CN1431232A - Catalyst containing phenoxy side chain metallocene and its usage - Google Patents

Abstract

A metallocene catalyst containing phenoxy side chain is disclosed, which can be used for the homopolymerization and copolymerization of alpha-olefins (ethyl, propene, 1-butyene, etc). Its advantages are high stability and high catalytic activity.

Description

Contain phenoxy group side chain metallocene catalyst and uses thereof

Technical field

The present invention relates to olefin polymerization catalysis and application thereof, concrete, the present invention relates to the substituted cyclopentadienyl metallocene compound that contains the phenoxy group side chain of specific type, it has unusual effect as olefin polymerization catalysis, is specially adapted to the copolymerization of ethene and high alpha-olefin.

Background technology

In recent years, a large amount of facts is verified, in field of olefin polymerisation, the unique distinction of metallocene compound is, by changing the substituting group on the metallocene compound part, can change the catalytic performance of metallocene compound, as polymerization activity to polyreaction, the molecular weight of polymkeric substance and distribution thereof, co-monomer content etc.But can produce which type of effect for substituent change, still will lean on test to a great extent.

With the most close background technology of the present invention is in disclosed publication number U.S.Pat.No.5 on January 5th, 1999,856,258 patent, people such as Tobin J.Marks disclose with the dibenzyl titanium complex of the Cp part replacement amino-contained side chain Cp part that methylphenoxy is replaced and synthetic, and the complex structure formula is as follows.

This catalyzer is for ethene, and propylene and cinnamic catalyzed polymerization all have higher activity.But they only synthesize a kind of dibenzyl titanium compound.

Summary of the invention

The purpose of this invention is to provide some constrained geometry configuration metallocene compounds that contain the phenoxy group side chain and preparation method thereof and the application aspect synthesis of polyolefins.Specifically, the structure expression that has of catalyzer of the present invention is as follows:

Wherein luxuriant ring Cp is single the replacement or polysubstituted cyclopentadienyl group, and substituent R is selected from hydrogen, alkyl, aryl, alkenyl, alkyl silyl, alkenyl silyl etc. respectively; M is IVB family metal, i.e. transition metals Ti, zirconium or hafnium; Two X can be identical or different, can be aromatic yl alkyl group except halogen, alkoxy base, amine groups, alkyl group, aromatic yl group, kiki alkenyl group, kiki fang alkyl group, aromatic yl alkenyl group, silylation group or the benzyl etc.; R ₁Be phenoxy group adjacent substituting group, R ₂Be all the other locational one or more substituted radicals of phenoxy group phenyl ring.

Two adjacent substituting groups of above-mentioned polysubstituted cyclopentadiene group can be interconnected to condensed ring, generate indenes, replace indenes, fluorenes or substituted fluorene; Above-mentioned R ₁Being phenoxy group adjacent substituting group, can be hydrogen, alkyl group, aromatic yl group, substituted aryl group, aromatic yl alkenyl group, aromatic yl alkyl group, alkyl silyl group and silica-based alkyl group etc.; R ₂Be all the other locational one or more substituted radicals of phenoxy group phenyl ring, they can be the same or different, and can be hydrogen, alkyl group, aromatic yl group, substituted aryl group, aromatic yl alkenyl group, aromatic yl alkyl group, alkyl silyl group and silica-based alkyl group etc.

Cp encircles preferred cyclopentadienyl in the described catalyst structure formula, indenyl, and the above-mentioned group that fluorenyl or alkyl or aryl replace, wherein R can be a methyl, ethyl, propyl group, sec.-propyl, butyl, phenyl, the more preferably cyclopentadienyl of tetramethyl-and phenylbenzene replacement, most preferably tetramethyl-ring pentadienyl; Preferred titanium of M or zirconium; The preferred chlorine of X, methyl, trimethyl silicane ylmethyl or neo-pentyl; R ₁, R ₂Preferred alkyl, more preferably tertiary alkyl; R ₂The contraposition of optimum seeking site phenoxy group.

The comparatively preferred catalyzer of the present invention comprises: [2,4-di-t-butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] titanium dichloride, [the 2-tertiary butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] titanium dichloride, [2,4-dimethyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] titanium dichloride, [2-methyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] titanium dichloride, [2,4-diethyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] titanium dichloride, [2-ethyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] titanium dichloride, [2,4-dipropyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] titanium dichloride, [2-propyl group-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] titanium dichloride, [2,4-di-isopropyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] titanium dichloride, [2-sec.-propyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] titanium dichloride, [2,4-dibutyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] titanium dichloride, [2-butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] titanium dichloride,, [2,4-diisobutyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] titanium dichloride, [2-isobutyl--6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] titanium dichloride, [2,4-di neo-pentyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] titanium dichloride, [2-neo-pentyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] titanium dichloride, [2,4-dicyclohexyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] titanium dichloride, [2-cyclohexyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] titanium dichloride, [2,4-phenylbenzene-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] titanium dichloride, [2-phenyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] titanium dichloride, [2,4-di-t-butyl-6-(3,4-phenylbenzene cyclopentadienyl) phenoxy group] titanium dichloride, [the 2-tertiary butyl-6-(3,4-phenylbenzene cyclopentadienyl) phenoxy group] titanium dichloride, [2-phenyl-6-(3,4-phenylbenzene cyclopentadienyl) phenoxy group] titanium dichloride, [2-methyl-6-(3,4-phenylbenzene cyclopentadienyl) phenoxy group] titanium dichloride, [2,4-di-t-butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] the dimethyl titanium, [the 2-tertiary butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] the dimethyl titanium, [2,4-di-t-butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) the benzene oxidation] zirconium dichloride, [the 2-tertiary butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] zirconium dichloride, [2,4-dimethyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] zirconium dichloride, [2-methyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] zirconium dichloride, [2,4-diethyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] zirconium dichloride, [2-ethyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] zirconium dichloride, [2,4-dipropyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] zirconium dichloride, [2-propyl group-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] zirconium dichloride, [2,4-di-isopropyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] zirconium dichloride, [2-sec.-propyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] zirconium dichloride, [2,4-dibutyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] zirconium dichloride, [2-butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] zirconium dichloride, [2,4-diisobutyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] zirconium dichloride, [2-isobutyl--6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] zirconium dichloride, [2,4-di neo-pentyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] zirconium dichloride, [2-neo-pentyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] zirconium dichloride, [2,4-dicyclohexyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] zirconium dichloride, [2-cyclohexyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] zirconium dichloride, [2,4-phenylbenzene-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] zirconium dichloride, [2-phenyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] zirconium dichloride, [2,4-di-t-butyl-6-(3,4-phenylbenzene cyclopentadienyl) phenoxy group] zirconium dichloride, [the 2-tertiary butyl-6-(3,4-phenylbenzene cyclopentadienyl) phenoxy group] zirconium dichloride, [2-phenyl-6-(3,4-phenylbenzene cyclopentadienyl) phenoxy group] zirconium dichloride, [2-methyl-6-(3,4-phenylbenzene cyclopentadienyl) phenoxy group] zirconium dichloride, [2,4-di-t-butyl-6-(3,4-phenylbenzene cyclopentadienyl) phenoxy group] two (trimethyl silicane methyl) zirconium, [the 2-tertiary butyl-6-(3,4-phenylbenzene cyclopentadienyl) phenoxy group] two (trimethyl silicane methyl) zirconium, [2-phenyl-6-(3,4-phenylbenzene cyclopentadienyl) phenoxy group] two (trimethyl silicane methyl) zirconium, [2-methyl-6-(3,4-phenylbenzene cyclopentadienyl) phenoxy group] two (trimethyl silicane methyl) zirconium, [2,4-di-t-butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] the di neo-pentyl zirconium, [the 2-tertiary butyl-6-(3,4-phenylbenzene cyclopentadienyl) phenoxy group] the di neo-pentyl zirconium, [2-phenyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] the di neo-pentyl zirconium, [2-methyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] the di neo-pentyl zirconium.

Catalyzer of the present invention can prepare with following eight kinds of methods.

First method comprises the steps:

(1) in ether solvent, making strongly alkaline compound and a kind of ligand derivatives that contains the phenoxy group side chain is 2: 1 ratio stirring reaction in molar ratio, removes and desolvates, and obtains the metal-salt of part.

(2) in organic solvent, make the metal-salt and the MCl of part ₄By waiting molar ratio reaction, filter, gained filtrate is concentrated into solid separate out, collect solid and obtain metal chloride.

(1) step of aforesaid method, described strongly alkaline compound was selected from basic metal, alkalimetal hydride, alkali metal alkyl compound, alkali metal amino compound or alkyl halide magnesium, preferred lithium, sodium, potassium, sodium hydride, potassium hydride KH, butyllithium, sodium amide, lithium methide, methylmagnesium-chloride or benzylmagnesium chloride, described ether solvent is selected from ether or tetrahydrofuran (THF).This step, suitable temperature of reaction was-80～180 ℃, preferably-20～80 ℃, reaction times is 1～48 hour, preferred 1～12 hour, can earlier strongly alkaline compound be dissolved in the ether during operation, the ethereal solution that adds ligand derivatives more also can be opposite, and the add-on of ether solvent should be controlled at 20～100 times of reactant gross weight.

Second kind of preparation method's step of described catalyzer is as follows:

In ether solvent, make strongly alkaline compound and a kind of MCl ₄Be 2: 1 ratio stirring reaction in molar ratio, add the hydrocarbon solution of part then, heating systems filters, and gained filtrate is concentrated into solid separates out, and collects solid and obtains metal chloride.The described ether solvent of this method is identical with first method with strongly alkaline compound, and varsol is selected from saturated alkane or aromatic hydrocarbon, preferred hexane, toluene or dimethylbenzene.Its suitable temperature of reaction is-80～150 ℃, and preferred-20～100 ℃, the reaction times is 0.5～72 hour, preferred 2～36 hours.The reaction consumption of organic solvent should be 20～100 times of reaction raw materials summation.

The third preparation method's step of described catalyzer is as follows:

In organic solvent, the ligand derivatives and the MCl of mol ratios such as adding ₄, add the tertiary amine that doubles the part molar weight again, fully stir, solids removed by filtration is concentrated into solid with gained filtrate and separates out, and collects solid and obtains metal chloride.The preferred triethylamine of described tertiary amine, organic solvent is selected from ether, tetrahydrofuran (THF), methylene dichloride or toluene.Suitable temperature of reaction is-50～150 ℃, and preferred-10～100 ℃, the reaction times behind the adding tertiary amine is 0.5～108 hour, and preferred 5～48 hours, the reaction consumption of organic solvent should be 20～100 times of reaction raw materials.

The 4th kind of preparation method's step of described catalyzer is as follows:

In ether solvent, making strongly alkaline compound and a kind of ligand derivatives that contains the phenoxy group side chain is 2: 1 ratio stirring reaction in molar ratio, adds two normal trimethylchlorosilanes then, removes and desolvates, and obtains the part of trimethyl silicon based replacement.In varsol, make the part and the MCl of this replacement ₄By waiting molar ratio reaction, filter, gained filtrate is concentrated into solid separate out, collect solid and obtain metal chloride.Described varsol is selected from saturated alkane or aromatic hydrocarbon, preferred own a heatable brick bed or toluene.Suitable reaction is-50～150 ℃, and preferred-10～100 ℃, the reaction times is 0.5～108 hour, and preferred 1～72 hour, the reaction consumption of organic solvent should be 20～100 times of reaction raw materials.

