KR20010031855A - Process for the Preparation of Fulvene-Metal Complexes - Google Patents

Abstract

The present invention relates to a process for the preparation of fulven metal complexes, to novel metal complexes and to unsaturated compound polymerizations, in particular the use of such complexes as catalysts for the polymerization and copolymerization of olefins and / or dienes.

Description

Process for the Preparation of Fulvene-Metal Complexes

The present invention relates to the preparation of fulbene-metal complexes and novel fulbene-metal complexes and their use as catalysts for the polymerization of unsaturated compounds, in particular for the polymerization and copolymerization of olefins and / or dienes.

Metal complexes with cyclopentadienyl ligands have been the subject of heated research since the discovery of ferrocene. The use of cyclopentadienyl-metal complexes, especially metallocene complexes, as a activating promoter, preferably a mixture with alumoxane, in the polymerization of olefins and diolefins is known for a long time (for example EP- A 69 951, 129 368, 351 392, 485 821, 485 823). Metallocenes have proven to be very specific catalysts that are very active in the polymerization of olefins. Many new metallocene catalysts and metallocene catalyst systems for the polymerization of olefinic compounds have recently been developed to improve activity, selectivity, control of microstructure, molecular weight and molecular weight distribution.

Little is known about metal complexes with relatively fulbene ligands.

J. Am. Chem. Soc. 1997, 119, 5132] tris (pentafluoro, a specific (η ⁵ -2,3,4,5-tetramethylcyclopentadienyl-1-methylene) (η ⁵ -pentamethylcyclopentadienyl) zirconium compound A zwitterionic olefin polymerization catalyst formed by reacting with phenyl) boron or bis (pentafluorophenyl) borane is disclosed. Synthesis of (η ⁶ -2,3,4,5, -tetramethylcyclopentadienyl-1-methylene) (η ⁵ -pentamethylcyclopentadienyl) zirconium compounds is very expensive and pentamethylcyclopenta Metallocenes with dienyl ligands must first be prepared, which are decomposed by the pyrolysis reaction in the final synthesis step. Such pyrolysis reactions are described in the literature. According to Bercaw et al., JACS (1972), 94,1219, fulven complexes (η ⁶ -2,3,4,5-tetramethylcyclopentadienyl-1-methylene) (η ⁵ −) Pentamethylcyclopentadienyl) titanium-methyl is produced by pyrolysis of bis (η ⁵ -pentamethylcyclopentadienyl) titanium-dimethyl. TJMarks et al., JACS (1988), 110, 7701, describe the thermal decomposition of pentamethylcyclopentadienyl complexes of zirconium and hafnium. Fulbene complex (η ⁶ -2,3,4,5, -tetramethylcyclopentadienyl-1-methylene) (η ⁵ -pentamethylcyclopentadienyl) zirconium-phenyl is bis (η ⁵ -pentamethylcyclopenta Produced by pyrolysis of dienyl) zirconium-diphenyl.

The preparation of fulven complexes by the heating method is limited to some structural modifications. Heating methods do not always produce a single product.

See G. Wilkinson et al., J. Chem. Soc. 1960, 1321-1324 discloses the reaction of 6,6-dialkylpulbene with chromium-hexacarbonyl or molybdenum-hexacarbonyl. However, cyclopentadienyl-metal complexes are obtained instead of fulven metal complexes.

J. Chem. Soc. Dalton Trans. (1985), 2037, MLH Green ( Green), etc.] in the bis (toluene) has been reported bis (η ⁶ -6,6- diphenyl fulvene) Synthesis of titanium to react with the titanium 6,6-diphenyl fulvene. However, bis (toluene) titanium must be prepared by a technique that evaporates complex and expensive metal atoms. For this reason, metal titanium was evaporated and condensed in a matrix with toluene gas. The yield of bis (toluene) titanium is very low. Therefore, bis (toluene) titanium can be used only in a limited range.

It is therefore an object of the present invention to find an improved method for producing fulvene-metal complexes without the abovementioned disadvantages. It has now been surprisingly found that fulvene-metal complexes can be prepared by reacting fulvene compounds with a suitable transition metal complex in the presence of a reducing agent.

Accordingly, the present invention provides a fulbene-metal of formula (Ia) or (Ib), characterized in that the transition metal compound of formula (IIa) or (IIb) is reacted with a fulvene compound of formula (III) in the presence of a reducing agent. Provided are methods for preparing the complexes.

