JP2000510117A - Cyclopentadiene compounds substituted with branched alkyl groups - Google Patents

Abstract

(57) Abstract: In a polysubstituted cyclopentadiene compound, at least one substituent has a formula —RDR ′ _n (where R is a bonding group, and D is a group 15 or A heteroatom selected from group 16; R ′ is a substituent; and n is the number of R ′ groups attached to D) and at least one further substituent Is a branched alkyl group. A metal complex in which at least one of these cyclopentadiene compounds exists as a ligand is useful as an α-olefin polymerization catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION   Cyclopentadiene compounds substituted with branched alkyl groups   The present invention relates to a polysubstituted cyclopentadiene compound.   Cyclopentadiene compounds are usually used as catalyst components, especially for the polymerization of olefins. Used as ligand in metal complexes that are active as a moiety.   J. of Organomet. Chem., No. 479 (1994), pp. 1-29, in metal complexes. An overview of the effect of substituents on cyclopentadiene as a ligand is provided. On the other hand, the chemical and physical properties of metal complexes depend on the specific position on the cyclopentadiene ring. It has now been observed that it can be varied over a wide range by the choice of substituents. On the other hand, it is not possible to predict the expected effect of a particular substituent. It is stated. Depending on the metal, its valence state and the ligand used, The complexes appear to have varying suitability for particular applications. Polyolefin Polymerization often involves the use of one or more α-olefins, such as ethene or propene. Other vinyl monomers containing the above other olefins and / or vinyl aromatic monomers Is to copolymerize with Most frequently used cyclopentadiene compounds Is an unsubstituted cyclopentadiene or a cyclopentadiene substituted with 1 to 5 methyl groups. It is ntadien. However, metal complexes And especially above where the metal is not in the highest valence state Metal complex (therefore the metal is, for example, Ti (III), Hf (III), Zr (III) or V (IV) These cyclopentadiene compounds when used as ligands in When used as a catalyst compound for olefin polymerization, the molecular weight and comonomers To provide a catalyst component for the production of copolymers with disadvantageous combinations of You can see that it is offered. This favors the production of higher molecular weight copolymers. Polymerization under certain conditions results in polymers with relatively low comonomer incorporation Means to do that. In addition, J. of Organomet. Overview at Chem. The article further states, "An important feature of these catalyst systems is that the tetravalent Ti center is Is required. " In this regard, Ti Metals Suitable as Metals in Clopentadienyl-Substituted Metal Complexes It should be noted that this is an example of   In the following, cyclopentadiene will be abbreviated as Cp. The same omission , Which means either cyclopentadiene itself or its anion, from the context If clear, it would be used for the cyclopentadienyl group.   The predicate olefin is used herein and hereinafter to refer to α-olefins, diolefins and And other unsaturated monomers. If the predicate "polymerization of olefins" is not used This is below Wherein the polymerization of a single type of olefinic monomer and one or more Olefin copolymerization.   An object of the present invention is to provide a metal complex in which the metal is not in the highest valence state. When used as a ligand, more preferred is the incorporation of molecular weight and comonomer Given a catalyst that can be used to produce copolymers with combinations It is to provide a Cp compound at this time.   For this purpose, at least one substituent is of the formula   -RDR '_n (Where R is the linking group between the Cp and DR 'groups and D is group 15 of the periodic table Or a heteroatom selected from Group 16; R 'is a substituent; and n is Is the number of R 'groups attached to D) And at least one further substituent is a branched alkyl group This is achieved according to the invention.   Surprisingly, when used as a ligand in the above metal complexes, this The substituted Cp compound is used as a catalyst component for the polymerization of olefins. When compared with known compounds, ethene having the same molecular weight is Providing a catalytic component in producing copolymers with higher incorporation of nomers You can see that Preferably, the compound has at least two branched radicals as substituents. It contains an alkyl group. This is because this is the ratio between molecular weight and comonomer incorporation. Because it brings further improvement in is there.   Corresponding complexes where the Cp compound is not substituted in the disclosed manner are unstable , Or if they were stabilized in some other way, In particular, in the case of the polymerization of α-olefins, the substituted Cp compounds according to the invention are included. It can be seen that this gives a catalyst having lower activity than the complex.   Furthermore, the Cp compounds according to the invention can be used as reactive intermediates, for example organometallic hydrides. , Organometallic borohydride, organometallic alkyl and organometallic cation It can be seen that it can be stabilized. Further, the metal complex containing the Cp compound according to the present invention may be a gold complex. Suitable as a stable and volatile precursor for use in genus chemical vapor deposition I understand.   J. of Organomet. Chem., 486 (1995), pp. 287-289, shows the fifth substitution. Discloses tetramethylcyclopentadiene having ethyldimethylamine as a group ing. This publication has improved upon the copolymerization of olefins as catalyst components. As ligands in metal complexes that result in the incorporation of comonomers No suitability of the following Cp compound is given or suggested. This This is especially true for this effect involving complexes of metals where they are not in the highest valence state. Aimed more powerfully.   In fact, the Cp compounds according to the invention are also, in fact, their highest Can be used as ligands in metals in different valence states.   The branched alkyl groups can be the same or different. Preferably, the substitution The resulting Cp compound contains from 1 to 4 branched alkyl groups as substituents. Branched alkyl As the number of substituents in the form of the group increases, so substituted Cp compounds are distributed. The activity of the metal complex, which exists as a ligand, is It can be seen that it increases when used as a catalyst component. A branched alkyl group is a periodic Does not include any heteroatoms from Group 16 of the Table. Particularly suitable branched alkyl groups Is, for example, 2-propyl, 2-butyl, 2-pentyl, 2-hexyl, 2-heptyl, 2- Octyl, 2-nonyl, 2-decyl, 3-pentyl, 3-hexyl, 3-heptyl, 3-octyl Tyl, 3-nonyl, 3-decyl, 3-undecyl, 3-dodecyl, 2- (3-methylbutyl), 2- (3-methylpentyl), 2- (4-methylpentyl), 3- (2-methylpentyl), 2- (3,3 -Dimethylbutyl), 2- (3-ethylpentyl), 2- (3-methylhexyl), 2- (4-methyl Ruhexyl), 2- (5-methylhexyl), 2- (3,3-dimethylpentyl), 2- (4,4-dimethyl Tylpentyl), 3- (4-methylhexyl), 3- (5-methylhexyl), 3- (2,4-dimethyl Rupentyl), 3- (2-methylhexyl), 3- (4,4-dimethylpentyl), 1- (2-ethyl Butyl), 1- (2-methyl-3-chloropropyl), 2- (1-chloropropyl), 1- (3-methyl Butyl), 4- (2-methylbutenyl), 1- (2-methylpropyl), 1- (2-ethylbutyl ), 1- (3-chloro-2-methylpropyl), 2- (1-chloropropyl), 1- (2-methylbute Enyl), 1- (2-methylpropyl), cyclopentyl and cyclohexyl. Minute Cp compounds di- or tri-substituted by a branched alkyl group are preferred.   These branched alkyls whose presence is required within the scope of the invention In addition to the groups, further substituents such as linear alkyl groups, alkenyl and aralkyl A radical may also be present. In addition to carbon and hydrogen, from groups 14-17 of the periodic table Include one or more heteroatoms, such as O, N, Si or F It is also possible for them. Examples of suitable groups are methyl, ethyl, n-butyl, n-pentyl, n-hexyl and n-octyl, benzyl, phenyl, p-tolyl and Limethylsilyl.   For the Periodic Rule, Handbook of Chemistry and Physics, 70th Edition, 1989/1990 See the new IUPAC notation found inside the year cover.   The substituted Cp compound is, for example, a Cp compound and a base in the presence of a phase transfer catalyst. By reacting the halide of the compound to be replaced in a mixture of aqueous solutions Can be prepared.   