NL1003006C2 - Cyclopentadiene compound substituted with branched alkyl groups. - Google Patents

Description

- 1 -

BRANCHED ALKYL GROUPS SUBSTITUTED CYCLOPENTADIENE COMPOUND

The invention relates to a multi-substituted cyclopentadiene compound

Cyclopentadiene compounds, both substituted and unsubstituted, are widely used as a starting material for the production of ligands in metal complexes with catalytic activity.

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

In the vast majority of cases, either unsubstituted or one to five methyl groups substituted cyclopentadiene is used. These metal complexes are often synthesized in polar solvents, of which ethers, including tetrahydrofuran, THF are known examples.

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 compound is that the solubility of a metal complex in which the known Cp compound is present as a ligand in polar solvents is moderate, which complicates the production of metal complexes with the substituted Cp compounds.

1003006 - 2 -

The object of the invention is to provide substituted Cp compounds, the said metal complexes of which have an improved solubility in polar solvents.

This object is achieved according to the invention in that at least two of the substituents are branched C 5, C 1 or C 7 alkyl groups.

The presence of at least two such branched alkyl groups in place of hydrogen or methyl groups appears to bring about improved solubility in polar solvents. In general, compounds are supplied with larger hydrocarbons, including the branched alkyl groups, to improve their solubility in non-polar solvents.

The branched alkyl groups can be the same or different. Particularly suitable branched alkyl groups are, for example, 2-pentyl, 2-hexyl, 2-heptyl, 3-pentyl, 3-hexyl, 3-heptyl, 2- (3-methylbutyl), 2- (3-methylpentyl), 2- ( 4-methylpentyl), 3- (2-methylpentyl), 2- (3,3-dimethylbutyl), 2- (3-ethylpentyl), 2- (3-methylhexyl), 2- (4-methylhexyl), 2- ( 5-methylhexyl), 2- (3,3-dimethylpentyl), 2- (4,4-dimethylpentyl), 3- (4-methylhexyl), 3- (5-methylhexyl), 25- (2,4-dimethylpentyl) ), 3- (2-methylhexyl), 3- (4,4-dimethylpentyl), 1- (2-ethylbutyl), 1- (2-methyl-3-chloropropyl), 2- (1-chloropropyl), 1- (3-methylbutyl), 4- (2-methylbutenyl), 1- (2-methylpropyl), 1- (2-ethylbutyl), 1- (3-chloro-2-methylpropyl), 2- (1-30 chlorpropyl), 1- (2-methylbutenyl) and 1- (2-methylpropyl). Preferably, the Cp compound of the invention contains 2, 3 or 4 branched alkyl groups as substituents. These branched alkyl groups do not contain a heteroatom.

In addition to these branched alkyl groups, which do not contain a heteroatom, the presence of which is required in the context of the invention, the Cp compound 1003006-3 can also contain other substituents. Examples thereof are alkyl groups, both linear and branched and cyclic, alkenyl and aralkyl groups. In addition to carbon and hydrogen, one or more heteroatoms from the groups 14-17 of the periodic Table may also be present, for example 0, N, Si or F, in which a heteroatom is not directly bound to the Cp. Examples of suitable groups are methyl, ethyl, (iso) propyl, secondary butyl, pentyl, -10 hexyl and octyl, (tertiary) butyl and higher homologues, cyclohexyl, benzyl.

The Cp compound can also be a heterocyclopentadiene compound. Here and hereafter, a heterocyclopentadiene compound is understood to mean a compound derived from cyclopentadiene, but in which at least one of the C atoms in its 5-ring is replaced by a heteroatom, wherein the heteroatom can be selected from group 14 , 15 or 16 of the Periodic System of 20 Elements. If there is more than one heteroatom in the 5-ring, these heteroatoms 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 substituting compound in a mixture of the Cp compound and an aqueous solution of a base in the presence of a phase transfer catalyst.

Cp compounds are here understood to mean Cp itself and Cp already substituted 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 monosubstituted or multiply substituted, but also one or several times substituted Cp-derived compounds can be further substituted, whereby also 10:> 6 - 4 - ring closure is possible. belongs.