Where

M is a Group IIIb, IVb, Vb or VIb or lanthanide or actan group metal on the periodic table of elements according to IUPAC,

A optionally represents an anionic ligand with one or more bridges,

X is a hydrogen atom, a C ₁ -C ₁₀ -alkyl group, a C ₁ -C ₁₀ -alkoxy group, a C ₆ -C ₁₀ -aryl group, a C ₆ -C ₁₀ -aryloxy group, a C ₂ -C ₁₀ -alkenyl group, Of a C ₇ -C ₄₀ -arylalkyl group, a C ₇ -C ₄₀ -alkylaryl group, a C ₈ -C ₄₀ -arylalkenyl group, a silyl group substituted with a C ₁ -C ₁₀ -hydrocarbon radical, a halogen atom or an NR ⁷ ₂ An amide having the formula,

L represents a neutral ligand,

R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and are hydrogen, halogen, cyano group, C ₁ -C ₂₀ -alkyl group, C ₁ -C ₁₀ -fluoroalkyl group, C ₆ -C ₁₀ -fluoroaryl group, C ₁ -C ₁₀ -alkoxy group, C ₆ -C ₂₀ -aryl group, C ₆ -C ₁₀ -aryloxy group, C ₂ -C ₁₀ -alkenyl group, C ₇ -C ₄₀ -arylalkyl group, C ₇ -C ₄₀ -alkylaryl group, C ₈ -C ₄₀ -arylalkenyl group, C ₂ -C ₁₀ -alkynyl group, silyl group substituted with C ₁ -C ₁₀ -hydrocarbon radical, C ₁ A sulfide group substituted with a -C ₁₀ -hydrocarbon radical or an amino group optionally substituted with a C ₁ -C ₂₀ -hydrocarbon radical, or

R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in each case together with the atoms to which they are attached form at least one aliphatic or aromatic ring system and at least one heteroatom (O, N , S) and 5 to 10 carbon atoms,

R ⁷ is hydrogen, C ₁ -C ₂₀ -alkyl group, C ₆ -C ₂₀ -aryl group, C ₇ -C ₄₀ -arylalkyl group, C ₇ -C ₄₀ -alkylaryl group, C ₁ -C ₁₀ -hydrocarbon radical A substituted silyl group or an amino group optionally substituted with a C ₁ -C ₂₀ -hydrocarbon radical,

m, p represent the number 0, 1, 2, 3 or 4 when the valence of M and the state of bonding,

k represents the numbers 1, 2 and 3 according to the oxidation number of M, and the sum of k + m + p is 1 to 5,

n is a number from 0 to 10.

A _m X _s M

A _m X _s L _n M

Where

A, X, L, M, m, s and n have the meanings mentioned above,

s is 2, 3, 4, 5 or 6, and s> p.

Where

R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ have the meanings mentioned above.

The preparation of the fulbene-metal complex of formula (I) is shown in the following scheme.

The reaction can be carried out in a single reaction step, for example in a one-pot reaction, in which the order of addition of the individual reaction components is not fixed. The reaction can also be carried out in separate reaction steps. For example, the transition metal compound of formula (IIa) or (IIb) is first contacted with a reducing agent and reacted with the fulbene compound of formula (III) in a separate reaction step. More preferably, the transition metal compound of the formula (IIa) or (IIb) is first added to the fulvene compound (III), and then a reducing agent is added.

Examples of suitable reducing agents are alkali metals, alkaline earth metals, aluminum, zinc, alkali metal alloys such as sodium-potassium alloys or sodium amalgams, alkaline earth metal alloys and metal hydrides. Examples of metal hydrides are lithium hydride, sodium hydride, magnesium hydride, aluminum hydride, lithium aluminum hydride and sodium borohydride. Specific examples of reducing agents include sodium naphthalene, potassium graphite, lithium-alkyl, magnesium-butadiene, magnesium-anthracene, trialkylaluminum compounds and Grignard reagents. Preferred reducing agents are alkali or alkaline earth metals, C ₁ -C ₆ -alkyllithium, tri-C ₁ -C ₆ -alkylaluminum compounds and Grignard reagents. Preferred reducing agents are lithium, magnesium, n-butyllithium, triethylaluminum and triisobutylaluminum. Instead of the above mentioned reducing agents, it is also possible to carry out the electrochemical reduction reaction.

The process for preparing the fulbene-metal complex of formula (I) is carried out in a suitable reaction medium at a temperature of -100 to + 250 ° C, preferably -78 to + 130 ° C, more preferably -10 to + 120 ° C. .

Examples of possible suitable reaction media are aliphatic or aromatic hydrocarbons, halogenated hydrocarbons, ethers and cyclic ethers. Examples of such media include unbranched aliphatic hydrocarbons such as butane, pentane, hexane, heptane and octane, branched aliphatic hydrocarbons such as isobutane, isopentane and isohexane, cyclic aliphatic such as cyclohexane and methylcyclohexane Hydrocarbons, aromatic hydrocarbons such as benzene, toluene and xylene, and ethers such as dialkyl ethers, dimethoxyethane, tetrahydrofuran. Mixtures of various solvents are also suitable.

The fulbene-metal complex of formula (I) is prepared by excluding air and water under inert gas and handled (inert gas technology). Examples of inert gases are nitrogen or argon. Suitable inert gas techniques are, for example, conventional Schlenk techniques which are common for organometallic materials.

The fulbene-metal complex of formula (I) can be isolated or used directly for further reaction. If isolation is required, the resulting byproducts can be removed by conventional purification methods (eg filtration). In addition, the desired product can be extracted with a solvent. If necessary, purification operations (eg recrystallization) can be carried out.