The predicate Cp compound refers to Cp itself and Cp already substituted at positions 1-3, Optionally two substituents may form a closed ring. By the method according to the invention, namely: Unsubstituted compounds can be converted to single or multiple substituted compounds, but Cp It is also possible that the mono- or polysubstituted compounds derived therefrom can be further substituted. Yes, and additionally, ring closure is optionally selected. Halogenation of Cp compounds Substantially equivalent amounts of the substituted compounds used can be used. The equivalent is the desired permutation multiplex Is understood as the molar amount corresponding to the degree, for example, if If substitution is intended, it is understood to be 2 moles per mole of Cp compound.   Depending on the size of the compound to be substituted and the associated steric hindrance, tri- to penta-substitution The obtained Cp compound can be obtained. If the compound is substituted with a tertiary halide If the product reaction is carried out, it is generally possible to obtain only trisubstituted Cp compounds. Yes, but to the contrary, the compounds that replace primary and secondary halides In general, tetra- and often even penta-substitution can be achieved.   Particularly suitable branched alkyl substituents have already been detailed above. this The number of substituents introduced as above is still in a free position as defined above Is 1 to 4 for Cp compounds according to the invention, in addition to other groups to be substituted.   Substituents are preferably used in the process in their halide form, and And more preferably in the form of its bromide. If bromide is used If a smaller amount of phase transfer catalyst is found to be sufficient, It is found that higher yields of the compound are obtained.   In this way, a particular combination of substituents can be used without isolation or purification of the intermediate. It is also possible to obtain Cp compounds that are substituted. So, for example, Disubstitution with some halide, the compound to be replaced, is performed first And, in the same reaction mixture, a third displacement occurs after some time By adding a second, different, halide to the mixture as a displacing compound. And may be implemented by different substituents. This can be repeated, Thus, it is also possible to prepare Cp derivatives with three or more different substituents. It is possible.   The substitution occurs in a mixture of an aqueous solution of the Cp compound and the base. Concentration of the base in the solution The degree ranges from 20 to 80% by weight. Hydroxides of alkali metals, for example K or Na But are very suitable as bases. The base is 5 to 60 moles per mole of the Cp compound, Preferably it is present in 6 to 30 molar amounts. If a solution of a base, for example, Firstly mixed with the other components of the reaction mixture, and after some time the aqueous phase is separated off, and It is refreshed again during the reaction by replacing it with a fresh amount of a solution of the base. It has been found that the reaction time can be considerably shortened if it is done. The substitution is, inter alia, When volatile components are present, at atmospheric or elevated pressure, e.g. up to 100 MPa Be done. The temperature at which the reaction takes place is in a wide range, for example, -20 to 120 ° C, preferably It can be varied at 10-50 ° C. It is usually appropriate to start the reaction at room temperature, Thereafter, the temperature of the reaction mixture is increased as a result of the heat released during the course of the resulting reaction. Can rise.   Substitution transfers OH ions from the aqueous phase to the organic phase containing Cp compounds and halides. In the presence of a phase transfer catalyst, where the OH ion is converted to a Cp compound. Minutes from things Reacted in the organic phase with H-atoms that can be cleaved. Phase transfer contacts that can be used The medium is quaternary ammonium, phosphonium, arsonium, stibonium, bis Masonium and tertiary sulfonium salts. More preferably, ammonium And phosphonium salts, for example, the trademark Aliquat 336 (Fluka AG, Switzerland; General  Mills Co., USA) and Adogen 464 (Aldrich Chemical Co., USA) Tricaprylmethylammonium chloride marketed under the United States It is. Benzyltriethylammonium chloride (TEBA) or benzyltriethyl bromide Ammonium (TEBA-Br), benzyltrimethylammonium chloride, benzyl bromide Trimethylammonium or benzyltrimethylammonium hydroxide (Triton B) , Tetra-n-butylammonium chloride, tetra-n-butylammonium bromide , Tetra-n-butylammonium iodide, tetra-n-butylammonium hydrogen sulfate Or tetra-n-butylammonium hydroxide and cetyltrimethyl bromide Ammonium or cetyltrimethylammonium chloride, benzyltributyl-, Tora-n-pentyl-, tetra-n-hexyl- and trioctylpropyl chloride Compounds such as ammonium and their bromides are also suitable. Can use Phosphonium salts include, for example, tributylhexadecylphosphonium bromide, Ethyltriphenylphosphonium, tetraphenylphosphonium chloride, Including benzyltriphenylphosphonium and tetrabutylphosphonium chloride. Crown ethers and cryptands, for example, 15-crown-5, 18-crown-6, Dibenzo-18-crown-6, dicyclohexano-18-crown-6, 4,7,13,16,21-pe Nantaoxa-1,10-diazabicyclo [8.8.5] tricosan (Kryptofix 221), 4,7,13,1 8-tetraoxa-1,10-diazabicyclo [8.5.5] eicosan (Kryptofix 211) and 4 , 7,13,16,21,24-Hexaoxa-1,10-diazabicyclo [8.8.8] -hexacosan ("[ 2.2.2] ”) and its benzo-derived Kryptofix 222 B are also used as phase transfer catalysts Can be done. Polyethers, for example ethers of ethylene glycol, are also It can be used as a kinetic catalyst. Quaternary ammonium salt, phosphonium salt, phosphate Liamides, crown ethers, polyethers and cryptands are also, for example, It can be used on carriers such as cross-linked polystyrene or other polymers. Interphase movement contact The medium is used in 0.01 to 2, preferably 0.05 to 1 equivalent, based on the amount of Cp-compound.   In carrying out the method, the components may be added to the reactor in various orders.   After the reaction is completed, the aqueous phase and the organic phase containing the Cp compound are separated. Necessary The Cp compound is then obtained from the organic phase by fractional distillation.   The Cp compound so substituted is then of the formula -RDR '_nGroup I can.   R groups are Cp and DR '_nConstitute a bond between Shortest bond between Cp and D Is the length of the Cp compound When used as a ligand in_nThe accessibility of the metal to the base This is important because it is determined to achieve the desired intramolecular coordination. R If the group (i.e. the bridge) is too short, due to ring tension, DR '_nGroup effectively It may mean that it cannot coordinate. Therefore, R is small Both have a length of one atom.   The R 'groups are each independently a hydrocarbon residue containing 1-20 carbon atoms (e.g., Alkyl, aryl, aralkyl, etc.). Examples of such hydrocarbon residues Is methyl, ethyl, propyl, butyl, hexyl, decyl, phenyl, benzyl And P-tolyl. R 'can also be in addition to or in place of carbon and / or hydrogen, Substitutions containing one or more heteroatoms from groups 14 to 16 of the periodic table Group. For example, the substituent may be a N, O and / or Si containing group.   The R group is a hydrocarbon group having 1 to 20 carbon atoms (eg, alkylidene, aryl Den, arylalkylidene, etc.). Examples of such groups are substituted Methylene, ethylene, propylene, butylene with or without side chains , Phenylene. Preferably, the R group has the following structure: (-ER^Two _Two−)_p Here, p = 1 to 4, and E represents an atom from Group 14 of the periodic table. R^Two The groups may be groups defined for H or R ', respectively.   Thus, the backbone of the R group may also include silicon or germanium in addition to carbon. . Examples of such R groups are dialkylsilylene, dialkylgermylene, tetra -Alkyldisilylene or dialkylsilaethylene (-(CH_Two) (SiR^Two _Two) −). The alkyl group (R^Two) Is preferably 1 to 4 charcoals And a methyl or ethyl group.   DR ’_nThe group is linked to a heteroatom D and D selected from groups 15 or 16 of the periodic table. Consisting of one or more substituents R 'combined. The number (n) of R 'groups is Is n = 2 if is a group 15 and n = 1 if D is a group 16 In some sense it is associated with the type of heteroatom D. Preferably, Heteroatom D consists of nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S) Selected from the group, more preferably the heteroatom is nitrogen (N) or phosphorus (P). You. Also, the R 'group is preferably alkyl, more preferably 1-20 carbon atoms. N-alkyl group. More preferably, the R 'group contains 1 to 10 carbon atoms. N-alkyl. DR ’_nTwo R 'groups in a group are linked together to form (D R '_nIt is also possible to provide a ring-shaped structure (such that the group can be a pyrrolidinyl group). Noh. DR ’_nThe group can be coordinated to the metal.   