It is preferred to work with almost equivalent amounts of the halogenated substituents. 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 groups, as a rule only three-substituted Cp compounds can be obtained, with primary and secondary groups generally four and often even five-fold substituted.

With this method it is thus possible to obtain Cp-compounds substituted two, three, four or five times with the desired linear alkyl and optionally substituted with other groups at other positions. 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 is found to suffice and a higher yield of the target compound is found to be obtained.

It is also possible with this method to obtain Cp compounds substituted with specific combinations of substituents without intermediate separation or purification. For example, a two-fold substitution can be carried out first using a certain halide and in the same reaction mixture a third substitution with another substituent by adding a second, different halide to the mixture after some time. This can be repeated 1003006-5 so that it is also possible to manufacture Cp derivatives with three or more different substituents.

The substitution takes place in a mixture of the Cp compound and an aqueous solution of a base. The concentration of the base in the solution is between 20 and 80%. Hydroxides of an alkali metal, for example K or Na, are very suitable. The base is present in an amount of 5-60 moles, preferably 6-30 moles, per mole of Cp compound. It has been found that a significant reduction in 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 temperature at which the reaction takes place can vary between wide limits, for example from -20 to 120 ° C, preferably between 10 and 50 eC. Starting the reaction at room temperature is usually a suitable step, after which the temperature of the reaction mixture can rise due to the heat released during the reactions that occur.

The substitution takes place in the presence of a phase transfer catalyst capable of transferring OH ions from the aqueous phase to the Cp- and halide-containing organic phase, which react there with an H-atom which can be split off from the Cp-compound 30 . As the phase transfer catalyst, quaternary ammonium, phosphonium, arsonium, antimony, bismuthonium, and tertiary sulfonium salts can be used. More preferably, ammonium and phosphonium salts are used, for example tricaprylmethyl ammonium chloride, commercially available under the name Aliquat 336 (Fluka AG, Switzerland? General Mills Co., USA) and 1003006-6.

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, iodide, hydrogen sulfate or hydroxonium hydroxide and cetyl trimide or chloride, benzyltributyl, tetra-n-pentyl, tetra-n-hexyl and trioctylpropyl ammonium chlorides and bromides are also suitable. Useful phosphonium salts are, for example, tributyl hexadecyl phosphonium bromide, ethyl triphenyl phosphonium bromide, tetraphenyl phosphonium chloride, benzyl triphenyl phosphonium iodide, and tetrabutyl phosphonium chloride. Crown ethers and crypt teeth can also be used as phase transfer catalyst, for example 15-crown-5, 18-crown-6, dibenzo-18-crown-6, dicyclohexano-18-crown-6, 4,7,13,16,21- pentaoxa-1,10-diazabicyclo [8.8.5] tr icosane (Kryptofix 221), 4,7,13,18-tetraoxa-1,1,10-diazabicyclo [8.5.5] eicosane (Kryptofix 211) and 4.7, 13,16,21,24-hexaoxa-1, 10-diazabicyclo (8.8.8) -hexacosane (“[2.2.2]”) and its benzo derivative Kryptofix 222 B. Polyethers such as ethylene glycol ethers can also be used as phase transfer catalyst. Quaternary ammonium salts, phosphonium salts, phosphoric acid triamides, crown ethers, polyethers and crypt teeth can also be used on a support, such as, for example, on a geeross-inked polystyrene or other polymer. The phase transfer catalysts are used in an amount of 0.01-2, preferably 0.05-1 equivalent to the amount

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. 1003006-7 is then recovered from the organic asse by fractional distillation.

By this method, two, three, four fivefold Cp compounds substituted with the desired branched alkyl 5 can be obtained.

The substituted Cp compounds of the invention and other second Cp compound substituted with at least two branched alkyl groups are particularly suitable as a ligand in a metal complex and the invention therefore also relates to the use of an at least two branched alkyl groups substituted cyclopentadiene compound for manufacturing a metal complex in a polar solvent. These metal complexes have better thermal stability than complexes with Cp ligands to which no branched groups are substituted. Also, when further substituting these Cp compounds, less geminal substitution occurs, which is advantageous if one wishes to further incorporate substituted Cp compound into a metal complex.