Possible transition metal complexes of the formula (IIa) or (IIb) are in particular

M is a metal selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium,

A is a pyrazolate of formula N ₂ C ₃ R ⁸ ₃ , wherein R ⁸ is hydrogen or a C ₁ -C ₁₀ -alkyl group or a C ₆ -C ₁₀ -aryl group, formula R ⁷ B (N ₂ C ₃ R _{⁸³⁾ 3-pyrazol-daily} rate, the formula oR ⁷ of an alcoholate or phenolate, siloxane, thiolate of formula SR ⁷ of the formula OSiR ⁷ _3, formula (R ⁷ CO) ₂ acetylacetonate of CR ^7, the formula ( Diimine of R ⁷ N = CR ⁷ ) _2, an amidate of formula R ⁷ C (NR ⁷ ₂ ) ₂ , formula C ₈ H _q R ⁷ _8-q , wherein q is 0, 1, 2, 3, Cyclooctatetraenyl of 4, 5, 6 or 7, cyclopentadienyl of the formula C ₅ H _q R ⁷ _5-q , wherein q is 0, 1, 2, 3, 4 or 5, formula ^{_{C 9 H 7-r R 7}} r ( wherein, r is 0, 1, 2, 3, 4, 5, 6 or 7, Im) of the indenyl, the formula ^{_{C 13 H 9-s R 7}} s ( where, s Is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9) fluorenyl, or a C ₁ -C ₃₀ -alkyl radical, a C ₆ -C ₁₀ -aryl radical or C ₇ -C _{A 40} -alkylaryl radical,

L, X, R ⁷ , m, s and n have the meanings mentioned above.

Particularly preferred transition metal complexes of the above formula (IIa) or (IIb) are

M represents titanium, zirconium or hafnium,

A is bis (trimethylsilyl) amide, dimethylamide, diethylamide, diisopropylamide, 2,6-di-tert-butyl-4-methylphenolate, cyclooctatetraenyl, cyclopentadienyl, methylcyclo Pentadienyl, benzylcyclopentadienyl, n-propylcyclopentadienyl, n-butylcyclopentadienyl, iso-butylcyclopentadienyl, t-butylcyclopentadienyl, cyclopentylcyclopentadienyl, octa Decylcyclopentadienyl, 1,2-dimethylcyclopentadienyl, 1,3-dimethylcyclopentadienyl, 1,3-diisopropylcyclopentadienyl, 1,3-di-t-butylcyclopenta Dienyl, 1-ethyl-2-methylcyclopentadienyl, 1-isopropyl-3-methylcyclopentadienyl, 1- (n-butyl) -3-methylcyclopentadienyl, 1- (t-butyl ) -3-methylcyclopentadienyl, penta-methylcyclopentadienyl, 1,2,3,4-tetramethylcyclopentadienyl, 1,2,4-trimethylcyclopentadienyl, 1,2,4 -T Isopropylcyclopentadienyl, 1,2,4, -tri- (t-butyl) -cyclopentadienyl, indenyl, tetrahydroindenyl, 2-methylindenyl, 4,7-dimethylindenyl, 2 -Methyl-4,5-benzoindenyl, 2-methyl-4-phenylindenyl, fluorenyl or 9-methylfluorenyl,

X represents fluorine or chlorine,

L, m, s, n have the meanings mentioned above.

Particularly possible fulven compounds among the compounds of formula (III) are

R ¹ to R ⁶ are C ₁ -C ₃₀ -alkyl groups, C ₆ -C ₁₀ -aryl groups or C ₇ -C ₄₀ -alkylaryl groups, in particular hydrogen, methyl, trifluoromethyl, ethyl, n-propyl, iso Propyl, n-butyl, isobutyl, tert-butyl, phenyl, pentafluorophenyl, methylphenyl, cyclohexyl or benzyl.

Preferred compounds of the formula (III) are fulbene compounds of the formula (IV) or (V).

Where

R ¹ , R ² , R ³ and R ⁴ have the meanings mentioned above.

Particularly preferred compounds of formula (III) are 6-cyclohexylpulbene, 6-isopropylpulbene, 6-tert-butylpulbene, 6-phenylpulbene, 6- (dimethylamino) pulbene, 6,6-bis (dimethylamino ) Fulbene, 6,6-dimethylpulbene, 6,6-bis (trifluoromethyl) pulbene, 6,6-diphenylpulbene, 6,6-bis (pentafluorophenyl) pulbene, 6,6-pentamethylene Fulvene, 6,6-tetramethylenepulbene, 6,6-trimethylenepulbene, 2- (2,4-cyclopentadiene-1-ylidene) -1,3-dithiolane, 5-benzylidene-1 , 2,3-triphenyl-1,3-cyclopentadiene, 1,2,3,4-tetramethylpulbene, 1,2,3,4-tetraphenylpulbene, 2,3-dimethylpulbene, 2,3 Diisopropyl fulvene, 2,3-diphenyl fulvene, 1,4-dimethyl-2,3-diphenyl fulvene and 1,4-diethyl-2,3-diphenyl fulvene.

The synthesis of fulven compounds of the formulas (III), (IV) and (V) is described, for example, in J. Org. Chem., Vol. 49, no. 11 (1984), 1849].

Formula (I) given above as a fulbene-metal complex is considered to be a typical example of the binding environment. The binding environment of the metal complex depends in particular on the central metal, oxidation state and substituents of the pullbene ligand.