For the purpose of preparing such Cp compounds, as described above, Is then substituted, for example, via a synthetic route of the formula -RDR '_nBase Replace with Can be done.   During the first step of this pathway, the substituted Cp compound may be a base, sodium or potassium. Deprotonated by reaction with lithium.   Bases that can be used are, for example, organolithium compounds (R^ThreeLi) or organic mug Nesium compounds (R^ThreeMgX), where R^ThreeIs alkyl, aryl or An aralkyl group and X is a halide, for example, n-butyllithium or i-Propyl magnesium chloride. Potassium hydride, sodium hydrogen Chlorides, inorganic bases such as NaOH and KOH, and alcoholates of Li, K and Na are also , As a base. Mixtures of the above compounds may also be used.   The reaction can be performed in a polar dispersion such as, for example, an ether. Appropriate Examples of suitable ethers are tetrahydrofuran (THF) or dibutyl ether . For example, a non-polar solvent such as toluene may also be used.   Next, during the second stage of the synthetic route, the cyclopentadienyl anion formed Is the formula (R ′)_nDRY) or a compound according to (XR-Sul) It is. Here, D, R, R 'and n are as defined above. Y Is a halogen atom (X) or a sulfonyl group (Sul). Halo to be mentioned Gen atoms (X) are chlorine, bromine and iodine. Preferably, the halogen atom X is , A chlorine atom or a bromine atom. The sulfonyl group has the formula -OSO_TwoR⁶ , Where R⁶Is a hydrocarbon residue containing 1 to 20 carbon atoms, e.g. Kill, aryl and alkaryl. An example of such a hydrocarbon residue is butane , Pentane, hexane, benzene and naphthalene. Carbon and / or hydrogen Alternatively or additionally, R⁶Is also one or more members from groups 14-17 of the periodic table , For example, N, O, Si or F. Examples of sulfonyl groups are Phenylmethanesulfonyl, benzenesulfonyl, 1-butanesulfonyl, 2, 5-dichlorobenzenesulfonyl, 5-dimethylamino-1-naphthalenesulfo Nil, pentafluorobenzenesulfonyl, p-toluenesulfonyl, trichloro Romethanesulfonyl, trifluoromethanesulfonyl, 2,4,6-triisoprop Propylbenzenesulfonyl, 2,4,6-trimethylbenzenesulfonyl, 2- Mesitylenesulfonyl, methanesulfonyl, 4-methoxybenzenesulfonyl, 1-naphthalenesulfonyl, 2-naphthalenesulfonyl, ethanesulfonyl, 4 -Fluorobenzenesulfonyl and 1-hexadecanesulfonyl. Preferred Alternatively, the sulfonyl group may be p-toluenesulfonyl or trifluoromethanesulfonyl. Nil.   If D is a nitrogen atom and Y is a sulfonyl group, the formula (R ′)_nD- The compound according to RY) is an amino alcohol compound (R ′)_Two(NR-OH) Reaction with a base, potassium or sodium, as defined in Reaction with sulfonyl genoide (Sul-X) And formed on the spot.   The second reaction step is also carried out in a polar dispersant as described for the first step. Can be done. The temperature at which the reaction is carried out is between -60 and 80C. XR-Sul and R ’_nThe reaction with DRY is usually carried out at a temperature of -20 to 20 ° C. Where Y is B r or I. R '_nReaction with DRY is usually at higher temperatures (10-80 ° C) Executed in Here, Y is Cl. Upper temperature limit at which the reaction is performed Is, inter alia, a compound R '_nDepending on the boiling point of DRY and the solvent used Is determined.   After reaction with a compound according to formula (XR-Sul), a further reaction is carried out with DR '_nGovernment LiDR 'to replace X by performance_nOr HDR '_nIs executed by To that end, the reaction is carried out at 20-80 ° C., possibly in the same dispersant as indicated above. Be executed.   In the synthesis process according to the invention, the geminal product may be partially formed. You. Geminal substitution increases the number of substituents by one, but increases the number of substituted carbon atoms. A substitution where the number does not increase. If the synthesis is substituted with one substituent Performed starting from the Cp compound that was substituted, and the substituted Cp compound If increased to include groups, the amount of geminal product formed is small. Jee Terminally substituted Cp compounds are not suitable for use as ligands and Are not considered to be within the scope of the present invention. Sterically bulky in substituted Cp compounds Substituent When no is present, no or substantially no geminal product is formed. Three-dimensional Examples of particularly bulky substituents are secondary or tertiary alkyl substituents. If the reaction Is the Lewis base where the conjugate acid has a pKa dissociation constant of -2.5 or less If carried out under the influence of, the amount of geminal product formed is also small. pK a value is D.D.Perrin: Dissociation Constants of Organic Bases in Aqueous Sol ution, International Union of Pure and Applied Chemistry, Butterworths, Lon don Based on 1965. The value is H_TwoSO_FourMeasured in aqueous solution. Ether is appropriate It can be mentioned as an example of a weak Lewis base.   If a geminal product is formed during the process according to the invention, these The products of are geminal and non-diamine by reaction with potassium, sodium or base. The mixture of the eminally substituted product is converted to a salt, which is then converted to a non-gemina Washing with dispersing agents where the product salts are insoluble or only slightly soluble Can be separated in a simple manner from non-geminal products. Bases that can be used are , Including the compounds listed above. Suitable dispersants are non-polar dispersants, for example, Lucan. Examples of suitable alkanes are heptane and hexane.   Metal complexes that are catalytically active, if one of their ligands is If it is a compound that complies, a metal complex from groups 4 to 10 of the periodic table and lanthanides It is. In this connection, metal complexes from Groups 4 and 5 are preferred. Or as a catalyst component for olefin polymerization, in addition to Group 6 and Group Metal complexes from group 7 also provide catalysts for metathesis and ring-opening metathesis polymerization. And the metal complex from groups 8 to 10 is a polar comonomer of an olefin. It is used as a catalyst component for copolymerization with copolymers, hydrogenation and carbonylation. Such a metal complex wherein the metal is selected from the group consisting of Ti, Zr, Hf, V and Cr Are particularly suitable for olefin polymerization.   In particular, if the metal, in particular the five metals listed above, respectively, If not in its highest valence state, the Cp compound can block the active site. Without giving the formed complex excellent stability, so that the catalytic activity is It can be seen that it is higher when other Cp compounds are used. Therefore, the present invention also Wherein at least one ligand is a substituted Cp compound according to the invention, and Or a metal complex where the metal is in a lower valence state than the highest valence state Olefins and other olefins and usually vinyl monomers and especially Use of such metal complexes as catalyst components for copolymerization with vinyl aromatic monomers Related to using.   The vinyl aromatic monomers that are effectively incorporated by these catalysts are Containing styrene, chlorostyrene, n-butylstyrene and p-vinyltoluene; And especially styrene.   Metals containing the above specific Cp compounds as ligands The synthesis of the complexes can be carried out according to methods known per se for that purpose. these The use of Cp compounds does not require any improvement of the known method.   α-olefins such as ethene, propene, butene, hexene, octene and And mixtures thereof as well as the polymerization of the combination with a diene, It can be carried out in the presence of a metal complex containing a lopentadienyl compound. Highest atom Transition metal complexes that are not in a valence state are particularly suitable for this purpose, Wherein only one of the cyclopentadienyl compounds according to the invention is present as a ligand And the metal is cationic during the polymerization. These polymerizations are intended for that purpose Metal complex which can be carried out in a manner known to Use does not require any significant improvement of these methods. Known polymerizations are: Performed in suspension polymerization, solution polymerization, emulsion polymerization, gas phase polymerization or as bulk polymerization You. As the co-catalyst, an organometallic compound is usually used, wherein the metal is a periodic compound. Selected from the first, second, twelfth or thirteenth groups of the table. For example, alkyl aluminum Noxane (eg, methylaluminoxane), tris (pentafluorophenyl) Baud rate, dimethylanilinium tetra (pentafluorophenyl) boray Or mixtures thereof. The polymerization is carried out at -50 to + 350 ° C, more preferably at 25 ° C. Runs at temperatures of ~ 250 ° C. The pressure used is usually between atmospheric pressure and 250 MPa. More preferably 50 to 250 MPa for bulk polymerization, and other polymerization 0.5 to 25MPa for the law. As dispersants and solvents to be used, for example, Including hydrocarbons such as pentane, heptane and mixtures thereof. Aromatic, any Intentionally perfluorinated hydrocarbons are also suitable. Things applied to polymerization Mers can also be used as dispersants or solvents.   