Metal complexes that are catalytically active when one of their ligands is a compound of the invention are complexes of metals from groups 4-10 of the Periodic System and rare earths. Group 4 and 5 metal complexes are preferably used as a catalyst component for the polymerization of olefins, group 6 and 7 metal complexes, in addition also for metathesis 30 and ring-opening metathesis polymerisations 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.

1003006 - 8 -

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

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

The synthesis of metal complexes with the specific Cp compounds described above as a ligand in polar and other types of solvents 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 combination 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. As a co-catalyst, a 1003006-9 organometallic compound is usually used, the metal being selected from Group 1, 2, 12 or 13 of the Periodic Table of the Elements. Mention may be made, for example, of trialkylaluminum, alkylaluminum-5-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. Applied pressures are between generally between atmospheric pressure and 250 HPa for bulk polymerizations more in particular between 50 and 250 Mpa, for the other polymerization processes between 0.5 and 25 MPa. and solvents, for example, hydrocarbons can be used as pentane, heptane and mixtures thereof, aromatic, optionally perfluorinated hydrocarbons may also be used, and the monomer to be used in the polymerization can also be used as a dispersing or solvent.

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

The following analysis methods are used in the characterization of the products obtained. Gas chromatography (GC) was performed on a Hewlett-Packard 5890 Series II with an HP Crosslinked Methyl Silicon Gum (25mx0.32mmx1.05pm) column. Combined Gas Chromatography / Mass Spectrometry (GC-MS) was performed with a Fisons MD800 equipped with a quadrupole mass detector, autoinjector Fisons AS800 and CPSil8 column (30mx0.25mmxlf / m, low bleed).

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

1003006 - 10 -

Example I

Preparation of di (cclohexvl) cvclopentadiene

A 1 L double-walled reactor equipped with baffles, cooler, overhead stirrer, thermometer and dropping funnel was charged with 600 g of clear 50% NaOH (7.5 mol) and cooled to 8 ° C. Then 20 g of Aliguat 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% of 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, GC-MS, 13C and 1H NMR.

20

Example II

Preparation of di- and tri (3-pentyl-cyclopentadiene)

A 1 L double-walled reactor equipped with baffles, cooler, overhead stirrer, thermometer and dropping funnel was charged with 430 g (5.4 mol) of clear 50% NaOH. Then 23 g of Aliguat 336 (57 mmol) and 27 g (0.41 mol) of freshly cracked cyclopentadiene were added. The reaction mixture was stirred turbulently for several minutes, then 150 g of 3-pentyl bromide (1.0 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 70 ° C and stirred for another 3 hours. Stirring was stopped and phase 35 separation was awaited. The water layer was drained and 540 g (6.70 mol) of fresh 50% NaOH were added. Stirring was then continued at 70 ° C for 4 hours. GC showed that 1003006-11 at that time the mixture consisted of di- and tri (3-pentyl) cyclopentadiene (about 3: 2). The products were distilled at 0.2 mbar, 51 * C and 0.2 mbar, 77-80 * C, respectively. After distillation, 32 g of di- and 18 g of tri (3-pentyl) cyclopentadiene were obtained. The characterization was done by GC, GC-MS, 13C and 1 H NMR.

Example III

Preparation of Triflclohexyllloplopadadiene

A 1 L double-walled reactor equipped with baffles, cooler, overhead stirrer, thermometer and dropping funnel was charged with 600 g of clear 50% NaOH (7.5 mol) and cooled to 8 ° C. Then 20 g of Aliguat 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 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, followed by stirring 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. Then 25 was stirred for another 4 hours at 70 ° C. 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. C. After distillation, 87.4 g of tri (cyclohexyl) cyclopentadiene 30 were obtained. The characterization was done by GC, GC-MS, 13C and 1H NMR.

Example IV

Preparation of di- and tri (2-pentyl) cyclopentadiene 35 A 1 L double-walled reactor equipped with baffles, cooler, overhead stirrer, thermometer and dropping funnel was filled with 900 g 1003006 - 12 - (11.25 mol) clear 50% NaOH. Then 31 g of Aliquat 336 (77 mmol) and 26.8 g (0.41 mol) of freshly cracked cyclopentadiene were added. The reaction mixture was stirred turbulently for a few minutes, then 5 155 g of 2-pentyl bromide (1.03 mol) was added over an hour.