Figure 1 shows a perspective structure of a fulbene-metal complex prepared according to the present invention obtained by X-ray structural analysis, taking (6-tert-butylfulbenyl) pentamethylcyclopentadienyl) titanium chloride compound as an example. Presented.

The preparation according to the invention gave access to a novel fulbene-metal complex of formula (I) which could not be made by pyrolysis.

Therefore, the present invention also

M is a metal selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum and chromium,

k is 1,

A, X, m, p, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ have the meanings mentioned above,

Provided that R ¹ and R ² represent hydrogen, at the same time R ³ , R ⁴ , R ⁵ and R ⁶ represent a methyl group, and at the same time A represents a pentamethylcyclopentadienyl group or a carboranedi of formula C ₂ B ₉ H ₁₁ The compound of formula (I), which represents a diary, provides the fulbene-metal complex of formula (I).

The invention also

a) a fulbene-metal complex of formula (I) prepared by the process according to the invention, wherein M is a metal selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum and chromium,

k is 1,

A, X, m, p, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ have the meanings mentioned above), and

b) a promoter suitable for activating the metal complex a), wherein the molar ratio of component a) to component b) is from 1: 0.1 to 1: 10,000, preferably from 1: 1 to 1: 1,000.

Possible cocatalysts are cocatalysts known in the metallocene catalyst art, such as polymer or oligomeric aluminoxanes, Lewis acids and aluminates and borates. In this regard, reference is made in particular to alumoxanes in Macromol. Symp. Vol. 97, July 1995, p. 1-246, EP 277 003, EP 277 004 for borates and Organicmetallics 1997, 16, 842-857, EP 573 403 for aluminates.

Particularly suitable cocatalysts are triisobutylaluminum, trialkylaluminum compounds (e.g. trimethylaluminum, triethylaluminum, triisobutylaluminum and triisooctylaluminum), and also dialkylaluminum compounds (e.g. hydrogenated diisobutyl) Methylaluminoxane, methylalumoxane and diisobutylalumoxane, substituted triarylaluminum compounds (e.g. tris (pentafluorophenyl) aluminum) modified with aluminum, fluorinated diisobutylaluminum and diethylaluminum chloride) And ionic compounds containing tetrakis (pentafluorophenyl) aluminate as anions (eg triphenylmethyltetrakis (pentafluorophenyl) aluminate and N, N-dimethylanilinium tetrakis (pentafluorophenyl) Aluminate), substituted triarylboron compounds (e.g. tris (pentafluorophenyl) borone) Ionic compounds containing tetrakis (pentafluorophenyl) borate as an anion (e.g. triphenylmethyltetrakis (pentafluorophenyl) borate and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate) to be. Mixtures of various cocatalysts are also suitable for activating the fulven metal complex of formula (I) above.

The present invention also provides the use of a novel catalyst system for the polymerization of unsaturated compounds, in particular olefins and dienes. Both homopolymerization and copolymerization of the above-mentioned unsaturated compounds herein are understood to be polymerizations. Particularly used compounds in the polymerization are C ₂ -C ₁₀ -alkenes (for example ethylene, propylene, but-1-ene, pent-1-ene, hex-1-ene, oct-1-ene and isobutylene ) And arylalkenes (for example styrene). Particularly used dienes include conjugated dienes (eg 1,3-butadiene, isoprene and 1,3-pentadiene) and unconjugated dienes (eg 1,4-hexadiene, 1,5-heptadiene, 5,7-dimethyl-1,6-octadiene, 4-vinyl-1-cyclohexene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene and dicyclopentadiene).

The catalyst according to the invention is suitable for the preparation of copolymer based rubbers of ethylene and at least one α-olefin mentioned above and dienes mentioned above. The catalyst system according to the invention is furthermore suitable for the polymerization of cyclo-olefins (for example norbornene, cyclopentene, cyclohexene and cyclooctene) and the copolymerization of cycloolefins with ethylene or α-olefins.

The polymerization can be carried out in the liquid phase, with or without an inert solvent, or in the gas phase. Suitable solvents are aromatic hydrocarbons (eg benzene and / or toluene) or aliphatic hydrocarbons (eg propane, hexane, heptane, octane, isobutane) or cyclohexane or mixtures of various hydrocarbons.

It is possible to use the catalyst system according to the invention applied to the support. Suitable supports that may be mentioned are, for example, inorganic or organic polymeric supports (eg silica gel, zeolites, carbon black, activated carbon, aluminum oxide, polystyrene and polypropylene).

The catalyst system according to the invention can be applied to a support by conventional methods. Methods of supporting the catalyst system are disclosed for example in US Pat. No. 4,808,561, 4 912 075, 5 008 228 and 4 914 253.

The polymerization reaction is generally carried out at a pressure of 1 to 1,000 atm, preferably 1 to 100 bar and a temperature of -100 to +250 ° C, preferably 0 to +150 ° C. The polymerization can be carried out continuously or discontinuously in conventional reactors.

The present invention is explained in more detail using the following examples.

