NL1003018C2 - Indene substituted with a heteroatom-containing group. - Google Patents

Description

- 1 -

GROUP SUBSTITUTED WITH A HETEROATOM-CONTAINING

INDEEN

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

In the following, inden will be abbreviated as 'Ind'. The same abbreviation will also be used for an indenyl group if it is clear from the context whether indene 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 olefins in particular. It is often stated that compounds such as indene 20 derived from cyclopentadiene can also be used as ligands. from

Macromolecules, 1993, 26, 5822-23, a mono-indenyl-TiCl3 complex is known, which uses methylaluminoxane as co-. catalyst is used to polymerize styrene. It is not known whether and, if so, in what other form, for instance substituted or unsubstituted, and in which metal complexes otherwise used and suitable as catalyst component in single use could be a useful ligand.

Surprisingly, it has now been found that very useful catalyst components can be obtained for olefin polymerizations when the Ind compounds of the invention are used singly as a ligand on a metal which is not in its highest valency state. Thus, a mono-35 Ind-substituted complex is obtained from metals in a valency state lower than the highest possible, in which the Ind-containing ligand exerts a strong stabilizing influence 1003018-2 without blocking the active sites of the complex so that the complexes have excellent catalytic performance. In the active catalyst, the metal is present in a cationic state. The skilled person cannot infer from the above-mentioned publications that the compounds according to the invention could have such a specific action. Corresponding complexes in which the Ind compound is not substituted in the manner indicated appear to be unstable or, if otherwise stabilized, to have poorer catalytic properties than the substituted Ind compound complexes of the invention.

Furthermore, the Ind 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.

Olefins here and hereinafter denote α-olefins, diolefins and other ethylenically unsaturated monomers. When speaking of polymerizing olefins, this is understood to mean both polymerizing a single type of olefinic monomer and copolymerizing two or more olefins. A substituted Ind compound is understood to include at least one group of the form RDR'n and additionally substituent substituted with 0 to 6 R2 groups hereinafter defined.

The Ind compound can also be a heteroindene compound. Here and hereafter, a heteroindene group is understood to mean a group derived from indene, but wherein at least one of the C atoms in its 5-ring is replaced by a heteroatom, the heteroatom being 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, 1003018-3 - these heteroatoms can be either 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, alkenyl, aralkyl, etc.). Examples of such hydrocarbon radicals are methyl, ethyl, propyl, butyl, hexyl, decyl, phenyl, benzyl and p-tolyl. R2 may also be a substituent containing, in addition to or instead of 10 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, and / or Si-containing group.

The R group forms the link between the Ind and the DR group. The length of the shortest link between the Ind and D, hereinafter referred to as the main chain of R, is critical in that it determines the accessibility of the metal by the DR group to thereby achieve the desired intraroolecular 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 group can be a hydrocarbon group of 1-20 carbon atoms (such as alkylidene, arylidene, aralkylidene, 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: 30 (-ER32-) p with p = 1-4 and E is an element of group 14 of the periodic table. The R3 groups are as defined for R2.

Thus, the main chain of the R group may contain, in addition to carbon, silicon or germanium. Examples of such R groups are: dialkylsilylene, 1003018-4 - dialkylgermylene, tetraalkyldisilylene 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 selected from group 15 or 16 of the Periodic Table of Elements and one or more substituent (s) R 'linked to D'. The number of R 'groups (n) is linked to the nature of the heteroatom D, and sheet in that n 10 = 2 if D is from group 15 and 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 carbon 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 may be a pyrrolidinyl group). The DR group can coordinate bonding with a metal.

The substituted Ind compounds of the invention, when used as the sole ligand in a metal complex in which the metal is not in the highest valency state, have been found to yield compounds of good stability and good catalytic activity.

The invention therefore also relates to this application. Incidentally, these compounds, single or multiple, can also be used with good results as ligands to metals, which are in their highest valence state. In this case too, active catalysts are obtained, which in many cases give better results in a specific application than the known Ind-containing ligands.

100301e - 5 -

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. Here, complexes of Group 4 and 5 metals are preferably used as a catalyst component for the polymerization of olefins, complexes of metals of groups 6 and 7, in addition also for metathesis and ring-opening metathesis polymerizations and complexes of metals of Group 8-10 10 for olefin 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.

The invention therefore also relates to the metal complexes thus composed and their use as catalysts in particular for the polymerization of olefins, both of linear and branched and cyclic olefins and conjugated and non-conjugated dienes and mixtures thereof.

From J. Org. Chem. 1984, 49, 4224-4237 and Chem. Lett., 1981, 729-730 and other publications are known, for example, methods of making substituted Ind. Substituted or unsubstituted indene can then be substituted a group of the form -RDR'n, for example, according to the following synthetic route, if at least the 1 and / or the 3 position is free.