It was cooled with water. After stirring at room temperature for 3 hours, the reaction mixture was heated to 70 ° C, followed by stirring for another 2 hours. Stirring was stopped and phase 10 separation was awaited. The water layer was drained and 900 g (11.25 mol) of fresh 50% NaOH were added. Stirring was then continued for 2 hours at 70 ° C. GC showed that at that time the mixture consisted of di- and tri (2-pentyl) cyclopentadiene (about 1: 1). The 15 products were distilled at 2 mbar, 79-81 * C and 0.5 mbar, 102 ° C, respectively. After distillation, 28 g of di- and 40 g of tri (2-pentyl) cyclopentadiene were obtained.

The characterization was done by GC, GC-20 MS, 13C and -NMR.

Example V

Preparation of di (2-propyl-cyclohexyl-cyclopentadiene)

150 g of clear 50% NaOH (1.9 mol), 7 g of Aliquat 336 (17.3 mmol) and 8.5 g (0.13 mol) were placed in a 200 ml double-walled reactor with a baffles, cooler, overhead stirrer, thermometer and dropping funnel. freshly cracked cyclopentadiene combined. The reaction mixture was stirred turbulently for a few minutes at a speed of 1385 rpm. Then 31.5 g of 2-propyl bromide (0.26 mol) was added. It was cooled with water. The total dosing time was 1 hour. After adding the bromide, the reaction mixture was heated to 50 C. C. After 2 hours, stirring was stopped and phase separation was awaited. The water layer was drained and 150 g (1.9 mol) of fresh 50% NaOH were added. Then 20.9 g (0.13 mole) of 1003 O3-13-cyclohexyl bromide was added, followed by stirring at 70 ° C for an additional 3 hours. GC showed that 80% di (2-propyl) cyclohexylcyclopentadiene was present in the mixture at that time. The product was distilled at 0.3 mbar and 80 C. C. After distillation, 17.8 g of di (2-propyl) cyclohexyl cyclopentadiene were obtained.

Characterization was done by GC, GC-MS, 13C and 1 H NMR.

10 1 o o: o o e

Claims (4)

1. Poly-substituted cyclopentadiene compound, characterized in that at least two substituents are branched C 5, C 6 or C 7 alkyl groups, with the exception of di and tricyclohexyl cyclopentadiene. 2. Use of substituted cyclopentadiene compound according to claim 1 for the manufacture of a metal complex in a polar solvent. Metal complex containing at least one with substituted cyclopentadiene compound according to claim 1 as a ligand. Use of a metal complex in which at least one substituted cyclopentadiene compound, in which at least two substituents are branched alkyl groups, is present as a ligand, as a catalyst component in the polymerization of α-olefins. 10 0 3 CO 6 SAMENWbHKiNtaijVtHUHAU (Kt- '.) REPORT ON NEWNESS RESEARCH OF INTERNATIONAL TYPE \ IDENTIFICATION OF OE NATIONAL £ APPLICATION Characteristic of cm applicant or of the gemacnsgoa 8644 NL Neoerianese application hr. ) DSM NV Oaten of the request for an investigation of maaaaaaaiai type Ooor de marante voor tnramatenaai Research (ISA) arat just request for a study of inramatorial type acc. SN 27493 EN L CLASSIFICATION OF THE SUBJECT (with the name of veraeidlanoe dattEcaee ». All the dasaificaoeymboia provided c According to o mramatonaie eraisriicate (IPC) Int. Cl. 6: C 07 C 13/15, C 07 F 17/00, C 08 F 10 / 00 II. RESEARCHED FIELDS OF TECHNIQUE Onaerzocftf minimum documentation I Classification system Classification vmoolen ~ I Int Cl.6 C 07 C, C 08 F Ono # rzocm · inoen eoofnvniiM dtn o · ff) r * mum doojminetii insofar as oerjiijki docummefl w \ the prayers examined sentence included M · '^ 1 NO EXAMINATION MAY BE FOR CERTAIN CONCLUSIONS (comments onututlingsofad) IV. 1 LACK OF UNIT OF INVENTION (oomenanoen oo supplementolad) I '5 ^ 1 -orm PC7 / ISA / Z0liaiC £ 19Si