General Information: Organometallic compounds were prepared and handled with air and moisture exclusion under argon protection (Schlenck technology). All of the required solvents were boiled for several hours before use, suitably dried, then sufficiently distilled under argon to make pure. Compounds were characterized by ¹ H-NMR, ¹³ C-NMR and mass spectroscopy.

Abbreviation:

Cp: cyclopentadienyl

Cp ^* : pentamethylcyclopentadienyl

HV: High Vacuum

RT: Room temperature

THF: Tetrahydrofuran

MS: mass spectrum

EA: Elemental Analysis

Tg: glass transition temperature (DSC measurement)

de: diastereomeric excess

<Synthesis of Compounds of Formula (I)>

<Example 1>

Synthesis of fulvene complexes by reacting 6,6-dimethylpulbene with Cp ^* TiCl _{3 in the} presence of magnesium [(C ₅ (CH ₃ ) ₅ ) (C ₅ H ₄ ) C (CH ₃ ) ₂ TiCl]

First, Cp ^* TiCl ₃ (0.610 g, 2.11 mmol) and 1.05 equivalents of magnesium (0.054 g, 2.21 mmol) were placed in 25 mL of THF. 1.05 equiv of 6,6-dimethylpulbene (0.227 g, 2.14 mmol) was added dropwise to this mixture at room temperature. The mixture was then stirred overnight at room temperature to consume all the magnesium. The solvent was removed under HV and the green residue was dissolved in hexane. The solid was filtered off and the solution was concentrated in half to precipitate a green shiny platy material. The mixture was recrystallized by cooling to -20 ° C. Olive-green crystals were isolated and dried under HV. 0.429 g (59%) of [(C ₅ (CH ₃ ) ₅ ) (C ₅ H ₄ ) C (CH ₃ ) ₂ TiCl] was obtained.

<Example 2>

Synthesis of fulvene complex by reacting 6,6-dimethylpulbene with Cp ^* TiCl _{3 in the} presence of butyllithium [(Cp ^* (C ₅ H ₄ = C (CH ₃ ) ₂ ) TiCl]

400 mg (1.38 mmol) of C _P * TiCl ₃ , 154 mg (1.45 mmol) of 6,6-dimethylpulbene, and 1.11 mL (2.76 mmol) of n-butyllithium in 25 mL of THF in a Schlenk vessel at a temperature of −78 ° C. Mixed. The mixture was slowly warmed to 0 ° C. and stirred at this temperature for an additional 2 hours to complete the reaction. The solvent was then removed under HV and the green residue was dissolved in n-hexane. The solid was filtered off and the solution concentrated in half to precipitate green crystals. [(C ₅ (CH ₃ ) ₅ ) (C ₅ H ₄ ) C (CH ₃ ) ₂ TiCl] 290 mg (65%) were obtained.

<Example 3>

Synthesis of fulvene complex by reacting 6,6-dimethylpulbene with Cp ^* ZrCl _{3 in the} presence of magnesium [(C ₅ (CH ₃ ) ₅ ) (C ₅ H ₄ ) C (CH ₃ ) ₂ ZrCl]

First, Cp ^* ZrCl ₃ (0.380 g, 1.14 mmol) and 1.1 equivalents of magnesium (0.031 g, 1.26 mmol) were added to 10 mL of THF. 1.1 equivalents of 6,6-dimethylpulbene (0.134 g, 1.26 mmol) were added dropwise to this solution. After 5 minutes the reaction solution was cloudy. The mixture was stirred overnight to dissolve the magnesium completely. After drying under HV, the residue was dissolved in 10 mL of hexane and the precipitate formed was filtered and removed. [(C ₅ (CH ₃ ) ₅ ) (C ₅ H ₄ ) C (CH ₃ ) ₂ ZrCl] 197 mg (47%) was isolated from the filtrate as a reddish brown solid.

<Example 4>

Synthesis of bis (η ⁶ -6,6-diphenylpulbene) titanium by reacting 6,6-diphenylpulbene with titanium tetrachloride in the presence of magnesium

610 mg (1.83 mmol) of TiCl ₄ (THF) ₂ and 89 mg (3.65 mmol) of magnesium peel and 841 mg (3.65 mmol) of 6,6-diphenylpulbene were mixed in 30 ml of THF, the reaction medium in a Schlenk vessel. The mixture was stirred for 12 hours until the magnesium peel was consumed completely to terminate the reaction. The reaction solution was concentrated to dryness to give a green solid, which could be dissolved in n-hexane and filtered to separate from the magnesium chloride formed. The filtrate was stepwise concentrated and cooled to give 640 mg (70%) of bis (η ⁶ -6,6-diphenylfulbene) titanium.

<Example 5>

Synthesis of fulvene complexes by reacting 6,6-dimethylpulbene with CpTiCl _{3 in the} presence of magnesium [(C ₅ H ₅ ) (C ₅ H ₄ ) C (CH ₃ ) ₂ TiCl]

First, CpTiCl ₃ (0.410 g, 1.87 mmol) and 1.05 equivalents of magnesium (0.048 g, 1.96 mmol) were placed in 20 mL of THF. 1.03 equiv. Of 6,6-dimethylpulbene (0.204 g, 1.92 mmol) was added dropwise to this yellow solution at room temperature and the mixture was stirred until all used magnesium was consumed. Concentrate under HV and dissolve the resulting green solid with 20 mL of hexane. The solid was filtered off and the dark green solution was concentrated in half at room temperature under HV. Recrystallization at -20 ° C yielded 0.2 g (42%) of [(C ₅ H ₅ (C ₅ H ₄ ) C (CH ₃ ) ₂ TiCl)) as a dark green solid.