The present invention is described with reference to the following non-limiting examples.   The synthesis of the catalyst component is performed by dry Ar or N_TwoMade below.   Characterization of the resulting product involves the following analytical methods.   Gas chromatography (GC) is performed using HP Crosslinked methylsilicon gum (25m × 0. (32 mm × 1.05 μm) column. Was. Combined gas chromatography / mass spectrometry (GC-MS) , Quadrupole mass detector, auto injector Fisons AS800 and CPSil8 color Performed by Fisons MD800 equipped with a system (30m x 0.25mm x 1um, low bleed) . NMR is from Bruker ACP200 (¹H = 200 MHz;¹³C = 50MHz) or Bruker ARX400 (¹ H = 400 MHz;¹³C = 100 MHz). To characterize metal complexes, Kratons MS80 mass spectrometer or Finnigan Mat 4610 mass spectrometer Data was used.   Example I Preparation of di (2-propyl) cyclopentadiene   Baffle, condenser, top stirrer, thermometer and dripping In a double-walled reactor with a volume of 200 ml equipped with a funnel, 180 g (2.25 mol) Clear 50% strength NaOH, 9.5 g (23 mmol) Aliquat 336 and 15 g (0.227 mol ) Freshly decomposed cyclopentadiene was mixed. The reaction mixture is The mixture was vigorously stirred at a speed of 85 rpm. Next, while cooling with water at the same time, 56g (0.46 2-) propyl bromide was added. 2-3 minutes after addition of 2-propyl bromide , The temperature rose to about 10 ° C. Stirring was then continued at 50 ° C. for 6 hours. GC uses As soon as possible, 92% of di (2-propyl) cyclopentadiene is It was shown to be present in a mixture of (2-propyl) cyclopentadiene. The raw The product was distilled at 10 mbar and 70 ° C. After distillation, 25.35 g of di (2-prop G) cyclopentadiene was obtained. Characterization includes GC, GC-MS,¹³C- and¹H-NMR Made byExample II Preparation of tri (2-propyl) cyclopentadiene   200mm with baffle, condenser, top stirrer, thermometer and dropping funnel 180 g (2.25 mol) of clear 50% strength Na in a double-wall reactor with a volume of 1 liter OH, 9.5 g (23 mmol) of Aliquat 336 and 15 g (0.227 mol) of freshly decomposed cyclo Pentadiene has been incorporated. The reaction mixture is intense at a speed of 1385 rpm for 2-3 minutes. Stirred. Next, while simultaneously cooling with water, 84 g (0.68 mol) of 2-propyl Lomid was added. After 2-3 minutes of addition of 2-propyl bromide, The temperature rose to about 10 ° C. GC is used to add the full amount of 2-propyl bromide After about 30 minutes, the formation of (monosubstituted) 2-propylcyclopentadiene I understood. The reaction mixture was then warmed to 50 ° C. After 2 hours, stirring stops And phase separation was awaited. The aqueous layer was withdrawn and 180 g (2.25 mol) Fresh 50% strength NaOH was added. Stirring is then continued for another hour at 50 ° C. Was. GC used immediately 90-95% tri (2-propyl) cyclopentadiene Is present in a mixture of di-, tri- and tetra (2-propyl) cyclopentadiene It was shown to be. The product was distilled at 1.3 mbar and 77-78 ° C. After distillation, 31.9 g of tri (2-propyl) cyclopentadiene were obtained. Characterization Means GC, GC-MS,¹³C- and¹H-NMR was used.   Example III Preparation of tetra (2-propyl) cyclopentadiene   114 g (0.93 mol) of 2-propyl bromide are added and after 7 hours the aqueous layer Was replaced with Example II except that was replaced once more. At the same time, To this was added 5 g (12 mmol) of Aliquat 336. Then heat at 55 ° C for about 16 hours Was done. As soon as the GC is used, 85% of tetra (2-propyl) cyclopentadi Ene is present in a mixture of tri- and tetra (2-propyl) cyclopentadiene Rukoto has been shown. The product was distilled at 1.0 mbar and 88-90 ° C. Steaming After distillation, 34.9 g of tetra (2-p (Ropyl) cyclopentadiene was obtained. Characterization includes GC, GC-MS,¹³C- and¹H -Made by NMR.   Example IV Preparation of di (cyclohexyl) cyclopentadiene   1 liter with baffle, condenser, top stirrer, thermometer and dropping funnel Double wall reactor with 600 g (7.5 mol) of clear 50% strength NaOH. And subsequently cooled to 8 ° C. Then 20 g (49 mmol) of Aliquat 336 and 3 3 g (0.5 mol) of freshly decomposed cyclopentadiene was added. The reaction mixture is 2 Vigorously stirred for ~ 3 minutes. Next, while simultaneously cooling with water, 172 g (1.05 mol) Of cyclohexyl bromide was added. After stirring for 2 hours at room temperature, the reaction mixture is 70 C. followed by stirring for a further 6 hours. GC is used and 79% (Cyclohexyl) cyclopentadiene was shown to be present. The product is , 0.04 mbar and 110-120 ° C. After distillation, 73.6 g of di (cyclo Hexyl) cyclopentadiene was obtained. Characterization includes GC, GC-MS,¹³C- and¹ H-NMR was used.   Example V Preparation of di- and tri (3-pentyl) cyclopentadiene   1 liter with baffle, condenser, top stirrer, thermometer and dropping funnel Double-walled reactor with a volume of 430 g (5.4 mol) of clear 50% strength NaOH. Was filled. Then 23 g (57 mmol) of Aliquat 336 and 27 g (0.41 Mol) of freshly decomposed cyclopentadiene was added. The reaction mixture is for 2-3 minutes Vigorously stirred. Next, while simultaneously cooling with water, 150 g (1.0 mol) of 3-pen Cilbromide was added. After stirring at room temperature for 1 hour, warm the reaction mixture to 70 ° C. Followed by stirring for another 3 hours. Stirring was stopped and phase separation was awaited . The aqueous layer was withdrawn and 540 g (6.70 mol) of fresh 50% strength NaOH was added. Followed by stirring at 70 ° C. for a further 4 hours. As soon as GC is used, the mixture is Has been shown to consist of di- and tri- (3-pentyl) cyclopentadiene (about 3: 2). Was. The product is distilled at 0.2 mbar, 51 ° C. and 0.2 mbar, 77-80 ° C. respectively. Was done. After distillation, 32 g of di (3-pentyl) cyclopentadiene and 18 g of tri ( 3-pentyl) cyclopentadiene was obtained. Characterization includes GC, GC-MS,¹³C- and¹ H-NMR was used.   Example VI Preparation of tri (cyclohexyl) cyclopentadiene   1 liter with baffle, condenser, top stirrer, thermometer and dropping funnel Double wall reactor with 600 g (7.5 mol) of clear 50% strength NaOH. And subsequently cooled to 8 ° C. Then 20 g (49 mmol) of Aliquat 336 and 3 3 g (0.5 mol) of freshly decomposed cyclopentadiene was added. The reaction mixture is 2 Vigorously stirred for ~ 3 minutes. Next, while simultaneously cooling with water, 256 g (1.57 mol) Of cyclohexyl bromide was added. 1 hour at room temperature After stirring, the reaction mixture was warmed to 70 ° C., followed by stirring for another 2 hours. 2 o'clock After a short time, stirring was stopped and phase separation was awaited. The water layer is withdrawn, and 60 0 g (7.5 mol) of fresh 50% strength NaOH is added, followed by a further 4 hours at 70 ° C. Stirred. As soon as GC is used, 10% of di- (cyclohexyl) cyclope Pentadiene and 90% tri- (cyclohexyl) cyclopentadiene in the mixture To be present. The product is distilled at 0.04 mbar and 130 ° C. Was. After distillation, 87.4 g of tri (cyclohexyl) cyclopentadiene were obtained . Characterization includes GC, GC-MS,¹³C- and¹H-NMR was used.   Example VII Preparation of di (2-butyl) cyclopentadiene   1 liter with baffle, condenser, top stirrer, thermometer and dropping funnel Double wall reactor with 600 g (7.5 mol) of clear 50% strength NaOH. And subsequently cooled to 10 ° C. Then 30 g (74 mmol) of Aliquat 336 and 48.2 g (0.73 mol) of freshly decomposed cyclopentadiene was added. Reaction mixture Was stirred vigorously for 2-3 minutes. Next, while cooling with water at the same time, 200g (1.46 2-butyl bromide) was added. After stirring for 2 hours at room temperature, the reaction mixture is Warmed to 0 ° C. and subsequently stirred for a further 4 hours. 90% as soon as GC is used Shows that more di- (2-butyl) cyclopentadiene is present in the mixture Was. The product comprises 20 mbar and 80 Distilled at ~ 90 ° C. After distillation, 90.8 g of di- (2-butyl) cyclopentadiene Obtained. Characterization includes GC, GC-MS,¹³C- and¹H-NMR was used.   