CN101045738A - Metallocene Zr-rare earth isodinuclear catalyst and preparation method and application thereof - Google Patents

本发明提供如下结构式表示的双核茂金属化合物，式中M为稀土元素，R选自H或C₁～C₁₀的烷基、C₂～C₁₀的烯基、C₇～C₁₀的芳烷基、C₆～C₁₀的环烷基或芳基。该化合物与助催化剂烷基铝氧烷配合用于烯烃聚合，具有高的聚合反应活性，并能得到高分子量和宽分子量分布的烯烃聚合产品。本发明还提供所述双核茂金属化合物的合成方法。

The present invention provides a dinuclear metallocene compound represented by the following structural formula, wherein M is a rare earth element, and R is selected from H or C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl, C ₇ -C ₁₀ arane group, C ₆ -C ₁₀ cycloalkyl or aryl group. The compound is used for olefin polymerization in combination with cocatalyst alkyl aluminoxane, has high polymerization activity, and can obtain olefin polymerization products with high molecular weight and wide molecular weight distribution. The invention also provides a synthesis method of the binuclear metallocene compound.

Metallocene Zr-rare earth isodinuclear catalyst and preparation method thereof and application

Technical field

The invention belongs to polyolefin field, relate to the catalyzer of olefinic polymerization, relate in particular to the bimetallic catalyst of ethene and propylene polymerization.

Background technology

Metallocene catalyst is single because of its active centre, the taxis of activity of such catalysts, polymkeric substance, molecular weight and molecular weight distribution can be by changing ligand structure the controlled extensive concern that is subjected to, but because the polyolefin molecular weight narrowly distributing that obtains, processing difficulties and limited its process of industrialization.People attempt with composite catalyzing (Kaminsky W, Steiger R.Polymerization of olefins with homogeneous zirconocene/alumoxane catalysts, Polyhedron, 1988,7 (22-23): 2375-2381) or double-core multinuclear catalyzer (Feng Zuofeng, Xie Jun, Chen Bin etc., organic chemistry, 2001,21 (1), 33-40) improve the molecular weight distribution of polymkeric substance, from J ü ngling (J ü ngling S in 1993, M ü lhaupt R, Cooperative effects in binuclear zirconecenes:their synthesis and use as catalyst in propenepolymerization, J.Organomet.Chem., 1993,460:191-195) since the reported first benzene bridged binuclear metallocene catalyzed ethylene polymerization, this respect has become the focus of research.

Green has found general method (G.M.Diamond, A.N.Cherega, P.Mountford, the M.L.H.Green of synthetic carbon bound, J.Chem.Soc., Dalton Trans, 1996,921), and synthesize a series of carbon bridging dis-cyclopentadiene compoundses, be used for ethene, third rare polyreaction.Find that the double-core zirconium compounds is than monokaryon zirconium compounds and its hafnium homologue catalytic activity height.This is because [M (η-C ₅H ₅) ₂] in the rotation of metal-metal key can M=Hf be 306KJ/mol, M=Zr is 284KJ/mol.The activity of isodigeranyl nuclear compound and close with binuclear compound, and be higher than its Hf analogue.Find that simultaneously the ethylene polymerization activity of binuclear compound depends primarily on C ₅H ₄The metal of the metal of one side rather than indenes one side.

Noh synthesized the carbon bridging of a series of different lengthss dicyclopentadiene two titanium compounds (S.K.Noh, J.Kim, J.Jung, C.S.Ra, D.Lee, H.B.Lee, S.W.Lee, W.S.Huh, J.Organomet.Chem., 1999,580,90-97).Be used for the catalyzed ethylene polymerization reaction.Discovery is along with (CH ₂) _nThe growth of bridge, polymericular weight reduces, and polymerization activity increases, and all than monokaryon compound activity height.This is because thereby long bridge can transmit higher electric density stabilizing active center, improves polymerization activity.Noh thinks that the interaction of atoms metal not only depends on the relative distance of metal center in the binuclear metallocene, and is also relevant with bridge construction.

Lang synthesized the luxuriant binuclear compound of two silyl-bridgeds (H.Lang, S.Blaw, A.Much, K.Wiess, U.Neugebauer, J.Organomet.Chem., 1995,490, c32-c36), catalyzed ethylene polymerization, active in 7.9 * 10 ⁵GPE/mol Ti h, molecular weight reaches 1.2 * 10 ⁶

CN1428355 discloses a kind of dinuclear metallocene compounds and preparation and the application in olefinic polymerization, discloses the binuclear compound of dimethyl-silicon bridging, and has been used for vinyl polymerization, and high reactivity can reach 10 ⁶GPE/mol Cat.

Summary of the invention

The purpose of this invention is to provide a class binuclear metallocene Catalysts and its preparation method, this compound is used for olefin polymerization catalysis, can obtain the polyethylene of high molecular and wide molecular weight distribution.

Another object of the present invention is above-mentioned dinuclear metallocene compounds is used for olefinic polymerization as catalyzer a method.

The isodigeranyl nuclear compound is to contain two different atoms metals in the same compound.Two atoms metals link to each other by part, part is by the cloud density on electronic effect, inductive effect, the modulation effects atoms metal, atoms metal also produces retroaction to part simultaneously, also can produce interaction between two atoms metals, thereby influence its catalytic activity by the transmission or the spatial transmission of part.In the isodigeranyl nuclear compound, we introduce rare earth atom in the metallocene compound first, there is the 4f track in rare earth atom, lanthanon 4f track is not participate in key directly by traditional theory of chemical bonds, but by in the localized 4f of occupying track, mixing a small amount of coupling thing track or in the delocalized molecular orbital(MO), mixing a small amount of 4f composition, make certain contribution, some difference to becoming key with the difference of chemical environment; By with the track of coupling thing is mixed the bond distance being shortened, bond energy increases, and generally can reach percentum; Along with the increase 4f track of group of the lanthanides ordination number reduces the contribution that becomes key; The coupling thing that electronegativity and valence state are high is stronger to the 4f rail effect, and the 4f track is to becoming the key influence bigger.Rare earth atom is introduced in the metallocene compound, can the character to the metallocene heterobimetallic compound be exerted an influence owing to the 4f track special one-tenth key effect of rare earth atom.