<Example 6>

Synthesis of fulvene complex with 6,6-diphenylpulbene reacted with Cp ^* TiCl _{3 in the} presence of magnesium [(C ₅ (CH ₃ ) ₅ ) (C ₅ H ₄ ) C (C ₆ H ₅ ) ₂ TiCl]

1.1 equivalents of Cp ^* TiCl ₃ (0.690 g, 2.38 mmol) and magnesium (0.064 g, 2.62 mmol) were placed in 20 mL THF. 1.1 equivalents of 6,6-diphenylpulbene (0.604 g, 2.62 mmol) were added dropwise to this solution at room temperature. The mixture was stirred overnight at room temperature to consume all magnesium. The solvent was removed under HV and the green residue was dissolved in hexanes. The precipitate was filtered off and the solution was concentrated in half. The mixture was cooled to −20 ° C. and recrystallized to give 0.29 g (27%) of [(C ₅ (CH ₃ ) ₅ ) (C ₅ H ₄ ) C (C ₆ H ₅ ) ₂ TiCl] as a green solid.

<Example 7>

Synthesis of fulvene complex with 6,6-diphenylpulbene reacted with Cp ^* ZrCl _{3 in the} presence of magnesium [(C ₅ (CH ₃ ) ₅ ) (C ₅ H ₄ ) C (C ₆ H ₅ ) ₂ ZrCl]

First, Cp ^* ZrCl ₃ (0.310 g, 0.93 mmol) and 1.05 equivalents of magnesium (0.024 g, 0.98 mmol) were added to 10 mL of THF. 1.05 equiv of 6,6-diphenylpulbene (0.225 g, 0.98 mmol) was added dropwise to this solution. The mixture was stirred overnight to allow the magnesium to react completely. Concentrated to dryness under HV, the residue was dissolved in 20 ml of toluene and the insoluble precipitate was filtered off. After being covered with a hexane layer at -20 ° C, 178 mg (39%) of [(C ₅ (CH ₃ ) ₅ ) (C ₅ H ₄ ) C (C ₆ H ₅ ) ₂ ZrCl] was obtained as a red solid.

<Example 8>

Synthesis of fulven complex by reacting 2,3,4,5-tetramethylpulbene with Cp ^* TiCl _{3 in the} presence of magnesium [(C ₅ (CH ₃ ) ₅ ) (C ₅ (CH ₃ ) ₄ ) CH ₂ TiCl]

First, Cp ^* TiCl ₃ (0.370 g, 1.28 mmol) and 1.05 equivalents of magnesium (0.033 g, 1.35 mmol) were added to 25 mL of THF. 1.05 equiv of 2,3,4,5-tetramethylpulbene (0.185 g, 1.35 mmol) was added dropwise to this red solution at room temperature. The mixture was stirred overnight at room temperature to consume all magnesium. The solvent was removed under HV and the green residue was dissolved in hexanes. The solid was filtered off and the solution was concentrated in half. The mixture was cooled to -20 ° C and recrystallized to give 0.23 g (52%) of [(C ₅ (CH ₃ ) ₅ ) (C ₅ (CH ₃ ) ₄ CH ₂ TiCl) as a green solid.

<Example 9>

Synthesis of fulvene complex by reacting 2,3,4,5-tetramethylpulbene with CpTiCl _{3 in the} presence of magnesium [(C ₅ H ₅ ) (C ₅ (CH ₃ ) ₄ ) CH ₂ TiCl]

First, CpTiCl ₃ (0.350 g, 1.60 mmol) and 1.05 equivalents of magnesium (0.041 g, 1.67 mmol) were placed in 20 mL of THF. 1.1 equivalents of 2,3,4,5-tetramethylpulbene (0.260 g, 1.67 mmol) were added dropwise to this solution at room temperature and the mixture was stirred until all used magnesium was consumed. It was concentrated under HV and the resulting green solid was dissolved in 20 mL of hexanes. After filtration of the solid, the dark green solution was concentrated in half under HV. 0.3 g (67%) of [(C ₅ H ₅ ) (C ₅ (CH ₃ ) ₄ ) CH ₂ TiCl] was recrystallized at −20 ° C. to obtain a dark green solid.