Example VIII Preparation of tri (2-butyl) cyclopentadiene   1 liter with baffle, condenser, top stirrer, thermometer and dropping funnel Double wall reactor with 400g (5mol) of transparent 50% strength NaOH Was done. Then 9.6 g (24 mmol) of Aliquat 336 and 15.2 g (0.23 mol) of fresh Decomposed cyclopentadiene was added. The reaction mixture is stirred vigorously for 2-3 minutes Was. Next, while simultaneously cooling with water, 99.8 g (0.73 mol) of 2-butyl bromide was added. Added in 0 minutes. After stirring for 30 minutes at room temperature, the reaction mixture was warmed to 70 ° C. Subsequently, the mixture was further stirred for 3 hours. Stirring was stopped and phase separation was awaited. Water layer Was extracted, and 400 g (5.0 mol) of fresh 50% strength NaOH was added, followed by And stirred at 70 ° C. for another 2 hours. As soon as GC is used, 90% of the tri- (2- Butyl) cyclopentadiene is di-, tri- and tetra (2-butyl) cyclopentene It was shown to be present in a mixture of tadiene. The product comprises 1 mbar and Distilled at 91 ° C. After distillation, 40.9 g of tri (2-butyl) cyclopentadiene Obtained. Characterization includes GC, GC-MS,¹³C- and¹H-NMR was used.   Example IX Preparation of di- and tri (2-pentyl) cyclopentadiene   1 liter with baffle, condenser, top stirrer, thermometer and dropping funnel Double-wall reactor with a volume of 900 g (11.25 mol) of transparent 50% strength NaOH Filled. Then 31 g (77 mmol) of Aliquat 336 and 26.8 g (0.41 mol) Fresh cracked cyclopentadiene was added. The reaction mixture is stirred vigorously for 2-3 minutes. It was stirred. Next, while simultaneously cooling with water, 155 g (1.03 mol) of 2-pentyl bromide The mid was added over one hour. After stirring for 3 hours at room temperature, the reaction mixture is And then stirred for a further 2 hours. Stirring is stopped and phase separation is awaited. I was drunk. The aqueous layer was withdrawn and 900 g (11.25 mol) of fresh 50% strength NaOH Was added, followed by stirring at 70 ° C. for a further 2 hours. The GC is used and immediately The mixture consists of di- and tri- (2-pentyl) cyclopentadiene (about 1: 1) It has been shown. The product is 2 mbar, 79-81 ° C. and 0.5 mbar, 102 ° C. Each was distilled. After distillation, 28 g of di (2-pentyl) cyclopentadiene and 40 g To give tri (2-pentyl) cyclopentadiene. Characterization includes GC, GC-MS,^{1 Three} C- and¹H-NMR was used.   Example X Preparation of di (2-propyl) cyclohexylcyclopentadiene   200mm with baffle, condenser, top stirrer, thermometer and dropping funnel Double-wall reactor with a volume of liters In, 150 g (1.9 mol) of clear 50% strength NaOH, 7 g (17.3 mmol) of Aliquat 3 36 and 8.5 g (0.13 mol) of freshly decomposed cyclopentadiene were mixed. Reaction mixture The mixture was stirred vigorously at 1385 rpm for 2-3 minutes. Next, simultaneously cool with water Meanwhile, 31.5 g (0.26 mol) of 2-propyl bromide was added. 1 hour in total And metered. After the addition of the bromide, the reaction mixture was warmed to 50 ° C. 2 After time, stirring was stopped and phase separation was awaited. The water layer is withdrawn, and 150 g (1.9 mol) of fresh 50% strength NaOH was added. Next, 20.9 g (0.13 Of cyclohexyl bromide are added and then stirring is carried out at 70 ° C. for a further 3 hours. Continued for hours. GC is used immediately and 80% of di (2-propyl) cyclohexyl Lecyclopentadiene was shown to be present in the mixture. The product is 0. Distilled at 3 mbar and 80 ° C. After distillation, 17.8 g of di (2-propyl) cyclohexane Xylcyclopentadiene was obtained. Characterization includes GC, GC-MS,¹³C- and¹H- Made by NMR.   Example XI 2- (N- In-situ preparation of (dimethylaminoethyl) tosylate   In a three-necked round bottom flask equipped with a magnetic stirrer and dropping funnel, 2- Add a solution of dimethylaminoethanol (1 equivalent) at -10 ° C under dry nitrogen. A solution of n-butyllithium (1 equivalent) in xane was added (at metering (Interval: 60 minutes). After all the butyllithium has been added, the mixture is brought to room temperature and allowed to cool. And stirred for 2 hours. The mixture is then cooled (-10 ° C) and p-toluene Sulphonyl chloride (1 equivalent) is then added, followed by the solution It was stirred at this temperature for 15 minutes before being added to the antadienyl anion.   Similarly, a comparative tosylate can be prepared. In a number of the following examples, The sylate is in each case linked to an alkylated Cp compound. Progress of the bond During the row, the desired substitution reaction also involves a geminal bond. In almost all cases In which the non-geminal isomer is converted to its slightly soluble potassium salt, and then By washing the salt with a solvent in which the salt is insoluble or slightly soluble, The geminal isomer could be separated from the emininal isomer.   Example XII a. Preparation of (dimethylaminoethyl) dicyclohexylcyclopentadiene   In a 250 ml 3-neck round bottom flask equipped with a magnetic stirrer and dropping funnel Dicyclohexylcyclopentadiene in anhydrous THF (125 ml) Example IV) A solution of (6.90 g; 30.0 mmol) in a cold solution (0 ° C) Solution of n-butyllithium in toluene (18.7 ml; 1.6 mol / l; 30.0 Mmol) was added dropwise. After stirring for 24 hours at room temperature, 30.0 mmol In-situ prepared 2- (dimethylaminoethyl) tosylate was added. 18 hours After stirring, the conversion was found to be 88% and water (100 ml) was Carefully added dropwise to the reaction mixture, and then the tetrahydrofuran is distilled off Was done. The crude product was extracted with ether, and the collected organic phase was then Dried (sodium sulfate) and evaporated to dryness. The residue is silica gel 7.4 g of (dimethylaminoethyl) dicyclohexylcycline This produced lopentadiene.   b.1 -(Dimethylaminoethyl) -2,4-dicyclohexylcyclopentadiene Dititanium (III) dichloride and [1- (dimethylaminoethyl) -2,4-dicyclo Cyclohexyl cyclopentadienyl] dimethyl titanium _{(III) [C 5 H 2} (c-C 6 H 11) 2 (CH_Two)_TwoNMe_TwoTi (III) Cl_Two] And [C_FiveH_Two(C-C₆H₁₁)_Two(CH_Two) ₂ NMe ₂ Ti (III) Me ₂ ]   In a Schlenk vessel, 1.37 g (4.54 mmol) of (dimethylaminoethyl) dicyclo Hexylcyclopentadiene is dissolved in 30 ml of diethyl ether And then the solution was cooled to -60 ° C. Then 2.84 ml n-Butyllithium (1.6 M in hexane; 4.54 mmol) was added dropwise. reaction The mixture was slowly brought to room temperature and stirring was continued for 2 hours. Yellow after solvent evaporation Powder remained, to which 30 ml of petroleum ether was added. Second Sc 40 millilitres in hlenk container 1.68 g (4.53 mmol) of Ti (III) Cl_Three・ In addition to 3THF Was done. Both Schlenk vessels are cooled to -60 ° C and then the organolithium The compound is Ti (III) Cl_ThreeAdded to the suspension. The reaction mixture was then stirred at room temperature for 18 hours. After stirring, the solvent was evaporated. 50 ml of petroleum ether to residue Was added and then again evaporated to dryness. 1- (dimethylaminoethyl)- A crude containing 2,4-dicyclohexylcyclopentadienyl titanium (III) dichloride. Solid remained.   In a Schlenk vessel, 0.31 g (0.671 mmol) of the above 1- (dimethylaminoethyl) Tyl) -2,4-dicyclohexylcyclopentadienyltitanium (III) dichloride Was dissolved in 30 ml of diethyl ether. The solution was cooled to -60 ° C. And then 0.73 ml of methyl lithium (in diethyl ether) 1.84M; 1.34 mmol) was added dropwise. The solution was slowly brought to room temperature and continued. And stirred for 1 hour. Then the solvent is evaporated and the residue is Extracted with petroleum ether. The filtrate is boiled down and dried under vacuum for 18 hours Was. [1- (dimethylaminoethyl) -2,4-dicyclohexylcyclopentadi [Enyl] 0.14 g of a black / brown oil containing dimethyltitanium (III) remained.   Example XIII a. Preparation of dimethylaminoethyl) di (2-pentyl) cyclopentadiene   In a 250 ml 3-neck round bottom flask equipped with a magnetic stirrer and dropping funnel Di (2-pentyl) cyclopen in anhydrous tetrahydrofuran (125 ml) Hexane was added to a cold solution (0 ° C) of tadiene (7.82 g; 38.0 mmol) under a nitrogen atmosphere. Solution of n-butyllithium in sun (24.0 ml; 1.6 mol / l; 38 Mmol) was added dropwise. After stirring for 24 hours at room temperature, the in-situ prepared 2- (Dimethylaminoethyl) tosylate (38.0 mmol) was added. 18 hours stirring Later, the conversion was found to be 92% and water (100 ml) was reacted The mixture is carefully added dropwise and then the tetrahydrofuran is distilled off. Was. The crude product is extracted with ether, and the collected organic phases are then dried (Sodium sulfate) and evaporated to dryness. The residue is silica gel Purified on a ram and 8.2 g of (dimethylaminoethyl) di (2-pentyl) cyclope This gave antadiene.   