In a first step of this route, a substituted Ind compound is de-pentotonated 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, 100301-6, 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, for example 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 indenyl 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).

As the halogen atom X, chlorine, bromine and iodine can be mentioned. Preferably, the halogen atom X is a chlorine atom. The sulfonyl group has 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. Rs 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 -butanesulfonyl, 2,5-dichlorobenzenesulfonyl, 5-dimethylamino-1-naphthalenesulfonyl, pentafluorobenzenesulfonyl, p-toluenesulfonyl, trichloromethanesulfonyl, trifluoromethanesulfonyl, 2,4,6-triisopropylbenzenesulfonyl, 2,4,6-30 trimethyl mesitylenesulfonyl, 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 formula 10 0 3 0 1 c? - 7 - (DR 'n-R-Y) formed in situ by reaction of an amino alcohol compound (R'2NR-OH) 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 specific Ind compounds described above as a ligand can take place according to the methods known per se. The use of these Ind compounds does not require modifications of these known methods. Here, the substituted Ind 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-Ind compound or corresponding Ind compound obtained with the Grignard compound can be converted into a Si or Sn-20 Ind 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 1003018-8 bulk polymerization. As the co-catalyst, an organometallic compound is usually used, the metal being selected from Group 1, 2, 12, 13 of the Periodic Table of the Elements. For example, mention may be made of trialkylaluminum, alkylaluminum halides, alkylaluminoxanes (such as methylaluminoxanes), tr is (pentafluorophenyl) borate, dimethylanilinium tetra (pentafluoronyl) 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 15 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 20 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 were used in the characterization.

Gas chromatography (GC) was performed on a

Hewlett-Packard 5890 Series II with an HP Crosslinked Methyl Silicon Gum (25mx0.32mmx1.05 / m) column.

Combined Gas Chromatography / Mass Spectrometry (GC-MS) was performed with a Fisons MD800 equipped with a 30 quadrupole mass detector, autoinjector Fisons AS800 and CPSil8 column (30mx0.25mmxl / 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.

1003018 - 9 -

Experiment I

Eereidina of 2- (NN-dimethlaminoethyl ethosylate 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) (dosing time: 60 minutes) After addition of all butyl lithium, the mixture was brought to room temperature for 10 and stirred for 2 hours, then the mixture was 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 an indenyl anion.

Similar tosylates can be prepared in an analogous manner. In some of the following examples, a tosylate is always coupled to substituted or unsubstituted Ind compounds. In special cases, in particular cases, in addition to the desired substitution reaction, geminal coupling also takes place. 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 (dimethvlaminoethvl) indene

In a 250 ml three-necked round bottom flask, equipped with magnetic stirrer and dropping funnel, 21.5 ml of a solution of 21.5 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 the 2- (dimethylaminoethyl) tosylate (35 mmol) in THF / hexane (see experiment 1) was added. After stirring for 18 hours, the 10 µl-10 conversion was found to be 93% 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 5.23 grams (82%) (dimethylaminoethyl) indene.

10 b. Synthesis of (fdimethvlaminoethvlHndenvl) titanium dichloride

In a 200 mL Schlenk flask, (dimethylaminoethyl) indene (1.82 grams, 10 mmol) dissolved in 30 mL of tetrahydrofuran, at 0 ° C (ice bath) 6.2 mL of a 1.6 molar butyllithium in hexane solution added. After stirring for 15 minutes, this mixture was further cooled to -78 degrees Celsius and a slurry of Ti (III) C13.3THF (3.71 g, 10 mmol) in 30 mL of THF, also cooled to -78 ° C, was 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 dark powder (3.5 g) was obtained containing ((dimethylaminoethyl) indenyl) titanium dichloride.

Example III

a. Preparation 1- (dimethylaminoethyl) -2-methyl-indene

The preparation was carried out as in Example II 30 but now with 2-methyl-indene (3.9 g; 30 mmol), 18.5 mL of a 1.6 molar solution of n-butyl lithium in hexane and 2- (dimethylaminoethyl) tosylate (30 mmol).

4.7 grams (80%) of 1- (dimethylaminoethyl) -2-methyl-indene 35 b were obtained. Synthesis of (1- (dimethylaminoethyl-2-methyl-indenyl-titanium-dichloride ide 1 o o v <o;> - 11 -

The synthesis was performed as in Example II, but now with 1- (dimethylaminoethyl) -2-methyl-indene (1.37 grams, 7 mmol), 4.3 mL of a 1.6 molar solution of n-butyl lithium in hexane and 2.6 grams of TiCl3.3THF.