<Example 10>

Fulven complex which reacts 1,2,3,4,6-pentamethylpulbene with CpTiCl _{3 in the} presence of magnesium [(C ₅ H ₅ ) (C ₅ (CH ₃ ) ₄ ) C (H) (CH ₃ ) TiCl] Synthesis

First, CpTiCl ₃ (0.450 g, 2.05 mmol) and 1.05 equivalents of magnesium (0.054 g, 2.15 mmol) were placed in 20 mL of THF. 1.03 equivalents of 1,2,3,4,6-pentamethylpulbene (0.320 g, 2.15 mmol) were added dropwise to this solution at room temperature and the mixture was stirred until all used magnesium was consumed. It was then concentrated under HV and the resulting green solid was dissolved in 20 mL of hexanes. After filtration of the solid, the dark green solution was concentrated in half under HV. 0.17 g (28%) of [(C ₅ H ₅ ) (C ₅ (CH ₃ ) ₄ ) C (H) (CH ₃ ) TiCl] was recrystallized at −20 ° C. to obtain a dark green solid.

de: 25%

<Example 11>

Synthesis of fulvene complex with 6-tert-butylpulbene reacted with Cp ^* TiCl _{3 in the} presence of magnesium [(C ₅ (CH ₃ ) ₅ ) (C ₅ H ₄ ) C (H) (C (CH ₃ ) ₃ ) TiCl]

First, Cp ^* TiCl ₃ (0.450 g, 1.55 mmol) and 1.05 equivalents of magnesium (0.039 g, 1.65 mmol) were placed in 15 mL of THF. 1.05 equiv of 6-tert-butylpulbene (0.249 g, 1.63 mmol) was added dropwise to this solution at room temperature. The mixture was stirred overnight at room temperature to consume all magnesium. The solvent was removed under HV and the green residue was dissolved in hexanes. After filtering off the solid, the solution was concentrated in half. The mixture was recrystallized at -20 ° C to give 0.35 g (64%) of [(C ₅ (CH ₃ ) ₅ ) (C ₅ H ₄ ) C (H) (C (CH ₃ ) ₃ ) TiCl] as green crystals.

X-ray structure analysis was performed (FIG. 1).

de: ≥98%

<Example 12>

Synthesis of fulvene complex with 6-tert-butylpulbene reacted with CpTiCl _{3 in the} presence of magnesium [(C ₅ H ₅ ) (C ₅ H ₄ ) C (H) (C (CH ₃ ) ₃ ) TiCl]

First, CpTiCl ₃ (0.420 g, 1.91 mmol) and 1.05 equivalents of magnesium (0.048 g, 2.01 mmol) were placed in 10 mL of THF. 1.03 equivalents of 6-tert-butylpulbene (0.295 g, 1.91 mmol) was added dropwise to this solution at room temperature and the mixture was stirred to consume all the used magnesium. It was then concentrated under HV and the resulting green solid was dissolved in 20 mL of hexanes. After filtration of the solid, the dark green solution was concentrated in half under HV. 0.23 g (44%) of [(C ₅ H ₅ ) (C ₅ H ₄ ) C (H) (C (CH ₃ ) ₃ ) TiCl] was recrystallized at -20 ° C to obtain dark green crystals.

de: ≥98%

<Polymerization Example>

<Example 13>

Catalyst Solution Preparation

8.3 mg (22.6 μmol) of [(Cp ^* ) (C ₅ H ₄ = C (CH ₃ ) ₂ ) ZrCl] of Example 3 was dissolved in 11.3 mL of toluene.

Ethylene Polymerization

First, 100 ml of toluene was placed in a 250 ml glass reactor, and 1 ml of a 0.1 mol solution of triisobutylaluminum in toluene and 0.5 ml of a catalyst solution were added. Ethylene was then passed through the solution continuously at 1.1 bar pressure under a gas introduction tube. The polymerization reaction was started by adding 1 ml of a 0.001 mol solution of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate in toluene. After ethylene was polymerized for 5 minutes at 40 ° C. and 1.1 bar pressure, 10 ml of methanol was added to stop the reaction, and the formed polymer was filtered off, washed with acetone and placed in a vacuum dryer to dry. 1.61 g of polyethylene was obtained.

<Example 14>

Copolymerization of Ethylene and Propylene

First, 500 ml of toluene and 5 ml of 10% MAO solution in toluene were placed in a 1.4 l steel autoclave equipped with a mechanical stirrer, pressure gauge, temperature probe, thermostat, catalyst valve and monomer weigher for ethylene and propylene for 10 minutes. Was stirred. 52 g of propylene were then weighed and fed. The internal temperature was adjusted to 40 ° C. with a thermostat. Ethylene was then weighed and supplied until the internal pressure of the reaction rose to 6 bar. 5 ml of the catalyst solution of Example 5 was added to initiate the polymerization, and ethylene was continuously weighed and fed at 40 ° C. to maintain an internal pressure of 6 bar. After polymerization for 1 hour, the polymerization was stopped with 1% HCl solution in methanol and the mixture was stirred for 10 minutes to precipitate the polymer in methanol. The polymer obtained was then washed with methanol, isolated and dried in vacuo at 60 ° C. for 20 hours, yielding 48 g of copolymer. The composition of the copolymer measured by IR spectroscopy showed the introduction of 82.9% ethylene and 17.1% propylene.

<Example 15>

Preparation of the catalyst

73.9 mg (0.221 mmol) of TiCl ₄ (THF) ₂ were dissolved in 3 mL of THF. 5.4 mg (0.22 mmol) of magnesium and 51 mg (0.221 mmol) of 6,6-diphenylpulbene were added. After stirring for 20 h at 20 ° C, a dark green solution was obtained. The solution was concentrated to dryness, and the resulting residue was dried under HV for 2 hours, after which 22 ml of toluene was added to form a dark green suspension. 1 ml of catalyst suspension contained 0.01 mmol of titanium.