b.1 -(Dimethylaminoethyl) -2,4-di (2-pentyl) cyclopentadie Nyltitanium (III) dichloride and [1- (dimethylaminoethyl) -2,4-di (2-pe Pentyl) cyclopentadienyl] dimethyl titanium _{(III) [C 5 H 2} (2-C 5 H 11 )_Two(CH_Two)_TwoNMe_TwoTi (III) Cl_Two] And [C_FiveH_Two(2-C_FiveH₁₁)_Two(CH ₂₎ Synthesis of _{2 NMe 2 Ti (III) Me} 2]   In a Schlenk container, 1.60 g (5.77 mmol) of (dimethylaminoethyl) di (2- (Pentyl) cyclopentadiene, Dissolved in 40 milliliters of diethyl ether and then the solution was Cooled to ° C. Then 3.6 ml of n-butyllithium (in hexane) 1.6M; 5.77 mmol) was added dropwise. The reaction mixture is slowly brought to room temperature and Stirring was continued for hours. In a second Schlenk vessel, 40 ml of tetrahydrid Lofran is 2.14 g (5.77 mmol) of Ti (III) Cl_Three-Added to 3THF. Both S The chlenk vessel is cooled to −60 ° C., and then the organolithium compound is replaced with Ti (III) C l_ThreeAdded to the suspension. The reaction mixture is then stirred at room temperature for 18 hours, after which The solvent was evaporated. 50 ml of petroleum ether is added to the residue, then Again evaporated to dryness. 1- (dimethylaminoethyl) -2,4-di (2-pen 1.60 g of crude solid containing (tyl) cyclopentadienyltitanium (III) dichloride Remained.   In a Schlenk vessel, 0.33 g (0.835 mmol) of 1- (dimethylaminoethyl) di 40 ml of (2-pentyl) cyclopentadienyltitanium (III) dichloride Was dissolved in diethyl ether. The solution is cooled to -60C and then 0.90 ml of methyllithium (1.84 M in diethyl ether; 1.66 mmol Was added dropwise. The reaction mixture is slowly brought to room temperature, followed by stirring for 1 hour. It was stirred. Next, the solvent was evaporated. The residue is 50 ml of petroleum ether And the filtrate was then boiled down. [1- (dimethylaminoethyl) -2,4 Black color containing -di (2-pentyl) cyclopentadienyl] dimethyltitanium (III) / 0.24 g of a brown oil remained.   Example XIV a. Preparation of (dimethylaminoethyl) tri (2-propyl) cyclopentadiene   In a dried 500 ml three-necked round bottom flask equipped with a magnetic stirrer, 6 2.5 ml solution of n-butyllithium (1.6 M in n-hexane; 100 mmol) Was 19.2 g (1%) in 250 ml of THF at -60 ° C under a dry nitrogen atmosphere. 00 mmol). After warming to room temperature (about 1 hour), another 2 hours Stirring was continued for a while. After cooling to -60 ° C, it was prepared in-situ (dimethylamid (Noethyl) tosylate (105 mmol) was added. The reaction mixture is warmed to room temperature And then stirred overnight. After addition of water, the product is Extracted (40-60 ° C). The collected organic phase is dried (Na_TwoSO_Four), And under reduced pressure Was evaporated. The conversion was more than 95%. Distilled product (triisopropyl The yield (based on rucyclopentadiene) was about 55%.   b. [1- (dimethylaminoethyl) -2,3,5-tri (2-propyl) cyclopen Tadienyl titanium (III) dichloride and [1- (dimethylaminoethyl) -2,3,5- Tri (2-propyl) cyclopentadienyl] dimethyl titanium (III) [C ₅ H ( iPr) ₃ (CH ₂ ) ₂ NMe ₂ Ti (III) Cl ₂ ] and [C ₅ H (iPr) ₃ (CH ₂ )_TwoNMe_TwoTi (III) M e ₂ ]   200 ml of petroleum ether in a 500 ml three-necked round bottom flask Is 8.5 g (28.18 mmol) of potassium 1- (dimethylaminoethyl) -2,3,5- Added to tri (2-propyl) cyclopentadienyl.   In a second (1 liter) three-necked round bottom flask, add 300 ml Drofuran is 10.5 g (28.3 mmol) of Ti (III) Cl_Three-Added to 3THF. Both Is cooled to −60 ° C. and then the organopotassium compound is converted to Ti (III) C l_ThreeAdded to the suspension. 1- (dimethylaminoethyl) -2,3,5-tri (2-pro The reaction mixture containing (pyr) cyclopentadienyltitanium (III) dichloride The mixture was brought to room temperature and stirring was continued for another 18 hours. This should be cooled to -60 ° C. And then 30.6 milliliters of methyllithium (diethyl 1.827M in toluene (55.9 mmol) was added. After stirring at room temperature for 2 hours The solvent was removed and the residue was dried under vacuum for 18 hours. Then the product , 700 ml of petroleum ether was added, followed by filtration. Boil the filtrate Packed and dried in vacuum for 2 days. [1- (dimethylaminoethyl) -2 , 3,5-Tri (2-propyl) cyclopentadienyl] dimethyltitanium (III) 9.2 g of a dark brown / black oil remained.   Example XV a . (Di-n-butylaminoethyl) di (2-pentyl) cyclo Preparation of lopentadiene   The reaction is performed using (dimethylaminoethyl) -di- (2-pentyl) cyclopentadiene. Performed in the same manner as for Here, N, N-di-n-butylaminoethyl Tanol was prepared in situ. The addition rate was 88%. (Di-n-butylamido Noethyl) -di- (2-pentyl) cyclopentadiene was sequentially added to petroleum ether (40 予 備 60 ° C.) and preliminary column purification on silica gel using THF, then vacuum Obtained by distillation below. The yield was 51%.   b.1 -(Di-n-butylaminoethyl) -2,4-di (2-pentyl) cyclopentadi Eniruchitan (III) _{dichloride) [C 5 H 2 (2} -C 5 H 11) 2 (CH 2) 2 N (n-C ₄ H ₉ ) ₂ Ti (III) Cl ₂ ]   In a Schlenk vessel 0.919 g (2.54 mmol) of (di-n-butylaminoethyl) ) Di (2-pentyl) cyclopentadiene is converted to 40 ml of diethyl ether And the solution was then cooled to -60 ° C. Then 1.6 milliliters N-butyllithium (1.6 M in hexane; 2.56 mmol) was added dropwise. Was. The reaction mixture was slowly brought to room temperature and stirring was continued for 2 hours. This is 960 mg (2.59 mmol) in 20 ml tetrahydrofuran at -60 ° C ) Ti (III) Cl_Three-Added to 3THF. The reaction mixture is then stirred at room temperature for 18 hours. And then the solvent was evaporated. The residue is 10 ml [lacuna (lacun a)]. 1- (di-n-butyl Aminoethyl) -2,4-di (2-pentyl) cyclopentadienyltitanium (III) 0.95 g of crude solid containing the chloride remained.   Example XVI a. Preparation of (dimethylaminoethyl) di (2-propyl) cyclopentadiene   The reaction is based on (dimethylaminoethyl) tri (2-propyl) cyclopentadiene. Was performed in the same way as The conversion was 97%. Dimethylamino Ethyl diisopropylcyclopentadiene was obtained by distillation, with a yield of 54%. Was.   b. [1- (dimethylaminoethyl) -2,4-di (2-propyl) cyclopentadie Niltitanium (III) dichloride and [1- (dimethylaminoethyl) -2,4-di (2- Propyl) cyclopentadienyl] dimethyltitanium (III) [C ₅ H ₂ (iPr) ₂ (CH_Two)_TwoNMe_TwoTi (III) Cl_Two] And [C_FiveH_Two(IPr)_Two(CH_Two)_TwoNMe ₂ Ti (III) Me ₂ ] In a 250 ml three-necked round bottom flask, add 100 ml 8.9 g (40.3 mmol) of (dimethylaminoethyl) -di- (2-propyl) in the run ) To cyclopentadiene was added 25.2 ml of n-butyllithium (1.6 M; 40.3 ml). Lmol) was added dropwise. In a second (500ml) three-necked round bottom flask In 100 ml of tetrahydrofuran, 14.93 g (40.3 mmol) of Ti (III) Cl_Three-Added to 3THF. Both flasks were cooled to -60 ° C and The organolithium compound is Ti (III) Cl_ThreeAdded to the suspension. 1- (Dimethyla Minoethyl) -2,4-di (2-propyl) cyclopentadienyltitanium (III) dichloro The reaction mixture containing the lid was slowly brought to room temperature and stirring was continued for another 18 hours . This was continued by cooling to -60 ° C and then 50.4 millilitres. Torr of methyl lithium (1.6M in diethyl ether; 80.6 mmol) was added. Was. After stirring at room temperature for 2 hours, the solvent was removed and the residue was dried in vacuo for 18 hours. It was dried. Then, 350 ml of petroleum ether was added to the product, It was subsequently filtered. The filtrate was boiled down and dried in vacuum for one day. [1- (Dimethylaminoethyl) -2,4-di (2-propyl) cyclopentadienyl] dim 11.6 g of a brown / black oil containing chiltitanium (III) remained.   Example XVII a. Preparation of (dimethylaminoethyl) di (2-butyl) cyclopentadiene   In a 250 ml 3-neck round bottom flask equipped with a magnetic stirrer and dropping funnel Di- (2-butyl) cyclopenta in anhydrous tetrahydrofuran (150 ml) Hexane was added to a cold solution (0 ° C) of diene (8.90 g; 50.0 mmol) under nitrogen atmosphere. Solution of n-butyllithium in toluene (31.2 ml; 1.6 mol / l; 50 ml Lmol) Was added. After stirring at room temperature for 24 hours, 2- (dimethylaminoethyl) tosylate (50 .0 mmol) was added. After stirring for 18 hours, the conversion was found to be 96% , And water (100 ml) are carefully added dropwise to the reaction mixture, and Then the tetrahydrofuran was distilled off. The crude product is extracted with ether. And the collected organic phase is then dried (sodium sulfate) and boiled down Was done. The residue was purified on a silica gel column and 8.5 g of (dimethylaminoethyl L) di (2-butyl) cyclopentadiene.   b.1- (Dimethylaminoethyl) -2,4-di (2-butyl) cyclopentadienylthi Tan (III) dichloride and [1- (dimethylaminoethyl) -2,4-di (2-butyl) cyclohexane Ropentajieniru] dimethyl titanium _{(III) [C 5 H 2} (2-C 4 H 9) 2 (CH 2) 2 NMe_TwoTi (III) Cl_Two] And [C_FiveH_Two(2-C_FourH₉)_Two(CH_Two)_TwoNMe_TwoTi ( III) Synthesis of Me ₂ ] In a Schlenk vessel, 2.36 g (9.48 mmol) of (dimethylaminoethyl) di (2- (Tyl) cyclopentadiene is dissolved in 50 ml of diethyl ether And then the solution was cooled to -60 ° C. Then 5.9 ml of n- Butyllithium (1.6M in hexane; 9.44 mmol) was added dropwise. Reaction mixing The material was slowly brought to room temperature and stirring was continued for 2 hours. In the second Schlenk vessel 3.51 g of 50 ml of tetrahydrofuran (9.44 mmol) Ti (III) Cl_Three-Added to 3THF. Both Schlenk vessels are -60 ° C and then the organolithium compound is converted to Ti (III) Cl_ThreeAdded to the suspension Was. The reaction mixture was then stirred at room temperature for 18 hours, after which the solvent was evaporated . 