The 5th kind of preparation method's step of described catalyzer is as follows:

In varsol, the ligand derivatives and the MCl of mol ratios such as adding ₄, stir after for some time, add a kind of lithium alkylide or alkyl Grignard reagent that doubles the part molar weight again, fully stir, solids removed by filtration is concentrated into solid with gained filtrate and separates out, and collects solid and obtains metal chloride.Described described varsol is selected from saturated alkane or aromatic hydrocarbon, preferred hexane or toluene.Lithium alkylide or alkyl Grignard reagent preferable methyl, phenyl, neo-pentyl, trimethyl silicane lithium methide or Grignard reagent, its suitable temperature of reaction is-80～150 ℃, preferred-20～100 ℃, the reaction times is 0.5～48 hour, preferred 2～12 hours.The reaction consumption of organic solvent should be 20～100 times of reaction raw materials summation.

The 6th kind of preparation method's step of described catalyzer is as follows:

In ether solvent, use a kind of lithium alkylide or alkyl Grignard reagent and a kind of MCl ₄Be 4: 1 ratio stirring reaction in molar ratio, add the hydrocarbon solution of part then, heating systems filters, and gained filtrate is concentrated into solid separates out, and collects solid and obtains metal alkyls.The described ether solvent of this method is identical with first method, and varsol is selected from saturated alkane or aromatic hydrocarbon, preferred hexane, toluene or dimethylbenzene.Lithium alkylide or alkyl Grignard reagent preferable methyl, phenyl, neo-pentyl, trimethyl silicane lithium methide or Grignard reagent, its suitable temperature of reaction is-80～150 ℃, preferred-20～100 ℃, the reaction times is 0.5～72 hour, preferred 2～24 hours.The reaction consumption of organic solvent should be 20～100 times of reaction raw materials summation.

The 7th kind of preparation method's step of described catalyzer is as follows:

In ether solvent, making strongly alkaline compound and a kind of ligand derivatives that contains the phenoxy group side chain is 2: 1 ratio stirring reaction in molar ratio, removes and desolvates, and obtains the metal-salt of part.Add this solution a kind of then by lithium alkylide or alkyl Grignard reagent and a kind of MCl ₄Be that the stirring reaction after-filtration is concentrated into solid with gained filtrate and separates out in the solution of gained behind 2: 1 the ratio stirring reaction in molar ratio, collect solid and obtain metal alkyls.The described ether solvent of this method is identical with first method, strongly alkaline compound is identical with first method, lithium alkylide or alkyl Grignard reagent preferable methyl, phenyl, neo-pentyl, trimethyl silicane lithium methide or Grignard reagent, its suitable temperature of reaction is-80～150 ℃, preferably-20～100 ℃, reaction times is 0.5～72 hour, preferred 2～36 hours.The reaction consumption of organic solvent should be 20～100 times of reaction raw materials summation.

The 8th kind of preparation method's step of described catalyzer is as follows:

Method one is dissolved in the ether solvent to method five resulting metal chlorides, under-78 ℃, in system, add a kind of lithium alkylide or alkyl Grignard reagent by two equivalents, kept this temperature 4 hours, room temperature reaction 2 hours, remove and desolvate, use hexane extraction, be concentrated into solid and separate out, collect solid and obtain metal alkyls.The described ether solvent of this method is identical with first method.Preferred ether.The reaction consumption of organic solvent should be 20～100 times of reaction raw materials summation.

The catalyzer that described eight kinds of methods obtain at last all need carry out purifying.The solvent that is used for purifying, alkane, halogenated alkane or their mixture of preferred C1～C10.

The purposes that contains the metallocene catalyst of phenoxy group side chain of the present invention is used for olefinic polymerization, and its method comprises with aforesaid any one metallocene compound and contacting with at least a alkene; With alkyl alumina a heatable brick bed, aluminum alkyls, alkyl aluminum halide, Ph ₃CB (C ₆F ₅) ₄, R ₄NB (C ₆F ₅) ₄, B (C ₆F ₅) ₃Or their mixture is a promotor; In the promotor in aluminium and the Primary Catalysts mol ratio of transition metal be 5～20000: 1, in the promotor in boron and the Primary Catalysts mol ratio of transition metal be 1～100: 1.

The constrained geometry configuration metallocene compound that the present invention contains the phenoxy group side chain cooperates with the promotor that suits, be used for ethene, propylene, iso-butylene, 1-butylene, the 1-hexene, the 1-octene, 1-decene and other end alkene less than 20 carbon, conjugation or unconjugated diene or polyenoid, vinylbenzene, norbornylene, the polymerization of olefinic monomers such as tetrahydrobenzene and ethene or propylene and iso-butylene, 1-butylene, the 1-hexene, the 1-octene, 1-decene and other end alkene less than 20 carbon also can be conjugation or unconjugated diene or polyenoid, vinylbenzene, norbornylene, the copolymerization of tetrahydrobenzene.

The example of suitable promotor generally comprised once and was total to any promotor of exhausted with the metallocene calalyst for polymerization of olefine that contains transition metal.Some typical examples comprise periodictable IA, the organo-metallic thing of IIA and IIIA family metal.The example of this compounds comprises organic metal halide, organo-metallic hydride or even metal hydride.Some concrete examples comprise trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, diethyl aluminum chloride, ADEH etc.An other class promotor is an alkylaluminoxane, is also referred to as poly-alkyl aluminum oxide sometimes, generally is that the prepared in reaction by organic hydrocarbyl aluminium compound and water obtains.Be widely known by the people most in the prior art.With regard to the present invention, most preferred promotor is organoboron compound (as: Ph ₃CB (C ₆F ₅) ₄, B (C ₆F ₅) ₃Or R ₄NB (C ₆F ₅) ₄) and the co-catalyst system formed of aluminum alkyls (as: trimethyl aluminium, triethyl aluminum or triisobutyl aluminium etc.).The amount of promotor can change in very wide scope.Aluminium wherein, the mol ratio of the transition metal in boron and the metallocene compound is preferably 1～1000: 1～10: 1, more preferably 1～150: 1～5: 1.Methylaluminoxane also is extraordinary promotor, but the active co-catalyst system that is lower than organoboron compound and aluminum alkyls composition.The mol ratio of the transition metal in aluminium and the metallocene compound is preferably 100～15000: 1, more preferably 1000～10000: 1.Polyreaction can be carried out in the liquor that catalyst system is had no adverse effect.This kind solvent comprises propane, butane, Trimethylmethane, pentane, hexane, heptane, octane, hexanaphthene, methylcyclohexane, toluene, dimethylbenzene or mixed alkanes etc.Polymeric reaction temperature can change in very wide scope, and typical temperature range is-20 ℃～200 ℃, and preferred scope is 20 ℃～160 ℃.Pressure range is 1～100 normal atmosphere or higher.

Catalyst structure of the present invention changes various, can significantly regulate and control the performance of catalyzer by the substituting group on change part and the central metal, thereby can be widely used in the homopolymerization and the copolymerization of catalyzed ethylene, propylene and various long-chain alpha-olefins, and the copolymerization of ethene, propylene and vinylbenzene, norbornylene.The good stability of catalyzer of the present invention, the catalytic activity height is particularly suitable for catalyzed ethylene, propylene and long-chain alpha olefin-copolymerization.

Embodiment

Further specify the present invention below by embodiment, but the present invention is not limited to this.

Embodiment 1 tetramethyl-ring pentadienyl replaces the preparation of part

With 2-bromo-4,6-DI-tert-butylphenol compounds 5g is dissolved in the 100mL anhydrous diethyl ether, adds two equivalent n-Butyl Lithiums down at-78 ℃, stirs 4 hours.Add 50mL and contain diethyl ether solution with the tetramethyl-ring pentenone of part equivalent, stirring is spent the night.With the saturated NH of 40mL ₄Cl aqueous hydrolysis and separatory add the 20mL concentrated hydrochloric acid in organic phase, stirring is spent the night, and use in the alkali and later separatory.Organic phase MgSO ₄Drying obtains pure products 2.9g, productive rate 50.7% through behind the silica gel column chromatography.

¹HNMR interpretation of result: δ=1.214 (d, 3H, C ₅Me ₄), 1.296 (s, 9H, Ar- ^tBu), 1.347 (s, 9H, Ar- ^tBu), 1.556 (s, 3H, C ₅Me ₄), 1.562 (s, 3H, C ₅Me ₄), 1.642 (s, 3H, C ₅Me ₄), 2.634 (q, 1H, Cp), 3.121 (s, 1H, OH), 7.031 (s, 1H, Ar), 7.091 (s, 1H, Ar).

Utilize this method can prepare the part that all contain the tetramethyl-ring pentadienyl, its process is narration one by one not.

Embodiment 23, and 4-phenylbenzene cyclopentadienyl replaces the preparation of part

4g is dissolved in the 100mL anhydrous diethyl ether with 2-bromo-6-tert.-butyl phenol, adds two equivalent n-Butyl Lithiums down at-78 ℃, stirs 4 hours.Add 50mL and contain and 3 of part equivalent, the diethyl ether solution of 4-phenylbenzene cyclopentenone, stirring is spent the night, and changes solvent into toluene, 75 ℃ of heating of water-bath three hours.With the saturated NH of 40mL ₄Cl aqueous hydrolysis and separatory, organic layer MgSO ₄Drying obtains pure products 2.2g, productive rate 46.6% through behind the silica gel column chromatography.

¹HNMR interpretation of result: δ=1.447 (s, 9H, Ar- ^tBu), 3.941 (s, 2H, Cp), 6.056 (s, 1H, OH), 6.990 (s, 1H, Cp), 6.894-7.373 (m, 13H, Ar).

Utilize this method can prepare all and contain 3, the part of 4-phenylbenzene cyclopentadienyl

Embodiment 3 1-indenyls replace the preparation of part

With 2-bromo-4,6-DI-tert-butylphenol compounds 5g is dissolved in the 100mL anhydrous diethyl ether, adds two equivalent n-Butyl Lithiums down at-78 ℃, stirs 4 hours.Add 50mL and contain diethyl ether solution with the 1-indone of part equivalent, stirring is spent the night.With the saturated NH of 40mL ₄Cl aqueous hydrolysis and separatory add the 20mL concentrated hydrochloric acid in organic phase, stirring is spent the night, and use in the alkali and later separatory.Organic phase MgSO ₄Drying obtains pure products 1.72g, productive rate 30.6% through behind the silica gel column chromatography.

¹HNMR interpretation of result: δ=1.332 (s, 9H, Ar- ^tBu), 1.455 (s, 9H, Ar- ^tBu), 3.610 (s, 2H, Cp), 5.581 (s, 1H, OH), 6.695 (s, 1H, Cp), 7.201-7.579 (m, 6H, Ar).

Utilize this method can prepare the part that all contain the 1-indenyl, its process is narration one by one not.

Embodiment 4 2-indenyls replace the preparation of part

6g is dissolved in the 100mL anhydrous diethyl ether with 2-bromo-4-tert.-butyl phenol, adds two equivalent n-Butyl Lithiums down at-78 ℃, stirs 4 hours.Add 50mL and contain diethyl ether solution with the 2-indone of part equivalent, stirring is spent the night, and changes solvent into toluene, 75 ℃ of heating of water-bath three hours.With the saturated NH of 40mL ₄Cl aqueous hydrolysis and separatory, organic layer MgSO ₄Drying obtains pure products 1.75g, productive rate 25.9% through behind the silica gel column chromatography.

¹HNMR interpretation of result: δ=1.443 (s, 9H, Ar- ^tBu), 3.766 (s, 2H, Ind), 5.987 (s, 1H, OH), 7.142 (s, 1H, Ind), 7.131-7.492 (m, 7H, Ar).

Utilize this method can prepare the part that all contain the 2-indenyl, its process is narration one by one not.