Ethylene Polymerization

First 90 ml of toluene and 5 ml of MAO solution (10% in toluene) were placed in a 250 ml glass reactor and stirred for 5 minutes. Then 5 ml of catalyst suspension were added and the mixture was stirred at 40 ° C. for 10 minutes. Ethylene was then passed continuously through the solution into the gas introduction tube. After the polymerization was carried out for 10 minutes at 40 ° C. under an ethylene atmosphere of 1.1 bar, the reaction was stopped by addition of 10 ml of a 1% HCl solution in methanol, and the formed polymer was filtered off and washed with methanol, and then vacuum dried. Dried. 8.9 g of polyethylene was obtained.

Claims (8)

A process for preparing a fulbene-metal complex of formula (Ia) or (Ib) comprising reacting a transition metal compound of formula (IIa) or (IIb) with a fulbene compound of formula (III) in the presence of a reducing agent. <Formula Ia> <Formula Ib> Where M is a Group IIIb, IVb, Vb or VIb or lanthanide or actan group metal on the periodic table of elements according to IUPAC, A optionally represents an anionic ligand with one or more bridges, X is a hydrogen atom, a C ₁ -C ₁₀ -alkyl group, a C ₁ -C ₁₀ -alkoxy group, a C ₆ -C ₁₀ -aryl group, a C ₆ -C ₁₀ -aryloxy group, a C ₂ -C ₁₀ -alkenyl group, C ₇ -C ₄₀ -arylalkyl group, C ₇ -C ₄₀ -alkylaryl group, C ₈ -C ₄₀ -arylalkenyl group, silyl group substituted with C ₁ -C ₁₀ -hydrocarbon radical, halogen atom or formula NR ⁷ ₂ Amide of L represents a neutral ligand, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and are hydrogen, halogen, cyano group, C ₁ -C ₂₀ -alkyl group, C ₁ -C ₁₀ -fluoroalkyl group, C ₆ -C ₁₀ -fluoroaryl group, C ₁ -C ₁₀ -alkoxy group, C ₆ -C ₂₀ -aryl group, C ₆ -C ₁₀ -aryloxy group, C ₂ -C ₁₀ -alkenyl group, C ₇ -C ₄₀ -arylalkyl group, C ₇ -C ₄₀ -alkylaryl group, C ₈ -C ₄₀ -arylalkenyl group, C ₂ -C ₁₀ -alkynyl group, silyl group substituted with C ₁ -C ₁₀ -hydrocarbon radical, C ₁ A sulfide group substituted with a -C ₁₀ -hydrocarbon radical or an amino group optionally substituted with a C ₁ -C ₂₀ -hydrocarbon radical, or R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in each case together with the atoms to which they are attached form one or more aliphatic or aromatic ring systems and comprise at least one heteroatom (O, N, S) and 5 to 10 carbon atoms, R ⁷ is hydrogen, C ₁ -C ₂₀ -alkyl group, C ₆ -C ₂₀ -aryl group, C ₇ -C ₄₀ -arylalkyl group, C ₇ -C ₄₀ -alkylaryl group, C ₁ -C ₁₀ -hydrocarbon radical A substituted silyl group or an amino group optionally substituted with a C ₁ -C ₂₀ -hydrocarbon radical, m and p represent the numbers 0, 1, 2, 3 or 4 of the valence and bonding state of M, k represents the number 1, 2 or 3, the sum of k + m + p is 1 to 5 and depends on the oxidation number of M, n is a number from 0 to 10. <Formula IIa> A _m X _s M <Formula IIb> A _m X _s L _n M Where A, X, L, M, m, s and n have the meanings mentioned above, s is 2, 3, 4, 5 or 6, and s> p. <Formula III> Where R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ have the meanings mentioned above. The process according to claim 1, wherein the reaction is carried out in a suitable reaction medium at a temperature of -100 to +250 ° C. The method of claim 1, wherein an alkali metal, alkaline earth metal or lithium-alkyl is used as the reducing agent. The method of claim 1 wherein the reaction is carried out in a solvent. The process according to claim 4, wherein the reaction is carried out in ether. In formula (la) or (lb), M is a metal selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum and chromium, k is 1, A, X, L, m, n, p, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ have the meanings mentioned above, Provided that R ¹ and R ² represent hydrogen, at the same time R ³ , R ⁴ , R ⁵ and R ⁶ represent a methyl group, and at the same time A represents a pentamethylcyclopentadienyl group or a carboranedi of formula C ₂ B ₉ H ₁₁ Fulbene-metal complexes excluding compounds representing the diary. a) a fulbene-metal complex of formula (la) or (lb) prepared according to the process of claim 1, Where M is a metal selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum and chromium, k is 1, A, X, L, m, n, p, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ have the meanings mentioned above), b) a catalyst system comprising a promoter suitable for activating the metal complex a), wherein the molar ratio of component a) to component b) ranges from 1: 0.1 to 1: 10,000. Use of the catalyst system according to claim 7 for the polymerization of olefins and / or dienes.