1. o 3 v; 1 COOPERATION TREATY (PCT) - ____ REPORT ON NEWNESS RESEARCH OF INTERNATIONAL TYPE IOENT1FIKAT1E OF THE NATIONAL APPLICATION Characteristic of the applicant 8757 NL Dutch application no. Mienngseekjm 1003017. May 3, 1996 Priority Daughter Applicant (Neem) DSM NV Daum of the request for a memoionai * type of turmoil By the tnsanie for Iniamaionaei Onurroek (ISA) ** reconcile for an enurai ^ yy jniegyiggy ^ p> e jptj ^ kana w SN 27504 EN I. CLASSIFICATION OF THE SUBJECT (for eepessmg of most refined ctasirtraara. all da »i6caee * ym boats declared) Voigene ae mwmaaonaie aatoftcaoe (IPC) '1 * ~ Int. Cl. 6: C 07 C 211/31, C 08 F 10/00, C 07 F 9/00, C 07 F 5/00, B 01 J 31/22, C 07 F 17/00 II. FIELDS OF TECHNIQUE EXAMINED ___._ Minimum documentation examined__. Classification system ClassificationvmPoland _ Int. Cl.6 C 07 C, C 07 F, C 08 F, B 01 J Untested anoere oocumenaoe oe ae minimum documenara insofar as such documents include the prayers examined III. HH DOES NOT INVESTIGATE FOR CERTAIN CONCLUSIONS (comments on Supplementary Olad) IIV. ' LACK OF UNIT OF INVENTION (Comments on Supplementary IAD) 1. I sorm PCT.1SA, '23l (a> Cê l9Srf I t