Embodiment 5 2-methyl isophthalic acid-indenyl replaces the preparation of part

5g is dissolved in the 100mL anhydrous diethyl ether with 2-bromo-6-tert.-butyl phenol, adds two equivalent n-Butyl Lithiums down at-78 ℃, stirs 4 hours.Add 50mL and contain diethyl ether solution with the 2-methyl isophthalic acid-indone of part equivalent, stirring is spent the night.With the saturated NH of 40mL ₄Cl aqueous hydrolysis and separatory add the 20mL concentrated hydrochloric acid in organic phase, stirring is spent the night, and use in the alkali and later separatory.Organic phase MgSO ₄Drying obtains pure products 2.15g, productive rate 35.4% through behind the silica gel column chromatography.

¹HNMR interpretation of result: δ=1.620 (s, 9H, Ar- ^tBu), 2.206 (s, 3H, Me), 3.63 (dd, 2H, Ind), 5.422 (s, 1H, OH), 7.08-7.57 (m, 7H, Ar).

Utilize this method can prepare the part that all contain 2-methyl isophthalic acid-indenyl, its process is narration one by one not.

Embodiment 6 2-ethyl～1-indenyl replaces the preparation of part

6g is dissolved in the 100mL anhydrous diethyl ether with 2-bromo-6-tert.-butyl phenol, adds two equivalent n-Butyl Lithiums down at-78 ℃, stirs 4 hours.Add 50mL and contain diethyl ether solution with the 2-ethyl-1-indone of part equivalent, stirring is spent the night.With the saturated NH of 40mL ₄Cl aqueous hydrolysis and separatory add the 20mL concentrated hydrochloric acid in organic phase, stirring is spent the night, and use in the alkali and later separatory.Organic phase MgSO ₄Drying obtains pure products 2.50g, productive rate 32.6% through behind the silica gel column chromatography.

¹HNMR interpretation of result: δ=1.15 (t, 3H, Me), 1.63 (s, 9H, Ar- ^tBu), 2.15 (q, 2H, CH ₂), 3.62 (dd, 2H, Ind), 5.46 (s, 1H, OH), 7.11-7.63 (m, 7H, Ar).

Utilize this method can prepare the part that all contain 2-ethyl-1-indenyl, its process is narration one by one not.

Embodiment 7 9-fluorenyls replace the preparation of part

5g is dissolved in the 100mL anhydrous diethyl ether with 2-bromo-6-tert.-butyl phenol, adds two equivalent n-Butyl Lithiums down at-78 ℃, stirs 4 hours.Add 50mL and contain diethyl ether solution with the 9-Fluorenone of part equivalent, stirring is spent the night.With the saturated NH of 40mL ₄Cl aqueous hydrolysis and separatory, concentrated organic phase gets pale yellow powder, is that solvent adds the HI solution of 0.8mL45% and the red phosphorus of 1.4g porphyrize with 20mL acetate, and saturated NaHCO is used in 105 ℃ of heating ₃The aqueous solution neutralizes with after-filtration, gained solid CH ₂Cl ₂Extraction, organic phase MgSO ₄Drying is removed and is desolvated crude product CH ₂Cl ₂With the hexane recrystallization, obtain pure products 2.3g, productive rate 27.5%.

¹HNMR interpretation of result: δ=1.475 (s, 9H, Ar- ^tBu), 4.987 (s, 1H, Cp), 5.775 (s, 1H, OH), 7.02-7.93 (m, 11H, Ar).

Utilize this method can prepare the part that all contain the 9-fluorenyl, its process is narration one by one not.

The preparation (Ti1) of embodiment 8 [2,4-di-t-butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] titanium dichloride

This compound can be prepared by following four kinds of methods.

Method one:

Under nitrogen atmosphere and-78 ℃ to containing 5mmolTiCl ₄With equivalent 2, in the 50mL toluene solution of 4-di-t-butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenol, drip two equivalents ⁿBuLi, stirring is spent the night.Filter with G4 fritted sand funnel, remove and desolvate crude product CH ₂Cl ₂With the hexane recrystallization.Get straight product 1.11g, productive rate 50.1%.

Method two:

Under nitrogen atmosphere and cryosel bath condition, to containing 5mmolTiCl ₄And 10mmol (Et) ₃The CH of N ₂Cl ₂Adding 20mL in the solution (50mL) contains and TiCl ₄2 of equivalent, the CH of 4-di-t-butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenol ₂Cl ₂Solution, stirring at room has a large amount of solids to separate out to system, filters with G4 fritted sand funnel, removes and desolvates crude product hexane recrystallization.Get straight product 0.74g, productive rate 33.4%.

Method three:

Under nitrogen atmosphere, with 1g 2,4-di-t-butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenol is dissolved in the 20mL ether, drips two equivalents under the cryosel bath temperature in system ⁿBuLi rises to and continues after the room temperature to stir two hours.System is placed again-15 ℃ cryosel bathe, in system, drip two equivalent (CH ₃) ₃The diethyl ether solution of SiCl (20mL).Rise to stir after the room temperature and spend the night.Remove ether, add the 30mL hexane.Under-78 ℃ of conditions, this solution added TiCl with the part equivalent ₄Hexane solution rose to after the room temperature water-bath (65～75 ℃) heating 24 hours.G4 fritted sand funnel filters, and behind the vacuum concentration, separates out straight product 0.51g, productive rate 37.6% under-20 ℃.

Method four:

Under nitrogen atmosphere and cryosel bath condition to containing 5mmol TiCl ₄The 20mL diethyl ether solution in drip two equivalent TMSCH ₂Li rises to and continues after the room temperature to stir one hour.System is placed again-15 ℃ cryosel bathe, drip in system and 2 of part equivalent, the 30mL toluene solution of 4-di-t-butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenol stirs water-bath after a hour (60 ℃) heating 24 hours.G4 fritted sand funnel filters, and removes and desolvates, and uses CH ₂Cl ₂With the hexane recrystallization.Get straight product 0.76g, productive rate 34.3%.

¹HNMR interpretation of result: δ=1.347 (s, 9H, Ar- ^tBu), 1.354 (s, 9H, Ar- ^tBu), 2.038 (s, 6H, C ₅Me ₄), 2.416 (s, 6H, C ₅Me ₄), 7.116 (d, 1H, Ar), 7.334 (d, 1H, Ar).

¹³CNMR interpretation of result: δ 171.6,146.9,145.7,143.6, and 134.8,130.1,128.9,123.4,123.1,35.0,34.8,31.7,29.5,13.5,13.0.

By the method among the embodiment 8, we have synthesized a series of compound, more than four kinds of methods all feasible for each compound, productive rate difference just.The highest method of the preferred productive rate of each compound in following examples.

The preparation (Ti2) of embodiment 9 [the 2-tertiary butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] titanium dichloride

Under nitrogen atmosphere and-78 ℃ to containing 5mmol TiCl ₄In the 50mL toluene solution of the equivalent 2-tertiary butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenol, drip two equivalents ⁿBuLi, stirring is spent the night.Filter with G4 fritted sand funnel, remove and desolvate crude product CH ₂Cl ₂With the hexane recrystallization.Get straight product 0.87g, productive rate 44.9%.

¹HNMR interpretation of result: δ=1.354 (s, 9H, Ar- ^tBu), 2.038 (s, 6H, C ₅Me ₄), 2.429 (s, 6H, C ₅Me ₄), 7.261 (s, 1H, Ar), 7.3 35 (d, 1H, AT), 7.352 (d, 1H, Ar).

¹³CNMR interpretation of result: δ 173.9,145.8,143.2,136.3, and 130.4,126.7,129.2,126.5,123.7,34.9,29.4,13.5,13.1.

The preparation (Ti3) of embodiment 10 [2-phenyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] titanium dichloride

Under nitrogen atmosphere and-78 ℃ to containing 5mmol TiCl ₄In the 50mL toluene solution of equivalent 2-phenyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenol, drip two equivalents ⁿBuLi, stirring is spent the night.Filter with G4 fritted sand funnel, remove and desolvate crude product CH ₂Cl ₂With the hexane recrystallization.Get straight product 0.82g, productive rate 40.3%.

¹HNMR interpretation of result: δ=2.113 (s, 6H, C ₅Me ₄), 2.444 (s, 6H, C ₅Me ₄), 7.243-7.640 (m, 8H, Ar)

¹³CNMR interpretation of result: δ 171.9,145.8,142.8,136.4, and 130.8,130.2,129.0,128.4,127.8,126.6,129.3,127.4,124.2,13.6,13.1.

The preparation (Ti4) of embodiment 11 [2-methyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] titanium dichloride

Under nitrogen atmosphere and-78 ℃ to containing 5mmolTiCl ₄In the 50mL toluene solution of equivalent 2-methyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenol, drip two equivalents ⁿBuLi, stirring is spent the night.Filter with G4 fritted sand funnel, remove and desolvate crude product CH ₂Cl ₂With the hexane recrystallization.Get straight product 0.45g, productive rate 26.1%.

¹HNMR interpretation of result: δ=2.177 (s, 3H, Ar-CH ₃), 2.060 (s, 6H, C ₅Me ₄), 2.426 (s, 6H, C ₅Me ₄), 7.033-7.359 (m, 3H, Ar).

¹³CNMR interpretation of result: δ 173.7,145.9,143.2,139.1, and 131.2,130.6,128.0,126.2,123.6,15.3,13.5,13.1.

The preparation (Ti5) of embodiment 12 [2,4-di-t-butyl-6-(2-indenyl) phenoxy group] titanium dichloride

Under nitrogen atmosphere, with 1g 2,4-di-t-butyl-6-(2-indenyl) phenol is dissolved in the 20mL ether, drips two equivalents under the cryosel bath temperature in system ⁿBuLi rises to and continues after the room temperature to stir two hours.System is placed again-15 ℃ cryosel bathe, in system, drip two equivalent (CH ₃) ₃The diethyl ether solution of SiCl (20mL).Rise to stir after the room temperature and spend the night.Remove ether, add the 30mL hexane.Under-78 ℃ of conditions, this solution added TiCl with the part equivalent ₄Hexane solution rose to after the room temperature water-bath (65～75 ℃) heating 24 hours.G4 fritted sand funnel filters, and behind the vacuum concentration, separates out straight product 0.53g, productive rate 38.8% under-20 ℃.

¹HNMR interpretation of result: δ=1.389 (s, 9H, Ar- ^tBu), 1.437 (s, 9H, Ar- ^tBu), 7.09 (s, 1H, Ind), 7.15-7.83 (m, 7H, Ar).

¹³CNMR interpretation of result: 171.6,147.9,145.7,143.6,136.5,134.8,132.2,130.3,126.7,124.5,123.1,35.0,34.8,31.8,29.5.

The preparation (Ti6) of embodiment 13 [the 2-tertiary butyl-6-(2-indenyl) phenoxy group] titanium dichloride

Under nitrogen atmosphere, the 1g 2-tertiary butyl-6-(2-indenyl) phenol is dissolved in the 20mL ether, under the cryosel bath temperature, in system, drip two equivalents ⁿBuLi rises to and continues after the room temperature to stir two hours.System is placed again-15 ℃ cryosel bathe, in system, drip two equivalent (CH ₃) ₃The diethyl ether solution of SiCl (20mL).Rise to stir after the room temperature and spend the night.Remove ether, add the 30mL hexane.Under-78 ℃ of conditions, this solution added TiCl with the part equivalent ₄Hexane solution rose to after the room temperature water-bath (65～75 ℃) heating 24 hours.G4 fritted sand funnel filters, and behind the vacuum concentration, separates out straight product 0.51g, productive rate 35.4% under-20 ℃.

¹HNMR interpretation of result: δ=1.443 (s, 9H, Ar- ^tBu), 7.13 (s, 1H, Ind), 7.24-7.78 (m, 7H, Ar).

¹³CNMR interpretation of result: δ 172.5,147.7,145.5,143.2, and 136.3,134.4,132.7,130.5,126.6,124.3,123.2,34.9,30.5.