50 ml of petroleum ether are added to the residue and then again steamed to dryness Was issued. 1- (dimethylaminoethyl) -2,4-di (2-butyl) cyclopentadie 2.15 g of unpurified solid containing nil titanium (III) dichloride remained.   In a Schlenk vessel, 0.45 g (1.22 mmol) of 1- (dimethylaminoethyl) di (2 -Butyl) cyclopentadienyltitanium (III) dichloride in 40 ml Dissolved in ethyl ether. The solution was cooled to -60 ° C and then 1. 33 ml of methyllithium (1.84 M in diethyl ether; 2.44 mmol) Was added dropwise. The reaction mixture was slowly brought to room temperature, followed by stirring for 1 hour. Was. Next, the solvent was evaporated. The residue was extracted with 50 ml petroleum ether. Discharged and then the filtrate was boiled down. [1- (dimethylaminoethyl) -2,4 Black / brown containing [-di (2-butyl) cyclopentadienyl] dimethyltitanium (III) 0.36 g of this oil remained.   Example XVIII a. Preparation of dimethylaminoethyl) tri (2-butyl) cyclopentadiene   The reaction is (dimethylaminoethyl) tri (2-propyl) It was performed in the same manner as for clopentadiene. The addition rate was 92%. The product was obtained by distillation and the yield was 64%.   b. [1- (dimethylaminoethyl) -2,3,5-tri (2-butyl) cyclopentadie Nyltitanium (III) dichloride and [1- (dimethylaminoethyl) -2,3,5-tri (2 - butyl) cyclopentadienyl] dimethyl titanium _{(III) [C 5 H (} 2-C 4 H 9 )_Three(CH_Two)_TwoNMe_TwoTi (III) Cl_Two] And [C_FiveH (2-C_FourH₉)_Three(CH_Two)_Two NMe_TwoTi (III) Me_Two] Synthesis   200 ml of petroleum ether in a 500 ml three-necked round bottom flask Is 6.28 g (20.6 mmol) of potassium 1- (dimethylaminoethyl) -2,3,5-tri (2-butyl) cyclopentadienyl. Second (1 liter) three In a round neck flask, 300 milliliters of tetrahydrofuran was added to 7.65 g (20.6 ml). Limol) Ti (III) Cl_Three-Added to 3THF. Both flasks are cooled to -60 ° C And then the organopotassium compound is Ti (III) Cl_ThreeAdded to the suspension. 1- Methylaminoethyl) -2,3,5-tri (2-butyl) cyclopentadienyltitanium (II I) The reaction mixture containing dichloride is slowly brought to room temperature and stirring is continued for another 18 hours. I was killed. This was continued by cooling to -60 ° C and then 22.3 Milliliter of methyllithium (1.827M in diethyl ether; 40.7mmol) Was added. Stir at room temperature for 2 hours After work-up, the solvent was removed and the residue was dried in vacuo for 18 hours. Then, To the product was added 700 ml of petroleum ether, followed by filtration. Filtration The liquor was boiled down and dried under vacuum for 2 days. [1- (dimethylaminoethyl Le) -2,3,5-tri (2-butyl) cyclopentadienyl] dimethyltitanium (III) 7.93 g of a brown / black oil remained.   Example XIX   (Preparation of dimethylaminoethyl) di (3-pentyl) cyclopentadiene   The reaction was performed with (dimethylaminoethyl) di (2-propyl) cyclopentadiene. This was performed in the same manner as described above. The conversion was 99%. (Dimethylamino Ethyl) di (3-pentyl) cyclopentadiene is sequentially converted to petroleum ether (40-60 ° C ) And preliminary column purification on silica gel using THF to give 85% yield. Was.   Example XX   (Of di-n-butylaminoethyl) -di- (3-pentyl) cyclopentadiene Preparation   The reaction is performed using (di-n-butylaminoethyl) di (2-propyl) cyclopentadie Performed in the same way as the The conversion was 95%. The product is Preliminary color on silica gel using petroleum ether (40-60 ° C) and THF After purification, a 75% yield was obtained.   Example XXI Preparation of (2-dimethylaminoethyl) -tri- (3-pentyl) cyclopentadiene Made   The reaction is based on (dimethylaminoethyl) tri (2-propyl) cyclopentadiene. Was performed in the same way as The conversion was 94%. (2-dimethyla Minoethyl) -tri- (3-pentyl) cyclopentadiene is successively After preliminary column purification on silica gel using (40-60 ° C) and THF, 61% yield was obtained. Rate obtained.   Example XXII a. Cyclohexyl (dimethylaminoethyl) -di- (2-propyl) cyclopen Preparation of Tadiene   In a Schlenk vessel, cyclohexyl (diisopropane) in anhydrous THF (150 ml) Hexane at room temperature in a solution of (ropyl) cyclopentadiene (9.28 g; 40.0 mmol) Solution of n-butyllithium in (25.0 ml; 1.6 mol / l; 40.0 ml Lmol) was added dropwise. Then, in another Schlenk vessel, n-butyl in hexane Solution of chilled lithium (25.0 ml; 1.6 mol / l; 40.0 mmol) But dimethylaminoethanol (3.56 g; 40.0 mmol) in THF (100 ml) Was added dropwise to a cold solution (-78 ° C). After stirring for 1 hour and 30 minutes at room temperature, the mixture Is again cooled to -78 ° C and solid tosyl chloride (8.10 g; 40.0 mmol) is added. It has been added. The mixture was brought to 0 ° C., stirred for 5 minutes and cooled again to −78 ° C. And then the mixture from the first Schlenk container is added all at once. I got it. After stirring at room temperature for 16 hours, the conversion was 100%. Column chromatography After the fee, 11.1 g of cyclohexyl (dimethylaminoethyl) -di- (2-prop L) cyclopentadiene was obtained.   b.1- (Dimethylaminoethyl) -4-cyclohexyl-2,5-di (2-propyl) Cyclopentadienyl titanium (III) dichloride and [1- (dimethylaminoethyl) Ru) -4-cyclohexyl-2,5-di (2-propyl) cyclopentadienyl] di Methyl titanium (III ) _{[C 5 H (c-Hex} ) (2-C 3 H 7) 2 (CH 2) 2 NMe 2 Ti (III) Cl_Two] And [C_FiveH (c-Hex (2-C_ThreeH₇)_Two(CH_Two)_TwoNMe_Two Ti (III) Me_Two] Synthesis   Lithium (dimethylamine) dissolved in 20 milliliters of tetrahydrofuran Noethyl) cyclohexyldi (2-propyl) cyclopentadiene (2.18 g, 7.20 g) Mmol) of Ti (III) Cl in 20 milliliters of tetrahydrofuran_Three・ 3THF (2. 67g, 7.20 mmol) of a cold slurry (-70 ° C) was added at -70 ° C. form The resulting dark green solution was stirred at room temperature for 72 hours. After this is boiled down, 30 Milliliter of petroleum ether (40-60) was added. To complete the drying again After evaporation, 1- (dimethylaminoethyl) -4-cyclohexyl-2,5-di (2- Propyl) cyclopentadienyltitanium (III) dichloride [lithium chloride] To obtain a green powder (2.73 g). Top in 30 ml diethyl ether Smell 0.63 g (1.36 mmol) of [1- (dimethylaminoethyl) -4-cyclohexane Xyl-2,5-di (2-propyl) cyclopentadienyltitanium (III) dichloride 1.70 ml of [lithium chloride] slurry cooled to -70 ° C Methyllithium (1.6M in diethyl ether; 2.72mmol) was added dropwise . The green-brown slurry darkened immediately. The mixture is then stirred at room temperature for 1 hour. And boiled until drying is complete, and in 40 milliliters of petroleum ether Dissolved. After completion of filtration and evaporation of the solvent, 1- (dimethylaminoethyl) -4 -Cyclohexyl-2,5-di (2-propyl) cyclopentadienyltitanium (III) A black powder containing dimethyl (0.47 g, 1.22 mmol) was obtained.   Example XXIII Preparation of (di-n-butylaminoethyl) di (2-propyl) cyclopentadiene   The reaction was performed with (dimethylaminoethyl) di (2-propyl) cyclopentadiene. This was performed in the same manner as described above. N, N-di-n-butylaminoethanol tosylate was prepared in situ. Turn The conversion was 94%. Non-geminal di-n-butylaminoethyl di (2-prop L) Cyclopentadiene was obtained by distillation in a yield of 53%.   Example XXIV Preparation of (dimethylaminoethyl) -tri- (2-pentyl) cyclopentadiene   The reaction is based on (dimethylaminoethyl) tri (2-propyl) cyclopentadiene. Was performed in the same way as The conversion was 90%. Non-geminal Dimethylaminoethyldiisopropylcyclopentadiene is obtained by distillation, The yield was 54%. (Dimethylaminoethyl) -tri- (2-pentyl) cyclo Pentadiene, in turn, silica gel using petroleum ether (40-60 ° C) and THF After preliminary column purification above, a yield of 57% was obtained.   Example XXV Preparation of bis (dimethylaminoethyl) triisopropylcyclopentadiene   In a dried 500 ml three-necked flask with a magnetic stirrer, Liter solution of n-butyllithium (1.6 mol in n-hexane; 100 mmol) Was 19.2 g (100 ml) in 250 ml of THF at -60 ° C under dry nitrogen atmosphere. Lmol) of triisopropylcyclopentadiene. Warm to room temperature After stirring (about 1 hour), stirring was continued for another 2 hours. After cooling to -60 ° C, In-situ prepared (dimethylaminoethyl) tosylate (105 mmol) for 5 minutes Was added. The reaction mixture was warmed to room temperature and then stirred overnight. After adding water, the product was extracted with petroleum ether (40-60 ° C). Collected organic The phases are dried (Na_TwoSO_Four) And evaporated to dryness under reduced pressure. The yield is 95% It was big. Part of the product thus obtained (10.1 g; 38.2 mM Is the same conditions as (dimethylaminoethyl) tosylate (39.0 mmol) It was alkylated again below. Bis (2-dimethylaminoethyl) triiso Propylcyclopentadiene is obtained in a 35% yield via column chromatography Obtained.   