A dark powder was obtained (2.6 grams) containing (1- (dimethylaminoethyl) -2-methyl-indenyl) titanium dichloride.

Example IV

A. Preparation 1- (dimethylaminoethyl) -3-methyl-indene

The preparation was carried out as in Example II but now with 3-methyl-indene (3.9 g; 30 mmol), 18.5 mL of a 1.6 molar solution of n-butyl lithium in hexane and 2- (dimethylaminoethyl) tosylate (30 mmol).

4.83 grams (82%) of 1- (dimethylaminoethyl) -3-methyl-indene were obtained.

b. Synthesis of (1-fdimethylaminoethyl-3-methyl-indenyl) titanium dichloride

The synthesis was performed as in Example II

but now with 1- (dimethylaminoethyl) -3-methyl-indene (0.98 grams, 5 mmol), 3.1 mL of a 1.6 molar solution of n-butyl lithium in hexane and 1.86 grams of TiCl3.3THF.

A dark powder was obtained (1.8 grams) containing 25 (1- (dimethylaminoethyl) -3-methyl-indenyl) titanium dichloride.

Comparative Experiment

Attempt to prepare (indenyl) titanium dichloride. The compound (indenyl) titanium trichloride was synthesized according to a procedure published in the open literature (Macromolecules 1993, 26, 5822-3). Then it was attempted to reduce this compound with zinc; however, this did not lead to the desired connection. An attempt to directly synthesize (indenyl) titanium dichloride, analogous to Example II with 0.93 grams of indene (8 mmol), 5 mL of 1.6 molar 1003010 - 12 - butyl lithium in hexane solution and 2.97 grams of TiCl3.3THF (8 mmol) ) yielded 2.8 grams of dark material, which could not be satisfactorily analyzed. It contains little to no (indenyl) titanium dichloride.

5

Examples V-VII

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.

25 ml of the alkane mixture as a solvent was dosed into a 100 ml catalyst dosing vessel. 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 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.

Can be varied: 1003018 - 13 -. i - metal complex - type and amount of scavenger - type and amount of cocatalyst - temperature. The catalysts obtained in Examples II - IV were used in the polymerization experiments V - VIII. For comparison, the compound obtained in Example A at the same temperatures was used in polymerization experiment B.

10

The current conditions are always stated in Table I.

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Claims (10)

1. Substituted indene compound of which at least one substituent has the form -RDR'n, wherein R is a linking group between the indene 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 R' groups attached to D. A compound according to claim 1, wherein the R group has the structure (-ER32-) p 15 wherein p ** 1-4, E is an element of group 14 or 15 of the Periodic Table and wherein the R3 groups are each separately H or a hydrocarbon radical. A compound according to claim 1 or 2, 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 D is nitrogen. Metal complex in which a compound according to any one of claims 1-4 is present as a ligand. Metal complex according to claim 5, wherein the metal 25 is present in a condition other than the highest valency. A metal complex according to claim 5 or 6, wherein the metal is a Group 5 or 6 transition metal of the Periodic Table or a lanthanide. A metal complex according to claim 7, wherein the transition metal is selected from the group consisting of Ti, Hf, Zr and V. Use of a metal complex according to any one of claims 5-8 as a catalyst. Use according to claim 9 for polymerizing α-olefins. 1003012 COOPERATION TREATY (PCT) --- REPORT ON NEWNESS RESEARCH OF INTERNATIONAL TYPE 0 LIFE APPLICATION NATIONAL APPLICATION Kennwrfc of the applicant ol van d # gamaenogd # _____8678NL________ Nadananosa application no tndienngsoatom 1003018. 3 May 1996 Invited priority application Applicant (Name) DSM NV Daum of wet request for an investigation of ntemaionaai type By ee insanae for Iniemaionaai Investigation (ISA) to the request conducted an investigation of ramaaonal type assigned nr. 3 May 1996 SN 27505 NL I. CLASSIFICATION OF THE SUBJECT (with a patong of veracMe daas * ca eat. All the dassificade cymboes statement) Follow imemaeonaie ctasaAcaee (IRC) Int. Cl. 6: C 07 C 211/30, C 07 F 7/28, C 08 F 10/00, C 07 F 9/50, C 07 F 17/00 II. FIELDS OF TECHNIQUE EXAMINED _ _ Unsolicited Minimum Documentation_ Classification System Classification VM Boats _ Int. Cl.6 C 07 C, C 07 F, C 08 F Undocumented documentation other than a documentation, insofar as such documentation has been included in the survey. III.! X i NO EXAMINATION FOR CERTAIN CONCLUSIONS (comments on supplementary sheet) j IV. LACK OF UNIT OF INVENTION (remarks on supplement sheet) '\ = crn PC7 / lSA, 20lia' CE 199 ^ I ^