The preparation (Ti7) of embodiment 14 [2.4-di-t-butyl-6-(9-fluorenyl) phenoxy group] titanium dichloride

Under nitrogen atmosphere, with 1g 2,4-di-t-butyl-6-(9-fluorenyl) phenol is dissolved in the 20mL ether, drips two equivalents under the cryosel bath temperature in system ⁿBuLi rises to and continues after the room temperature to stir two hours.System is placed again-15 ℃ cryosel bathe, in system, drip two equivalent (CH ₃) ₃The diethyl ether solution of SiCl (20mL).Rise to stir after the room temperature and spend the night.Remove ether, add the 30mL hexane.Under-78 ℃ of conditions, this solution added TiCl with the part equivalent ₄Hexane solution rose to after the room temperature water-bath (65～75 ℃) heating 24 hours.G4 fritted sand funnel filters, and behind the vacuum concentration, separates out straight product 0.44g, productive rate 33.5% under-20 ℃.

¹HNMR interpretation of result: δ=1.37 (s, 9H, Ar- ^tBu), 1.42 (s, 9H, Ar- ^tBu), and 7.00-8.19 (m, 10H, Ar).

¹³CNMR interpretation of result: δ 171.9,147.1,146.0,143.6, and 134.6,131.5,129.5,129.3,127.7,127.2,125.8,125.4,123.8,35.2,34.9,32.1,29.7.

The preparation (Ti8) of embodiment 15 [the 2-tertiary butyl-6-(9-fluorenyl) phenoxy group] titanium dichloride

Under nitrogen atmosphere, the 1g 2-tertiary butyl-6-(9-fluorenyl) phenol is dissolved in the 20mL ether, under the cryosel bath temperature, in system, drip two equivalents ⁿBuLi rises to and continues after the room temperature to stir two hours.System is placed again-15 ℃ cryosel bathe, in system, drip two equivalent (CH ₃) ₃The diethyl ether solution of SiCl (20mL).Rise to stir after the room temperature and spend the night.Remove ether, add the 30mL hexane.Under-78 ℃ of conditions, this solution added TiCl with the part equivalent ₄Hexane solution rose to after the room temperature water-bath (65～75 ℃) heating 24 hours.G4 fritted sand funnel filters, and behind the vacuum concentration, separates out straight product 0.43g, productive rate 31.4% under-20 ℃.

¹HNMR interpretation of result: δ=1.40 (s, 9H, Ar- ^tBu), and 7.01-8.14 (m, 11H, Ar).

¹³CNMR interpretation of result: δ 173.7,145.7,143.2,136.5, and 130.9,129.6,129.2,127.8,127.3,126.7,125.7,125.3,123.4,34.9,29.5.

Embodiment 16 [2,4-di-t-butyl-6-(3,4-phenylbenzene cyclopentadienyl) phenoxy group] dichloroChange the preparation (Ti9) of titanium

Under nitrogen atmosphere and cryosel bath condition,, add two equivalents in the 20mL diethyl ether solution of 4-di-t-butyl-6-(3,4-phenylbenzene cyclopentadienyl) phenol to containing 1g2 ⁿBuLi ₄, stirring at room two hours is added to the TiCl that is dissolved with the part equivalent with this drips of solution under-78 ℃ condition ₄Toluene solution in, be raised to room temperature, stirring is spent the night.Filter with G4 fritted sand funnel, remove and desolvate crude product CH ₂Cl ₂With the hexane recrystallization.Get straight product 0.72g, productive rate 56.4%.

¹HNMR interpretation of result: δ=1.365 (s, 18H, Ar- ^tBu), 7.184 (s, 2H, Cp), 7.330-7.572 (m, 12H, Ar).

¹³CNMR interpretation of result: δ 171.5,147.3,145.5,134.6, and 133.3,131.5,129.7,128.3,123.8,122.9,132.6,130.1,129.2,35.1,34.9,31.7,29.7.

Embodiment 17 [the 2-tertiary butyl-6-(3,4-phenylbenzene cyclopentadienyl) phenoxy group] titanium dichloridePreparation (Ti10)

Under nitrogen atmosphere and cryosel bath condition, in the 20mL diethyl ether solution that contains the 1g2-tertiary butyl-6-(3,4-phenylbenzene cyclopentadienyl) phenol, add two equivalents ⁿBuLi ₄, stirring at room two hours is added to the TiCl that is dissolved with the part equivalent with this drips of solution under-78 ℃ condition ₄Toluene solution in, be raised to room temperature, stirring is spent the night.Filter with G4 fritted sand funnel, remove and desolvate crude product CH ₂Cl ₂With the hexane recrystallization.Get straight product 0.63g, productive rate 47.8%.

¹HNMR interpretation of result: δ=1.366 (s, 9H, Ar- ^tBu), 7.165 (s, 2H, Cp), 7.107-7.581 (m, 13H, Ar).

¹³CNMR interpretation of result: δ 173.7,145.2,135.8,133.4, and 132.5,131.5,130.4,129.7,129.2,128.3,126.9,126.0,124.0,34.9,29.6.

The system of embodiment 18 [2-phenyl-6-(3,4-phenylbenzene cyclopentadienyl) phenoxy group] titanium dichlorideBe equipped with (Ti11)

Under nitrogen atmosphere and cryosel bath condition, in the 20mL diethyl ether solution that contains 1g2-phenyl-6-(3,4-phenylbenzene cyclopentadienyl) phenol, add two equivalents ⁿBuLi ₄, stirring at room two hours is added to the TiCl that is dissolved with the part equivalent with this drips of solution under-78 ℃ condition ₄Toluene solution in, be raised to room temperature, stirring is spent the night.Filter with G4 fritted sand funnel, remove and desolvate crude product CH ₂Cl ₂With the hexane recrystallization.Get straight product 0.52g, productive rate 39.9%.

¹HNMR interpretation of result: δ=7.214 (s, 2H, Cp), 7.0-7.74 (m, 18H, Ar).

¹³CNMR interpretation of result: δ 172.4,144.8,136.1,133.5, and 132.3,131.4,130.5,130.3,129.7,129.3,129.0,128.5,128.3,127.6,127.1,126.2,124.5.

Embodiment 19 [2-methyl-6-(3,4-phenylbenzene cyclopentadienyl) phenoxy group] titanium dichloridePreparation (Ti12)

Under nitrogen atmosphere and cryosel bath condition, in the 20mL diethyl ether solution that contains 1g2-methyl-6-(3,4-phenylbenzene cyclopentadienyl) phenol, add two equivalents ⁿBuLi ₄, stirring at room two hours is added to the TiCl that is dissolved with the part equivalent with this drips of solution under-78 ℃ condition ₄Toluene solution in, be raised to room temperature, stirring is spent the night.Filter with G4 fritted sand funnel, remove and desolvate crude product CH ₂Cl ₂With the hexane recrystallization.Get straight product 0.46g, productive rate 33.8%.

¹HNMR interpretation of result: δ=2.174 (s, 3H, CH ₃), 7.163 (s, 2H, Cp), 7.085-7.568 (m, 13H, Ar).

¹³CNMR interpretation of result: 173.6,153.6,145.2,133.6,132.6,131.8,131.6,130.0,129.5,128.6,125.8,124.3,123.3,15.5.

The system of embodiment 20 [2,4-di-t-butyl-6-(2-methyl isophthalic acid-indenyl) phenoxy group] titanium dichlorideBe equipped with (Ti13)

Under nitrogen atmosphere and cryosel bath condition,, add two equivalents in the 20mL diethyl ether solution of 4-di-t-butyl-6-(2-methyl isophthalic acid-indenyl) phenol to containing 1g2 ⁿBuLi ₄, stirring at room two hours is added to the TiCl that is dissolved with the part equivalent with this drips of solution under-78 ℃ condition ₄Toluene solution in, be raised to room temperature, stirring is spent the night.Filter with G4 fritted sand funnel, remove and desolvate crude product CH ₂Cl ₂With the hexane recrystallization.Get straight product 0.48g, productive rate 35.6%.

¹HNMR interpretation of result: δ=1.343 (s, 9H, Ar- ^tBu), 1.350 (s, 9H, Ar- ^tBu), 2.278 (s, 3H, CH ₃), 6.957 (s, 1H, Cp), 7.166-7.887 (m, 7H, Ar).

¹³CNMR interpretation of result: δ 175.7,148.5,145.2,136.8,136.3,129.0,128.6,128.0,127.5,127.5,126.6,124.3,123.9,119.5,109.8, δ 35.2,34.8,31.4,29.615.9.

The preparation of embodiment 21 [the 2-tertiary butyl-6-(2-methyl isophthalic acid-indenyl) phenoxy group] titanium dichloride(Ti14)

Under nitrogen atmosphere and cryosel bath condition, in the 20mL diethyl ether solution that contains the 1g2-tertiary butyl-6-(2-methyl isophthalic acid-indenyl) phenol, add two equivalents ⁿBuLi ₄, stirring at room two hours is added to the TiCl that is dissolved with the part equivalent with this drips of solution under-78 ℃ condition ₄Toluene solution in, be raised to room temperature, stirring is spent the night.Filter with G4 fritted sand funnel, remove and desolvate crude product CH ₂Cl ₂With the hexane recrystallization.Get straight product 0.44g, productive rate 31.0%.

¹HNMR interpretation of result: δ=1.350 (s, 9H, Ar- ^tBu), 2.299 (s, 3H, CH ₃), 6.974 (s, 1H, Cp), 7.163-7.867 (m, 7H, Ar).

¹³CNMR interpretation of result: δ 175.1,148.5,136.5,136.2, and 129.2,128.7,128.1,127.5,127.4,127.2,126.6,124.2,123.9,119.6,109.8,35.0,29.5,16.2.

Embodiment 22

The preparation (Ti15) of [2,4-di-t-butyl-6-(2-ethyl-1-indenyl) phenoxy group] titanium dichloride

Under nitrogen atmosphere and cryosel bath condition,, add two equivalents in the 20mL diethyl ether solution of 4-di-t-butyl-6-(2-ethyl-1-indenyl) phenol to containing 1g2 ⁿBuLi ₄, stirring at room two hours is added to the TiCl that is dissolved with the part equivalent with this drips of solution under-78 ℃ condition ₄Toluene solution in, be raised to room temperature, stirring is spent the night.Filter with G4 fritted sand funnel, remove and desolvate crude product CH ₂Cl ₂With the hexane recrystallization.Get straight product 0.50g, productive rate 37.5%.

¹HNMR interpretation of result: δ=1.347 (s, 9H, Ar- ^tBu), 1.353 (s, 9H, Ar- ^tBu), 1.17 (s, 3H, CH ₃), 2.28 (q, 2H, CH ₂), 7.09-7.88 (m, 7H, Ar).

¹³CNMR interpretation of result: δ 174.9,148.7,145.2,136.7, and 136.3,129.0,128.5,128.1,127.5,127.3,126.5,124.4,123.8,119.6,109.8,35.3,34.8,31.3,29.6,28.9,13.6.

The preparation of embodiment 23 [the 2-tertiary butyl-6-(2-ethyl-1-indenyl) phenoxy group] titanium dichloride(Ti16)

Under nitrogen atmosphere and cryosel bath condition, in the 20mL diethyl ether solution that contains the 1g2-tertiary butyl-6-(2-ethyl-1-indenyl) phenol, add two equivalents ⁿBuLi ₄, stirring at room two hours is added to the TiCl that is dissolved with the part equivalent with this drips of solution under-78 ℃ condition ₄Toluene solution in, be raised to room temperature, stirring is spent the night.Filter with G4 fritted sand funnel, remove and desolvate crude product CH ₂Cl ₂With the hexane recrystallization.Get straight product 0.48g, productive rate 34.3%.