Example XXVI a. Preparation of (dimethylaminoethyl) tricyclohexylcyclopentadiene   The reaction was carried out with (dimethylaminoethyl) dicyclohexylcyclopentadiene. This was performed in the same manner as described above. The conversion was 91%. The products are: Preparative on silica gel using petroleum ether (40-60 ° C) and THF as eluent Was obtained in an 80% yield through column purification.   b.1- (Dimethylaminoethyl) -2,3,5-tricyclohexylcyclopentadie Nyltitanium (III) dichloride and [1- (dimethylaminoethyl) -2,3,5-trisyl Clohexylcyclopentadienyl] dimethyltitanium (III )[C ₅ H (c-He _{x) 3 CH 2) 2 NMe} 2 Ti (III) Cl 2] and _{[C 5 H (c-Hex} ) 3 (CH 2) 2 NMe_TwoTi (III) Me_Two] Synthesis   Lithium (dimethylamine) dissolved in 20 milliliters of tetrahydrofuran Noethyl) tricyclohexylcyclopentadiene (2.11 g, 5.70 mmol) , Ti (III) Cl in 20 ml THF_Three・ 3THF (2.11g, 5.70mmol) Rally (-70 ° C) was added at -70 ° C. The formed dark green solution was stirred at room temperature for 72 hours. After this is boiled down, 30 ml of petroleum ether (40-60) was added. To complete drying again After evaporation to 1- (dimethylaminoethyl) -2,3,5-tricyclohexylcyclo A mint green powder (2.80 g) containing pentadienyl titanium (III) dichloride was obtained. Was done. 0.50 g (0%) obtained above in 30 ml of diethyl ether .922 mmol) of [1- (dimethylaminoethyl) -2,3,5-tricyclohexyl Clopentadienyl titanium (III) dichloride] [lithium chloride] Add 1.15 ml of methyl lithium (diethyl ether) to the cooled slurry. 1.6M; 1.84 mmol) was added dropwise. Green-brown slurry immediately turns black It is. The mixture is then stirred at room temperature for 1 hour and boiled down until drying is complete. , And dissolved in 40 milliliters of petroleum ether. Filtration and solvent evaporation After completion, (dimethylaminoethyl) -tricyclohexylcyclopentadie A black powder (0.40 g, 0.87 mmol) containing nil-Ti (III) dimethyl was obtained.   Example XXVII a. (Di-n-butylaminoethyl) -tri- (2-pentyl) cyclopentadie Preparation   The reaction was performed using (di-n-butylaminoethyl) -di- (3-pentyl) cyclopentane. Performed in the same manner as for diene. The conversion was 88%. (2- Di-n-butyl Aminoethyl) -tri- (2-pentyl) cyclopentadiene is Preparative column purification on silica gel using tel (40-60 ° C) and THF followed by reduction After distillation under pressure, a yield of 51% was obtained.   b.1- (Di-n-butylaminoethyl) -2,3,5-tri (2-pentyl) cyclopen Tadienyl titanium (III) dichlori DoSynthesis of _{[C 5 H (2-C} 5 H 11) 3 (CH 2) 2 N (n-Bu) 2 Ti (III) Cl 2] 2.633 g (6.11 mmol) of (di-n-butylaminoethyl) tri (2-pentyl) ) Cyclopentadiene is dissolved in 50 ml of diethyl ether and And cooled to -78 ° C. Then 3.8 ml of n-butyllithium (hexa 1.6 moles in ethylene glycol; 6.11 mmol). After stirring at room temperature for 18 hours, clear Light yellow solution is boiled down, followed by 25 ml of petroleum ether Once washed. Next, the solvent is completely evaporated and lithium 1- (di-n-butyl alcohol). Minoethyl) -2,3,5-tri (2-pentyl) cyclopentadienyl containing yellow 1.58 g of oil remained. Next, 50 ml of tetralithium organic lithium compound was added. 9.23 dissolved in drofuran and in 50 ml tetrahydrofuran g (24.9 mmol) Ti (III) Cl_Three• Added to -THF at -78 ° C. 18 at room temperature After stirring for an hour, a dark green solution was formed. After this solution is completely boiled down , 1- (di-n-butyl Aminoethyl) -2,3,5-tri (2-pentyl) cyclopentadienyltitanium (III) 1.52 g of a green oil containing dichloride remained.   Polymerization Examples XXVIII-XXXVII A. The copolymerization of propene and ethene was performed as follows. Under dry nitrogen, a 1-liter stainless steel reactor is placed in a 400 ml pen Tamethylheptane (PMH) and 30 μmol of triethylalal as a scavenger Filled with minium (TEA) or trioctyl aluminum (TOA). The reactor is Pressurized to 0.9 MPa by the monomer produced, and propene in gas on PMH : Ethene ratio was adjusted to be 1: 1. Place the reactor contents while stirring. The desired temperature was reached.   Beq metal complex used as catalyst component after conditioning the reactor (5 μmol) And cocatalyst (30 μmol BF₂₀) Is premixed for one minute and Supplied to the reactor. The mixture is always kept in a catalyst preparation vessel under a stream of dry nitrogen for about About 75 ml after premixed and rinsed in 25 ml PMH Replaced by PMH.   During the polymerization, the concentration of the monomer was added to the reactor with propene (125 liters [s.t.p.] / Time) and ethene (125 liters [s.t.p.] / Hour) It was kept as constant as possible. Reaction monitored based on temperature changes and progress of monomer feed Was done.   After 10 minutes of polymerization, the monomer feed was stopped and The solution was withdrawn under pressure and collected. Polymer at about 120 ° C for 16 hours While drying under reduced pressure.   B. The homopolymerization of ethene and the copolymerization of octene and ethene are carried out as follows. Was:   600 ml alkane mixture (pentamethylheptane or special boiling range The surrounding solvent has a 1.5 liter volume under dry nitrogen as the reaction medium. The reactor was supplied to a stainless steel reactor. At that time, the desired amount of dry octane is introduced into the reactor (This amount could also be zero). Then the reactor is The mixture was heated to the desired temperature with stirring under ethene pressure.   25 milliliters of solvent in a catalyst preparation vessel with a volume of 100 milliliters The alkane mixture was measured. In this container, the desired amount of the Al-containing catalyst is Of the metal complex such that the Al / (metal in complex) ratio in the reaction mixture is equal to 2000 Volume and premixed for 1 minute.   This mixture was then metered into the reactor, after which the polymerization was started. This The polymerization reaction started as described above was performed isothermally. The ethylene pressure is the set pressure Maintained constant in force. After the desired reaction time, the ethene feed is stopped, Then the reaction mixture was withdrawn and cooled with methanol.   The reaction mixture containing methanol is combined with water and HCl to remove catalyst residues. More washed. The mixture is then_ThreeNeutralized, then polymer stabilized To make In addition, the organic fraction was mixed with an antioxidant (Irganox 1076®). Polymer The was dried under reduced pressure at 70 ° C. for 24 hours. In both cases, the following conditions were changed. That is, -Metal complex The type and amount of the scavenger; The type and amount of cocatalyst; -Temperature It is.   The actual conditions are shown in Table I.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 212/00 C08F 212/00 (81) Designated country EP (AT, BE, CH, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, ML, MR, NE, SN, TD, TG), AP (GH, KE, LS, MW, SD, SZ, UG), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AU, BA, BB, BG, BR, CA, CN, CU, CZ, EE, GE, HU, IL, IS, JP, KP, KR, LC, LK, LR, LT, LV, MG, MK, N, MX, NO, NZ, PL, RO, SG, SI, SK, TR, TT, UA, US, UZ, VN, YU 10 (72) Inventors Ipey, Edvin, Gerald The Netherlands, 6136 JN Sittard, Frangendel 153

Claims (1)

[Claims] 1. In the polysubstituted cyclopentadiene compound, at least one substituent Is the expression   -RDR '_n (Where R is a bonding group and D is selected from Group 15 or 16 of the Periodic Table) R ′ is a substituent, and n is a heteroatom of R ′ group bonded to D. And the at least one further substituent is a branched alkyl A cyclopentadiene compound, which is a cyclopentadiene compound. 2. The method of claim 1, wherein two or three branched alkyl groups are present as substituents. The cyclopentadiene compound according to the above. 3. 3. At least one cyclopentadiene according to claim 1 or 2 as a ligand Metal complexes containing compounds. 4. The metal is a metal from Groups 4 to 10 of the periodic table and lanthanides. The metal complex according to claim 3. 5. Catalysts for copolymerization of olefins, especially for copolymerization of ethene with other olefins A method using the metal complex according to claim 3 or 4 as a component. 6. Wherein at least one other olefin is a vinyl aromatic monomer 6. Use according to claim 5. 7. 5. The method of claim 4, wherein the metal is in a lower valence state than the highest valence state. The metal complex mentioned. 8. Copolymerizing .ALPHA.-olefins with vinyl aromatic monomers A method of using the metal complex according to claim 7 as a catalyst component.