¹HNMR interpretation of result: δ=1.358 (s, 9H, Ar- ^tBu), 1.13 (s, 3H, CH ₃), 2.35 (q, 2H, CH ₂), 6.99-7.82 (m, 7H, Ar).

¹³CNMR interpretation of result: δ 174.9,147.8,136.4,136.2, and 129.4,128.6,128.0,127.6,127.4,127.2,126.5,124.3,123.8,119.6,109.8,35.3,29.9,28.5,13.7.

Embodiment 24 [2,4-di-t-butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group]The preparation of dimethyl titanium (Ti17)

Under nitrogen atmosphere and-78 ℃ to containing 0.5g[2,4-di-t-butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] add the diethyl ether solution of two equivalent MeLi in the 30mL diethyl ether solution of titanium dichloride, kept this temperature 4 hours, after rising to room temperature gradually, continue to stir 2 hours, remove and desolvate hexane extraction.Separate out faint yellow crystallization 0.16g behind the concentrated frozen, productive rate 35.2%.

¹HNMR interpretation of result: δ=-0.054 (s, 6H, Me), 1.343 (s, 9H, Ar- ^tBu), 1.350 (s, 9H, Ar- ^tBu), 2.010 (s, H, C ₅Me ₄), 2.395 (s, 6H, C ₅Me ₄), 7.108 (d, 1H, Ar), 7.287 (d, 1H, Ar).

Embodiment 25 [2,4-di-t-butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group]The preparation of phenylbenzene titanium (Ti18)

Under nitrogen atmosphere and-78 ℃ to containing 0.5g[2,4-di-t-butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] add the diethyl ether solution of two equivalent PhLi in the 30mL diethyl ether solution of titanium dichloride, kept this temperature 4 hours, after rising to room temperature gradually, continue to stir 2 hours, remove and desolvate hexane extraction.Separate out faint yellow crystallization 0.22g behind the concentrated frozen, productive rate 37.0%.

¹HNMR interpretation of result: δ=1.345 (s, 9H, Ar- ^tBu), 1.351 (s, 9H, Ar- ^tBu), 2.014 (s, 6H, C ₅Me ₄), 2.392 (s, 6H, C ₅Me ₄), 7.079-7.341 (m, 12H, Ar).

Embodiment 26 [the 2-tertiary butyl-6-(3,4-phenylbenzene cyclopentadienyl) phenoxy group] two (trimethylammoniumsThe silicon methyl) preparation of zirconium (Zr1)

Under nitrogen atmosphere and-78 ℃ to containing 0.3gZrCl ₄Add four equivalent TMSCH in the powder 30mL ether suspension liquid ₂The hexane solution of Li, rise to room temperature gradually after, continue to stir 4 hours, remove and desolvate, add 50mL toluene, stirring and dissolving places-15 ℃ cryosel to bathe, and drips and ZrCl in system ₄The 2-tertiary butyl-the 6-of equivalent (3,4-phenylbenzene cyclopentadienyl) phenol stirs under the room temperature and spends the night, water-bath (60 ℃) heating 24 hours.Remove and desolvate hexane extraction.Separate out faint yellow crystallization 0.35g behind the concentrated frozen, productive rate 43.1%.

¹HNMR interpretation of result: δ=-0.09 (s, 18H, Si-Me) ,-0.04 (s, 4H, CH ₂), 1.33 (s, 9H, Ar- ^tBu), and 6.01-7.57 (m, 15H, Cp, Ar).

Embodiment 27 [2,4-di-t-butyl-6-(3,4-phenylbenzene cyclopentadienyl) phenoxy group] two (threeMethyl silicon methyl) preparation (Zr2) of zirconium

Under nitrogen atmosphere and-78 ℃ to containing 0.3gZrCl ₄Add four equivalent TMSCH in the powder 30mL ether suspension liquid ₂The hexane solution of Li, rise to room temperature gradually after, continue to stir 4 hours, remove and desolvate, add 50mL toluene, stirring and dissolving places-15 ℃ cryosel to bathe, and drips and ZrCl in system ₄2 of equivalent, 4-di-t-butyl-6-(3,4-phenylbenzene cyclopentadienyl) phenol stirs under the room temperature and spends the night, water-bath (60 ℃) heating 24 hours.Remove and desolvate hexane extraction.Separate out faint yellow crystallization 0.43g behind the concentrated frozen, productive rate 48.7%.

¹HNMR interpretation of result: δ=-0.10 (s, 18H, Si-Me) ,-0.04 (s, 4H, CH ₂), 1.10 (s, 9H, Ar- ^tBu), 1.36 (s, 9H, Ar- ^tBu), and 6.15-7.59 (m, 14H, Cp, Ar).

Embodiment 28 [2-phenyl-6-(3,4-phenylbenzene cyclopentadienyl) phenoxy group] two (trimethylammoniumsThe silicon methyl) preparation of zirconium (Zr3)

Under nitrogen atmosphere and-78 ℃ to containing 0.3gZrCl ₄Add four equivalent TMSCH in the powder 30mL ether suspension liquid ₂The hexane solution of Li, rise to room temperature gradually after, continue to stir 4 hours, remove and desolvate, add 50mL toluene, stirring and dissolving places-15 ℃ cryosel to bathe, and drips and ZrCl in system ₄2-phenyl-the 6-of equivalent (3,4-phenylbenzene cyclopentadienyl) phenol stirs under the room temperature and spends the night, water-bath (60 ℃) heating 24 hours.Remove and desolvate hexane extraction.Separate out faint yellow crystallization 0.33g behind the concentrated frozen, productive rate 39.4%.

¹HNMR interpretation of result: δ=-0.11 (s, 18H, Si-Me) ,-0.04 (s, 4H, CH ₂), 6.00-7.97 (m, 20H, Cp, Ar).

Embodiment 29 [the 2-tertiary butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] twoThe preparation (Zr4) of (trimethyl silicane methyl) zirconium

Under nitrogen atmosphere and-78 ℃ to containing 0.3gZrCl ₄Add four equivalent TMSCH in the powder 30mL ether suspension liquid ₂The hexane solution of Li, rise to room temperature gradually after, continue to stir 4 hours, remove and desolvate, add 50mL toluene, stirring and dissolving places-15 ℃ cryosel to bathe, and drips and ZrCl in system ₄The 2-tertiary butyl-the 6-of equivalent (2,3,4,5-tetramethyl-ring pentadienyl) phenol stirs under the room temperature and spends the night, water-bath (60 ℃) heating 24 hours.Remove and desolvate hexane extraction.Separate out pale yellow powder 0.25g behind the concentrated frozen, productive rate 36.4%.

¹HNMR interpretation of result: δ=-0.11 (s, 18H, Si-Me) ,-0.03 (s, 4H, CH ₂), 1.34 (s, 9H, Ar- ^tBu), 1.95 (s, 6H, C ₅Me ₄), 2.33 (s, 6H, C ₅Me ₄), 7.19-7.35 (m, 1H, Ar).

Embodiment 30 [2,4-di-t-butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group]The preparation (Zr5) of two (trimethyl silicane methyl) zirconium

Under nitrogen atmosphere and-78 ℃ to containing 0.3gZrCl ₄Add four equivalent TMSCH in the powder 30mL ether suspension liquid ₂The hexane solution of Li, rise to room temperature gradually after, continue to stir 4 hours, remove and desolvate, add 50mL toluene, stirring and dissolving places-15 ℃ cryosel to bathe, and drips and ZrCl in system ₄2 of equivalent, 4-di-t-butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenol stirs under the room temperature and spends the night, water-bath (60 ℃) heating 24 hours.Remove and desolvate hexane extraction.Separate out pale yellow powder 0.33g behind the concentrated frozen, productive rate 43.4%.

¹HNMR interpretation of result: δ=-0.09 (s, 18H, Si-Me) ,-0.03 (s, 4H, CH ₂), 1.35 (s, 9H, Ar- ^tBu), 1.42 (s, 9H, Ar- ^tBu), 2.00 (s, 6H, C ₅Me ₄), 2.37 (s, 6H, C ₅Me ₄), 7.11 (d, 1H, Ar), δ=7.24 (d, 1H, Ar).

Embodiment 31 [2-phenyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] two (threeMethyl silicon methyl) preparation (Zr6) of zirconium

Under nitrogen atmosphere and-78 ℃ to containing 0.3gZrCl ₄Add four equivalent TMSCH in the powder 30mL ether suspension liquid ₂The hexane solution of Li, rise to room temperature gradually after, continue to stir 4 hours, remove and desolvate, add 50mL toluene, stirring and dissolving places-15 ℃ cryosel to bathe, and drips and ZrCl in system ₄2-phenyl-the 6-of equivalent (2,3,4,5-tetramethyl-ring pentadienyl) phenol stirs under the room temperature and spends the night, water-bath (60 ℃) heating 24 hours.Remove and desolvate hexane extraction.Separate out pale yellow powder 0.23g behind the concentrated frozen, productive rate 32.2%.

¹HNMR interpretation of result: δ=-0.10 (s, 18H, Si-Me) ,-0.04 (s, 4H, CH ₂), 2.08 (s, 6H, C ₅Me ₄), 2.35 (s, 6H, C ₅Me ₄), 7.13-7.68 (m, 8H, Ar)

Embodiment 32 [2, the 4--tertiary butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group]The preparation of zirconium dichloride (Zr7)

Under nitrogen atmosphere and cryosel bath condition to containing 2mmolZrCl ₄The 20mL diethyl ether solution in drip two equivalent TMSCH ₂Li rises to and continues after the room temperature to stir one hour.System is placed again-15 ℃ cryosel bathe, drip in system and 2 of part equivalent, the 30mL toluene solution of 4-di-t-butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenol stirs water-bath after a hour (60 ℃) heating 24 hours.G4 fritted sand funnel filters, and removes and desolvates, and uses CH ₂Cl ₂With the hexane recrystallization.Get straight product 0.34g, productive rate 34.9%.

¹HNMR interpretation of result: δ=1.36 (s, 9H, Ar- ^tBu), 1.40 (s, 9H, Ar- ^tBu), 2.04 (s, 6H, C ₅Me ₄), 2.42 (s, 6H, C ₅Me ₄), 7.13 (d, 1H, Ar), 7.34 (d, 1H, Ar).

Embodiment 33 [the 2-tertiary butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] dichloroChange the preparation (Zr8) of zirconium

Under nitrogen atmosphere and cryosel bath condition to containing 2mmolZrCl ₄The 20mL diethyl ether solution in drip two equivalent TMSCH ₂Li rises to and continues after the room temperature to stir one hour.System is placed again-15 ℃ cryosel bathe, the 30mL toluene solution of the 2-tertiary butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenol of dropping and part equivalent in system stirs water-bath after a hour (60 ℃) heating 24 hours.G4 fritted sand funnel filters, and removes and desolvates, and uses CH ₂Cl ₂With the hexane recrystallization.Get straight product 0.26g, productive rate 30.2%.

¹HNMR interpretation of result: δ=1.358 (s, 9H, Ar- ^tBu), 2.04 (s, 6H, C ₅Me ₄), 2.44 (s, 6H, C ₅Me ₄), 7.21-7.37 (m, 1H, Ar).

Embodiment 34 [2,4-di-t-butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group]The preparation (Zr9) of two (hot amyl group) zirconium

Under nitrogen atmosphere and-78 ℃ to containing 0.3gZrCl ₄The hexane solution that adds the hot amyl group lithium of four equivalents in the powder 30mL ether suspension liquid, rise to room temperature gradually after, continue to stir 4 hours, remove and desolvate, add 50mL toluene, stirring and dissolving places-15 ℃ cryosel to bathe, and drips and ZrCl in system ₄2 of equivalent, 4-di-t-butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenol stirs under the room temperature and spends the night, water-bath (60 ℃) heating 24 hours.Remove and desolvate hexane extraction.Separate out pale yellow powder 0.31g behind the concentrated frozen, productive rate 43.2%.

¹HNMR interpretation of result: δ=-0.01 (s, 4H, CH ₂), 1.19 (s, 18H, Me), 1.37 (s, 9H, Ar- ^tBu), 1.45 (s, 9H, Ar- ^tBu), 2.04 (s, 6H, C ₅Me ₄), 2.40 (s, 6H, C ₅Me ₄), 7.15 (d, 1H, Ar), δ=7.27 (d, 1H, Ar).

The polymerization of embodiment 35 ethene (withPh ₃CB (C ₆F ₅) ₄ With triisobutyl aluminium be promotor)

Be aggregated in the 250mL autoclave and carry out, reactor 110 ℃ of bakings 1 hour under vacuum charge into an atmospheric ethene before the polymerization, and 90mL is contained a certain amount of Ph ₃CB (C ₆F ₅) ₄Toluene solution add in the reactor, under agitation condition, reaction system is heated to assigned temperature, then, flow down and to contain in toluene solution (10mL) injecting reactor of 1mg catalyzer and certain proportion triisobutyl aluminium at ethylene gas by a special feeder, ethylene pressure is risen to 5 normal atmosphere, and pick up counting.Do not indicate as special, the reaction times is generally 30min.Reaction finishes back emptying reactor, stops polyreaction with the 5%HCl/ methanol solution.Leach polymkeric substance, water and methyl alcohol thorough washing, 60 ℃ of vacuum-dryings are to constant weight.

The results are summarized in table 35.1 to table 35.10 with what different catalysts obtained, wherein be respectively in each independently in the form by different experiment conditions by the difference of part.In table, polymerization continues 30 minutes, and the boron in the promotor and the mol ratio of the transition metal in the Primary Catalysts are 2, unless explanation is arranged in addition.By the molecular weight of limiting viscosity (Mn) comparative polymers, utilize the accurate capillary viscosimeter of Ubbelohde in perhydronaphthalene, to measure in 135 ± 0.1 ℃.Before measuring, polymer samples is weighed in sealable little flask and was dissolved 3～4 hours in 140～150 ℃ in the naphthalane of accurate weighed amount.Remove indissolvable component through the glass fiber heat filtering.Utilize existing working curve to determine inherent viscosity.

Table 35.1: with [the 2-tertiary butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) benzene oxidation] titanium dichloride is catalyzer.

????Al∶Ti	???B∶Ti	????T(℃)	??Wt?of ??polymer(g)	???Activity(× ??????10 -6)	????Mη	????Tm(℃)
							????100	???2	????80	??2.66	???2.06	????67000	????131.825
????75	???2	????80	??4.42	???3.42	????94000	????131.723
							????50	???2	????80	??3.43	???2.66	????59000	????130.558
????75	???2	????100	??2.25	???1.74	????42000	????130.189
							????75	???2	????60	??1.68	???1.30	????150000	????132.179
????75	???2	????40	??0.51	???0.39	????140000	????131.879

Table 35.2: with [2,4-di-t-butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) benzene oxidation] titanium dichloride is catalyzer.

????Al∶Ti	???B∶Ti	???T(℃)	??Wt?of ??polymer(g)	????Activity(× ???????10 -6)	????Mη	????Tm(℃)
							????100a	???2	???80	??3.43	????6.08	????76000	????132.207
????125	???2	???80	??2.53	????2.24	????73000	????129.708
							????100	???2	???80	??5.12	????4.54	????107000	????131.851
????75	???2	???80	??3.63	????3.22	????72000	????129.317
							????50	???2	???80	??2.30	????2.04	????72000	????129.167

Annotate: a: catalyst levels is 0.5 milligram.

Table 35.3: with [2-phenyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) benzene oxidation] titanium dichloride is catalyzer.

????Al∶Ti	???B∶Ti	???T(℃)	??Wt?of ??polymer(g)	???Activity(× ??????10 -5)	????Mη	????Tm(℃)
							????75	???2	???80	??0.29	???2.36	????23000	????130.259
????50	???2	???80	??0.56	???4.56	????35000	????130.508
							????30	???2	???80	??0.81	???6.60	????37000	????131.364
????20	???2	???80	??0.19	???1.55	????38000	????131.349

Table 35.4: with [2-methyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) benzene oxidation] titanium dichloride is catalyzer.

????Al∶Ti	???B∶Ti	???T(℃)	??Wt?of ??polymer(g)	????Activity(× ???????10 -5)	????Mη	????Tm(℃)
							????50	???2	???80	??0.97	????6.69	????43000	????131.249
????30	???2	???80	??1.53	????10.56	????45000	????130.897
							????20	???2	???80	??0.85	????5.87	????39000	????131.045

Table 35.5: with [2,4-di-t-butyl-6-(3,4-phenylbenzene cyclopentadienyl) benzene oxidation] titanium dichloride is catalyzer.

????Al∶Ti	???B∶Ti	???T(℃)	??Wt?of ??polymer(g)	???Activity(× ??????10 -6)	????Mη	????Tm(℃)
							????125	???2	???80	??0.85	???0.92	????43000	????121.149
????100	???2	???80	??1.97	???2.13	????32000	????125.749
							????75	???2	???80	??3.86	???4.16	????38000	????125.400
????50	???2	???80	??2.45	???2.64	????29000	????121.670

Table 35.6: with [the 2-tertiary butyl-6-(3,4-phenylbenzene cyclopentadienyl) benzene oxidation] titanium dichloride is catalyzer, with Ph ₃CB (C ₆F ₅) ₄With triisobutyl aluminium be promotor.

????Al∶Ti	????B∶Ti	???T(℃)	??Wt?of ??polymer(g)	????Activity(× ????????10 -6)	????Mη	????Tm(℃)
							????75	????2.0	???80	??1.87	????1.81	????120000	????122.354
????50	????2.0	???80	??2.55	????2.46	????89000	????124.260
							????40	????2.0	???80	??2.02	????1.95	????56000	????125.299
????30	????2.0	???80	??0.56	????0.54	????45000	????125.420

Table 35.7: with [2-phenyl-6-(3,4-phenylbenzene cyclopentadienyl) benzene oxidation] titanium dichloride is catalyzer.

??Al∶Ti	????B∶Ti	????T(℃)	??Wt?of ??polymer(g)	???Activity(× ??????10 -5)	??Mη	????Tm(℃)
							??50	????2.0	????80	??0.34	???3.42	??220000	????140.725
??30	????2.0	????80	??0.54	???5.43	??210000	????132.565
							??20	????2.0	????80	??0.22	???2.21	??120000	????140.5615
??30	????2.0	????100	??0.16	???1.61	??130000	????128.138
							??30	????2.0	????60	??0.14	???1.41	??140000	????127.138

Table 35.8: with [2-methyl-6-(3,4-phenylbenzene cyclopentadienyl) benzene oxidation] titanium dichloride is catalyzer.

?Al∶Ti

?B∶Ti

?T(℃)

??Wt?of ??polymer(g)

??Activity(× ?????10 -5)

????Mη

????Tm(℃)

????75	????2	????80	????0.53	????4.68	????130000	????121.012
							????50	????2	????80	????0.72	????6.35	????92000	????122.465
????30	????2	????80	????0.86	????7.59	????94000	????122.956
							????20	????2	????80	????0.69	????6.09	????100000	????l20.927

Table 35.9: with other titanium-containing compound is catalyzer.

??catalyst	??Al∶Ti	??Wt?of ??polymer(g)	??Activity(× ????10 -6)	??Mη	??Tm(℃)
						??Ti5	??75	??3.47	??3.03	??41000	??123.546
??Ti6	??50	??2.94	??2.24	??68000	??122.549
						??Ti7	??100	??2.81	??2.74	??39000	??123.541
??Ti8	??75	??1.97	??1.70	??34000	??123.672
						??Ti13	??100	??3.93	??3.55	??86000	??133.085
??Ti14	??75	??3.54	??2.80	??77000	??132.473
						??Ti15	??100	??4.11	??3.82	??59000	??127.433
??Ti16	??75	??3.52	??2.88	??63000	??127.137

Annotate: B: Ti=2, temperature of reaction is 80 ℃.

Table 35.10: with the zirconium-containing compound is catalyzer.

??catalyst	??Al∶Ti	??Wt?of ??polymer(g)	??Activity(× ????10 -6)	??Mη	??Tm(℃)
						??Zr1	??5	??2.49	??3.14	??45000	??126.538
??Zr2	??5	??3.32	??4.56	??56000	??124.687
						??Zr3	??5	??1.09	??1.42	??65000	??125.983
??Zr4	??5	??4.25	??4.54	??86000	??129.623
						??Zr5	??5	??4.87	??5.75	??69000	??131.716
??Zr6	??5	??1.12	??1.24	??36000	??130.347
						??Zr7	??100	??4.69	??4.56	??92000	??132.234
??Zr8	??75	??3.98	??3.43	??75000	??131.875

Annotate: B: Zr=2, temperature of reaction is 80 ℃.

The polymerization of embodiment 36 ethene (withCB (C ₆F ₅) ₃ With triisobutyl aluminium be promotor)

Be aggregated in the 250mL autoclave and carry out, reactor 110 ℃ of bakings 1 hour under vacuum charge into an atmospheric ethene before the polymerization, and 90mL is contained a certain amount of B (C ₆F ₅) ₃Toluene solution add in the reactor, under agitation condition, reaction system is heated to assigned temperature, then, flow down and to contain in toluene solution (10mL) injecting reactor of 1mg catalyzer and certain proportion triisobutyl aluminium at ethylene gas by a special feeder, ethylene pressure is risen to 5 normal atmosphere, and pick up counting.Do not indicate as special, the reaction times is generally 30min.Reaction finishes back emptying reactor, stops polyreaction with the 5%HCl/ methanol solution.Leach polymkeric substance, water and methyl alcohol thorough washing, 60 ℃ of vacuum-dryings are to constant weight.The results are summarized in table 36.1 to table 36.4 with what different catalysts obtained, wherein be respectively in each independently in the form by different experiment conditions by the difference of part.In table, polymerization continues 30 minutes, and the boron in the promotor and the mol ratio of the transition metal in the Primary Catalysts are 2, unless explanation is arranged in addition.Molecular weight by limiting viscosity (Mn) comparative polymers.

Table 36.1: with [2,4-di-t-butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) benzene oxidation] titanium dichloride is catalyzer.

????Al∶Ti	???B∶Ti	???T(℃)	??Wt?of ??polymer(g)	????Activity(× ???????10 -6)	????Mη	????Tm(℃)
							????125	???2	???80	??2.02	????1.79	????76000	????131.159
????100	???2	???80	??4.15	????3.68	????79000	????132.078
							????75	???2	???80	??2.87	????2.54	????81000	????129.571
????50	???2	???80	??1.86	????1.65	????71000	????131.664

Table 36.2: with [the 2-tertiary butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) benzene oxidation] titanium dichloride is catalyzer.

????Al∶Ti	???B∶Ti	???T(℃)	??Wt?of ??polymer(g)	???Activity(× ??????10 -6)	????Mη	????Tm(℃)
							????100	???2	???80	??2.15	???1.66	????95000	????131.719
????75	???2	???80	??3.54	???2.74	????87000	????130.852
							????50	???2	???80	??2.78	???2.15	????69000	????132.007

Table 36.3: with [2,4-di-t-butyl-6-(3,4-phenylbenzene cyclopentadienyl) benzene oxidation] titanium dichloride is catalyzer.

????Al∶Ti	???B∶Ti	???T(℃)	??Wt?of ??polymer(g)	???Activity(× ??????10 -6)	????Mη	????Tm(℃)
							????100	???2	???80	??1.63	???1.76	????42000	????125.643
????75	???2	???80	??3.09	???3.33	????48000	????125.421
							????50	???2	???80	??1.98	???2.14	????52000	????124.433

Table 36.4: with [the 2-tertiary butyl-6-(3,4-phenylbenzene cyclopentadienyl) benzene oxidation] titanium dichloride is catalyzer, with Ph ₃CB (C ₆F ₅) ₄With triisobutyl aluminium be promotor.

????Al∶Ti	????B∶Ti	???T(℃)	??Wt?of ??polymer(g)	????Activity(× ???????10 -6)	????Mη	????Tm(℃)
							????75	????2.0	???80	??1.51	????1.46	????56000	????124.654
????50	????2.0	???80	??2.09	????2.02	????63000	????125.032
							????40	????2.0	???80	??1.65	????1.59	????59000	????124.867

????30

?????2.0

????80

?????0.46

????0.44

??57000

??124.934

The polymerization of embodiment 37 ethene (methylaluminoxane is a promotor)

Be aggregated in the 250mL autoclave and carry out, reactor 110 ℃ of bakings 1 hour under vacuum before the polymerization, charge into an atmospheric ethene, the toluene solution that 90mL is contained a certain amount of methylaluminoxane (MAO) adds in the reactor, under agitation condition, reaction system is heated to assigned temperature, then, flow down and to contain in toluene solution (10mL) injecting reactor of 1mg catalyzer and certain proportion triisobutyl aluminium at ethylene gas by a special feeder, ethylene pressure is risen to 5 normal atmosphere, and pick up counting.Do not indicate as special, the reaction times is generally 30min.Reaction finishes back emptying reactor, stops polyreaction with the 5%HCl/ methanol solution.Leach polymkeric substance, water and methyl alcohol thorough washing, 60 ℃ of vacuum-dryings are to constant weight.The results are summarized in table 37.1 to table 37.4 with what different catalysts obtained, wherein be respectively in each independently in the form by different experiment conditions by the difference of part.In table, polymerization continues 30 minutes, and the boron in the promotor and the mol ratio of the transition metal in the Primary Catalysts are 2, unless explanation is arranged in addition.Molecular weight by limiting viscosity (Mn) comparative polymers.

Table 37.1: with [the 2-tertiary butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) benzene oxidation] titanium dichloride is catalyzer.

????Al∶Ti	????T(℃)	??Wt?of ??polymer(g)	???Activity(× ??????10 -5)	????Mη	????Tm(℃)
						????4000	????80	??1.10	???8.52	????75000	????131.719
????3000	????80	??0.83	???6.42	????87000	????130.852
						????2000	????100	??0.57	???4.41	????69000	????132.007
????1000	????60	??0.22	???1.70	????81000	????131.327

Table 37.2: with [2,4-di-t-butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) benzene oxidation] titanium dichloride is catalyzer.

????Al∶Ti	???T(℃)	??Wt?of ??polymer(g)	???Activity(× ??????10 -6)	????Mη	????Tm(℃)
						????4000	???80	??1.30	???1.15	????83000	????132.467
????3000	???80	??0.98	???0.87	????75000	????130.708
						????2000	???80	??0.55	???0.49	????86000	????129.911
????1000	???80	??0.30	???0.27	????79000	????131.381

Table 37.3: with [2,4-di-t-butyl-6-(3,4-phenylbenzene cyclopentadienyl) benzene oxidation] titanium dichloride is catalyzer.

??Al∶Ti

?T(℃)

??Wt?of ??polymer(g)

??Activity(× ?????10 -6)

??Mη

????Tm(℃)

????4000	????80	????0.95	????1.02	????54000	????125.988
						????3000	????80	????0.77	????0.83	????47000	????125.420
????2000	????80	????0.46	????0.50	????45000	????124.521
						????1000	????80	????0.20	????0.22	????54000	????125.982

Table 37.4: with [the 2-tertiary butyl-6-(3,4-phenylbenzene cyclopentadienyl) benzene oxidation] titanium dichloride is catalyzer.

????Al∶Ti	???T(℃)	??Wt?of ??polymer(g)	????Activity(× ????????10 -5)	????Mη	????Tm(℃)
						????4000	???80	??0.64	????6.18	????65000	????127.595
????3000	???80	??0.55	????5.32	????67000	????126.684
						????2000	???80	??0.37	????3.58	????57000	????127.137
????1000	???80	??0.11	????1.06	????61000	????128.175

The copolymerization of embodiment 38 ethene and hexene (withPh ₃CB (C ₆F ₅) ₄ With triisobutyl aluminium be promotor)

Be aggregated in the 250mL autoclave and carry out, reactor 110 ℃ of bakings 1 hour under vacuum charge into an atmospheric ethene before the polymerization, and 90mL is contained a certain amount of Ph ₃CB (C ₆F ₅) ₄Add in the reactor with the toluene solution of hexene, under agitation condition, reaction system is heated to assigned temperature, then, flow down and to contain in toluene solution (10mL) injecting reactor of 1mg catalyzer and certain proportion triisobutyl aluminium at ethylene gas by a special feeder, ethylene pressure is risen to 5 normal atmosphere, and pick up counting.Do not indicate as special, the reaction times is generally 30min.Reaction finishes back emptying reactor, stops polyreaction with the 5%HCl/ methanol solution.Leach polymkeric substance, water and methyl alcohol thorough washing, 60 ℃ of vacuum-dryings are to constant weight.The results are summarized in table 38.1 to table 38.5 with what different catalysts obtained, wherein be respectively in each independently in the form by different experiment conditions by the difference of part.In table, polymerization continues 30 minutes, and the boron in the promotor and the mol ratio of the transition metal in the Primary Catalysts are 2, unless explanation is arranged in addition.Molecular weight by limiting viscosity (Mn) comparative polymers.

Table 38.1: with [2,4-di-t-butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) benzene oxidation] titanium dichloride is catalyzer, with Ph ₃CB (C ₆F ₅) ₄With triisobutyl aluminium be promotor.

????Al∶Ti	????Hexene(mmol)	??Wt?of ??polymer(g)	????Activity(× ???????10 -6)	????Mη	????Tm(℃)
						????100	????10	??6.25	????5.54	????66000	????122.345
????100	????20	??7.11	????6.30	????76000	????111.179
						????100	????30	??7.04	????6.24	????72000	????93.204
????100	????40	??7.23	????6.41	????69000	????81.956

Table 38.2: with [the 2-tertiary butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) benzene oxidation] titanium dichloride is catalyzer, with Ph ₃CB (C ₆F ₅) ₄With triisobutyl aluminium be promotor.

??Al∶Ti	??Hexene(mmol)	??Wt?of ??polymer(g)	????Activity(× ???????10 -6)	????Mη	????Tm(℃)
						??75	??10	??5.45	????4.22	????63000	????121.214
??75	??20	??6.39	????4.95	????53000	????107.634
						??75	??30	??6.14	????4.75	????61000	????90.254
??75	??40	??6.37	????4.93	????69000	????84.897

Table 38.3: with [2,4-di-t-butyl-6-(3,4-phenylbenzene cyclopentadienyl) benzene oxidation] titanium dichloride is catalyzer, with Ph ₃CB (C ₆F ₅) ₄With triisobutyl aluminium be promotor.

????Al∶Ti	????Hexene(mmol)	??Wt?of ??polymer(g)	????Activity(× ???????10 -6)	????Mη	????Tm(℃)
						????75	????10	??4.32	????4.66	????46000	????122.564
????75	????20	??4.98	????5.37	????43000	????110.345
						????75	????30	??4.67	????5.04	????51000	????90.752
????75	????40	??4.87	????5.25	????41000	????83.518

Table 38.4: with [the 2-tertiary butyl-6-(3,4-phenylbenzene cyclopentadienyl) benzene oxidation] titanium dichloride is catalyzer, with Ph ₃CB (C ₆F ₅) ₄With triisobutyl aluminium be promotor.

????Al∶Ti	????Hexene(mmol)	??Wt?of ??polymer(g)	???Activity(× ??????10 -6)	????Mη	????Tm(℃)
						????50	????10	??3.42	???3.31	????38000	????121.289
????50	????20	??4.10	???3.96	????34000	????109.542
						????50	????30	??4.01	???3.88	????29000	????89.654
????50	????40	??4.23	???4.09	????37000	????83.347

Table 38.5: the polymerization of other catalyzer

????catalyst	????Al∶Ti	????Hexene(mmol)	??Wt?of ??polymer(g)	???Activity(× ??????10 -6)	??Mη	??Tm(℃)
							????Ti15	????100	????20	??5.76	???5.36	??47000	??108.258
????Ti16	????75	????30	??5.22	???4.27	??51000	??90.349
							????Zr1	????5	????20	??3.48	???4.38	??53000	??105.159
????Zr2	????5	????20	??5.01	???6.88	??60000	??104.617
							????Zr4	????5	????40	??6.33	???6.76	??74000	??80.531
????Zr5	????5	????20	??6.74	???7.96	??59000	??110.643
							????Zr7	????100	????30	??6.82	???6.64	??93000	??92.426
????Zr8	????75	????20	??6.40	???5.51	??85000	??106.964

The copolymerization of embodiment 39 ethene and octene (withPh ₃CB (C ₆F ₅) ₄ With triisobutyl aluminium be promotor)

Be aggregated in the 250mL autoclave and carry out, reactor 110 ℃ of bakings 1 hour under vacuum charge into an atmospheric ethene before the polymerization, and 90mL is contained a certain amount of Ph ₃CB (C ₆F ₅) ₄Add in the reactor with the toluene solution of octene, under agitation condition, reaction system is heated to assigned temperature, then, flow down and to contain in toluene solution (10mL) injecting reactor of 1mg catalyzer and certain proportion triisobutyl aluminium at ethylene gas by a special feeder, ethylene pressure is risen to 5 normal atmosphere, and pick up counting.Do not indicate as special, the reaction times is generally 30min.Reaction finishes back emptying reactor, stops polyreaction with the 5%HCl/ methanol solution.Leach polymkeric substance, water and methyl alcohol thorough washing, 60 ℃ of vacuum-dryings are to constant weight.The results are summarized in table 39.1 to table 39.5 with what different catalysts obtained, wherein be respectively in each independently in the form by different experiment conditions by the difference of part.In table, polymerization continues 30 minutes, and the boron in the promotor and the mol ratio of the transition metal in the Primary Catalysts are 2, unless explanation is arranged in addition.Molecular weight by limiting viscosity (Mn) comparative polymers.

Table 39.1: with [2,4-di-t-butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) benzene oxidation] titanium dichloride is catalyzer, with Ph ₃CB (C ₆F ₅) ₄With triisobutyl aluminium be promotor.

????Al∶Ti	??octene(mmol)	??Wt?of ??polymer(g)	????Activity(× ???????10 -6)	????Mη	????Tm(℃)
						????100	??10	??6.14	????5.44	????79000	????118.254
????100	??20	??7.08	????6.28	????81000	????104.348
						????100	??30	??6.98	????6.19	????72000	????86.221
????100	??40	??7.14	????6.33	????74000	????78.968

Table 39.2: with [the 2-tertiary butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) benzene oxidation] titanium dichloride is catalyzer, with Ph ₃CB (C ₆F ₅) ₄With triisobutyl aluminium be promotor.

????Al∶Ti	????octene(mmol)	??Wt?of ??polymer(g)	???Actiyity(× ??????10 -6)	????Mη	????Tm(℃)
						????75	????10	??5.66	???4.38	????65000	????119.320
????75	????20	??6.54	???5.06	????61000	????107.126
						????75	????30	??6.65	???5.15	????67000	????85.248
????75	????40	??6.49	???5.02	????63000	????79.787

Table 39.3: with [2,4-di-t-butyl-6-(3,4-phenylbenzene cyclopentadienyl) benzene oxidation] titanium dichloride is catalyzer, with Ph ₃CB (C ₆F ₅) ₄With triisobutyl aluminium be promotor.

??Al∶Ti	??octene(mmol)	??Wt?of ??polymer(g)	???Activity(× ??????10 -6)	????Mη	????Tm(℃)
						??75	??10	??4.01	???4.33	????47000	????121.632

????75	????20	????4.85	????5.23	????49000	????106.102
						????75	????30	????4.76	????5.13	????41000	????88.410
????75	????40	????4.99	????5.38	????38000	????83.010

Table 39.4: with [the 2-tertiary butyl-6-(3,4-phenylbenzene cyclopentadienyl) benzene oxidation] titanium dichloride is catalyzer, with Ph ₃CB (C ₆F ₅) ₄With triisobutyl aluminium be promotor.

????Al∶Ti	????octene(mmol)	??Wt?of ??polymer(g)	???Activity(× ??????10 -6)	????Mη	????Tm(℃)
						????50	????10	??3.35	???3.24	????36000	????120.231
????50	????20	??4.03	???3.89	????34000	????105.521
						????50	????30	??4.12	???3.98	????32000	????89.357
????50	????40	??4.32	???4.18	????28000	????84.440

Table 39.5: the polymerization of other catalyzer

????catalyst	????Al∶Ti	????octene(mmol)	??Wt?of ??polymer(g)	????Activity(× ???????10 -6)	??Mη	????Tm(℃)
							????Ti15	????100	????30	??5.98	????5.56	??51000	????89.652
????Ti16	????75	????20	??5.37	????4.39	??57000	????104.861
							????Zr1	????5	????20	??3.56	????4.49	??42000	????106.528
????Zr2	????5	????40	??4.82	????6.62	??49000	????82.207
							????Zr4	????5	????20	??6.21	????6.63	??75000	????106.139
????Zr5	????5	????30	??6.63	????7.82	??79000	????87.210
							????Zr7	????100	????20	??6.72	????6.54	??83000	????104.448
????Zr8	????75	????30	??6.28	????5.41	??74000	????86.357

The copolymerization of embodiment 40 ethene and decene (withPh ₃CB (C ₆F ₅) ₄ With triisobutyl aluminium be promotor)

Be aggregated in the 250mL autoclave and carry out, reactor 110 ℃ of bakings 1 hour under vacuum charge into an atmospheric ethene before the polymerization, and 90mL is contained a certain amount of Ph ₃CB (C ₆F ₅) ₄Add in the reactor with the toluene solution of decene, under agitation condition, reaction system is heated to assigned temperature, then, flow down and to contain in toluene solution (10mL) injecting reactor of 1mg catalyzer and certain proportion triisobutyl aluminium at ethylene gas by a special feeder, ethylene pressure is risen to 5 normal atmosphere, and pick up counting.Do not indicate as special, the reaction times is generally 30min.Reaction finishes back emptying reactor, stops polyreaction with the 5%HCl/ methanol solution.Leach polymkeric substance, water and methyl alcohol thorough washing, 60 ℃ of vacuum-dryings are to constant weight.The results are summarized in table 40.1 to table 40.5 with what different catalysts obtained, wherein be respectively in each independently in the form by different experiment conditions by the difference of part.In table, polymerization continues 30 minutes, and the boron in the promotor and the mol ratio of the transition metal in the Primary Catalysts are 2, unless explanation is arranged in addition.Molecular weight by limiting viscosity (Mn) comparative polymers.

Table 40.1: with [2,4-di-t-butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) benzene oxidation] titanium dichloride is catalyzer, with Ph ₃CB (C ₆F ₅) ₄With triisobutyl aluminium be promotor.

????Al∶Ti	????decene(mmol)	??Wt?of ??polymer(g)	???Activity(× ??????10 -6)	????Mη	????Tm(℃)
						????100	????10	??6.04	???5.35	????72000	????119.658
????100	????20	??6.99	???6.20	????80000	????107.648
						????100	????30	??7.04	???6.24	????76000	????85.437
????100	????40	??6.81	???6.04	????79000	????80.471

Table 40.2: with [the 2-tertiary butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) benzene oxidation] titanium dichloride is catalyzer, with Ph ₃CB (C ₆F ₅) ₄With triisobutyl aluminium be promotor.

??Al∶Ti	????decene(mmol)	??Wt?of ??polymer(g)	???Activity(× ??????10 -6)	????Mη	????Tm(℃)
						??75	????10	??5.74	???4.44	????66000	????121.495
??75	????20	??6.49	???5.02	????62000	????106.579
						??75	????30	??6.03	???4.67	????61000	????87.028
??75	????40	??6.67	???5.16	????58000	????81.670

Table 40.3: with [2,4-di-t-butyl-6-(3,4-phenylbenzene cyclopentadienyl) benzene oxidation] titanium dichloride is catalyzer, with Ph ₃CB (C ₆F ₅) ₄With triisobutyl aluminium be promotor.

????Al∶Ti	????decene(mmol)	??Wt?of ??polymer(g)	???Activity(× ??????10 -6)	????Mη	????Tm(℃)
						????75	????10	??4.31	???4.65	????51000	????113.119
????75	????20	??4.96	???5.35	????47000	????103.411
						????75	????30	??5.01	???5.40	????54000	????85.290
????75	????40	??5.14	???5.54	????43000	????79.995

Table 40.4: with [the 2-tertiary butyl-6-(3,4-phenylbenzene cyclopentadienyl) benzene oxidation] titanium dichloride is catalyzer, with Ph ₃CB (C ₆F ₅) ₄With triisobutyl aluminium be promotor.

??Al∶Ti	????decene(mmol)	????Wt?of ????polymer(g)	????Activity(× ???????10 -6)	????Mη	????Tm(℃)
						??50	????10	????3.41	????3.30	????42000	????118.505
??50	????20	????3.99	????3.86	????38000	????106.042
						??50	????30	????3.54	????3.42	????27000	????88.630
??50	????40	????4.10	????3.96	????29000	????84.873

Table 40.5: the polymerization of other catalyzer

????catalyst	????Al∶Ti	????decene(mmol)	????Wt?of ????polymer(g)	????Activity(× ???????10 -6)	??Mη	????Tm(℃)
							????Ti15	????100	????20	????6.01	????5.59	??45000	????105.647
????Ti16	????75	????40	????5.23	????4.28	??53000	????81.962
							????Zr1	????5	????30	????3.86	????4.86	??48000	????86.334
????Zr2	????5	????30	????4.67	????6.41	??53000	????88.249
							????Zr4	????5	????20	????6.05	????6.46	??79000	????104.532
????Zr5	????5	????40	????6.74	????7.96	??71000	????83.349
							????Zr7	????100	????20	????6.69	????6.51	??87000	????104.441
????Zr8	????75	????30	????6.31	????5.43	??73000	????87.690

Claims (10)

1. metallocene catalyst that contains the phenoxy group side chain, structural formula is: Wherein luxuriant ring Cp is single the replacement or polysubstituted cyclopentadienyl group, and substituent R is selected from hydrogen, alkyl, aryl, alkenyl, alkyl silyl, alkenyl silyl respectively; M is transition metals Ti, zirconium or hafnium; Two X are the aromatic yl alkyl groups except halogen, alkoxy base, amine groups, alkyl group, aromatic yl group, kiki alkenyl group, kiki fang alkyl group, aromatic yl alkenyl group, silylation group or the benzyl; R ₁Be phenoxy group adjacent substituting group, R ₂Be all the other locational one or more substituted radicals of phenoxy group phenyl ring.

2. according to the described metallocene catalyst that contains the phenoxy group side chain of claim 1, it is characterized in that two adjacent substituting groups of said polysubstituted cyclopentadiene group can be interconnected to condensed ring, generate indenes, replace indenes, fluorenes or substituted fluorene; Said substituent R ₁, R ₂Be hydrogen, alkyl group, aromatic yl group, substituted aryl group, aromatic yl alkenyl group, aromatic yl alkyl group, alkyl silyl group or silica-based alkyl group.

3. according to claim 1 or the 2 described metallocene catalysts that contain the phenoxy group side chain, it is characterized in that said X is halogen, methyl, phenyl, trimethyl silicane ylmethyl or neo-pentyl.

4. according to claim 1 or the 2 described metallocene catalysts that contain the phenoxy group side chain, it is characterized in that substituent R is alkyl group or aromatic yl group; Substituent R ₁Be alkyl group or aromatic yl group; Substituent R ₂Be hydrogen, alkyl group or aromatic yl group.

5. according to claim 1 or the 2 described metallocene catalysts that contain the phenoxy group side chain, it is characterized in that substituent R ₂Being the substituting group of phenoxy group contraposition, is hydrogen, alkyl group or aromatic yl group.

6. according to the described metallocene catalyst that contains the phenoxy group side chain of claim 4, it is characterized in that substituent R ₂Being the substituting group of phenoxy group contraposition, is hydrogen, alkyl group or aromatic yl group.

7. a purposes that contains the metallocene catalyst of phenoxy group side chain is used for olefinic polymerization, and its method comprises with described any one metallocene compound of claim 1 and contacting with at least a alkene; With alkylaluminoxane, aluminum alkyls, alkyl aluminum halide, Ph ₃CB (C ₆F ₅) ₄, R ₄NB (C ₆F ₅) ₄, B (C ₆F ₅) ₃Or their mixture is a promotor; In the promotor in aluminium and the Primary Catalysts mol ratio of transition metal be 5～20000: 1, in the promotor in boron and the Primary Catalysts mol ratio of transition metal be 1～100: 1.

8. according to the described purposes that contains the metallocene catalyst of phenoxy group side chain of claim 7, it is characterized in that, when being promotor with the alkylaluminoxane, alkylaluminoxane is methylaluminoxane, modified methylaluminoxane, ethyl aikyiaiurnirsoxan beta or isobutyl aluminium alkoxide, during polymerization in the promotor in aluminium and the Primary Catalysts mol ratio of transition metal be 100～20000: 1; When being promotor with the boron-containing compound, aluminum alkyls is trimethyl aluminium, triethyl aluminum, triisobutyl aluminium or aluminium diethyl monochloride, and boron compound is Ph ₃CB (C ₆F ₅) ₄, B (C ₆F ₅) ₃, during polymerization in the promotor in aluminium and the Primary Catalysts mol ratio of transition metal be 5～500: 1, the mol ratio of transition metal is 1～100: 1 in boron and the Primary Catalysts.

9. according to the described purposes that contains the metallocene catalyst of phenoxy group side chain of claim 7, it is characterized in that, alkene is ethene, propylene, iso-butylene, 1-butylene, 1-hexene, 1-octene, 1-decene and other end alkene less than 20 carbon, or conjugation or unconjugated diene or polyenoid, vinylbenzene, norbornylene, tetrahydrobenzene.

10. according to the described purposes that contains the metallocene catalyst of phenoxy group side chain of claim 7, it is characterized in that, one or more end alkene and ethene or propylene polymerization generate multipolymer, the comonomer that generates multipolymer with vinyl polymerization is propylene, iso-butylene, 1-butylene, 1-hexene, 1-octene, 1-decene and other end alkene less than 20 carbon, or conjugation or unconjugated diene or polyenoid, vinylbenzene, norbornylene, tetrahydrobenzene; The comonomer that generates multipolymer with propylene polymerization is iso-butylene, 1-butylene, 1-hexene, 1-octene, 1-decene and other end alkene less than 20 carbon, or conjugation or unconjugated diene or polyenoid, vinylbenzene, norbornylene, tetrahydrobenzene.