Under identical catalytic condition, the catalytic activity of binuclear metallocene catalyzer and monokaryon metallocene compound such as cyclopentadienyl titanium dichloride Cp ₂TiCl ₂Or cyclopentadienyl zirconium dichloride Cp ₂ZrCl ₂Catalytic activity belong to the same order of magnitude, but the binuclear metallocene catalyzer can make the molecular weight of polymkeric substance obviously increase, and molecular weight distribution is broadened.

The invention provides a kind of dinuclear metallocene compounds, have following structural formula:

M=rare earth in the formula; R is selected from H or C ₁～C ₁₀Alkyl, C ₂～C ₁₀Thiazolinyl, C ₇～C ₁₀Aralkyl, C ₆～C ₁₀Cycloalkyl or aryl.

Preferably, R is selected from H, sec.-propyl, allyl group, butenyl, pentenyl, hexenyl or benzyl.

Preferably, M is selected from Y, Nd or Sm.

The present invention also provides the synthetic method of described dinuclear metallocene compounds, comprises the following steps:

1) C ₉H ₆R is dissolved in the organic solvent, is cooled to-90 ℃～-60 ℃; C ₉H ₆The concentration of R in organic solvent is 0.1～0.2mol/L;

2) at-90 ℃～-60 ℃, the organic solution of n-Butyl Lithium slowly adds in the reactant of step 1), adds HPT hexamethyl phosphoric triamine then; N-Butyl Lithium and C ₉H ₆The ratio of R is 1～1.2: 1; The add-on of HPT hexamethyl phosphoric triamine is C ₉H ₆0.1～10% of R, mol ratio; Stirred 2～8 hours at 0～40 ℃;

3) solution step 2) is cooled to-90 ℃～-60 ℃, and 1-bromo-2-(9-fluorenes) ethane is added drop-wise to step 2) solution in, dropwise at 0-40 ℃ and stirred 24-70 hour; 1-bromo-2-(9-fluorenes) ethane and C ₉H ₆The mol ratio of R is 1: 1～1.2;

4) the product hydrolysis of step 3), organic layer anhydrous sodium sulfate drying, solvent removed in vacuo; Resistates is dissolved in pentane and purifies with silicagel column, gets part C ₁₃H ₈-CH ₂CH ₂-C ₉H ₆R;

5) part that step 4) is obtained is dissolved in the normal hexane, drips n-Butyl Lithium, and dropping temperature is-30～20 ℃, and the mol ratio of part and n-Butyl Lithium is 1: 2.0～2.5, and progressively increasing finishes, and rises to room temperature naturally, reacts 8～15 hours; Remove by filter solvent, the decompressing and extracting solvent obtains the part lithium salts.

6) add toluene in the part lithium salts that step 5) obtains, obtain white opacity liquid, i.e. the suspension of above-mentioned lithium salts ,-20～30 ℃ add CpZrCl down ₃DME, wherein DME is a glycol dimethyl ether, Cp is a cyclopentadienyl.CpZrCl ₃The mol ratio of DME and part lithium salts is 1: 1～1.2, temperature of reaction is-20～30 ℃, stirring reaction 15～24 hours, reaction product is through centrifugation, residual solid is used dichloromethane extraction again, all extraction liquids and the centrifugal liquid that obtains are merged, be concentrated into and solid occurs, place for-25 ℃～-15 ℃ and promptly got compound (I) in 20～30 hours.

7) under organic medium, the compound of formula (I) and expression formula are CpMCl ₃The cyclopentadiene muriate according to 1: 1～1.25 molar ratio reaction, temperature of reaction is 130～170 ℃, the time is 10～40 hours, filter then, filtrate is concentrated the back use the organic solvent recrystallization, obtain the C2 bridged metallocene double-core catalyst, structure is shown below:

Step 2) needs in to add HPT hexamethyl phosphoric triamine (HMPT), to avoid generating 4,5,6,7-hexichol spiral shell [2,4] heptane.

Organic solvent in the reaction is selected from: a kind of in ether, sherwood oil, methyl ether, hexane, pentane, toluene, methylene dichloride, tetrahydrofuran (THF), the normal hexane;

Preferably, the dropping temperature in the step 5) is-10～0 ℃.

Preferably, the organic solvent in the step 1) is selected from ether, sherwood oil or methyl ether; Step 2) organic solution in is hexane solution or pentane solution; Organic medium in the step 7) is benzene or toluene, and the used organic solvent of recrystallization is selected from one or more in toluene, methylene dichloride, tetrahydrofuran (THF), normal hexane, the sherwood oil.

R ¹Be selected from H or C ₁～C ₁₀Alkyl, C ₂～C ₁₀Thiazolinyl, C ₇～C ₁₀Aralkyl, C ₆～C ₁₀Cycloalkyl or aryl.Preferably, R ¹Be selected from H or C ₁～C ₄Alkyl, C ₂～C ₈Thiazolinyl, C ₇～C ₉Aralkyl.Preferred, R ¹Be selected from H, sec.-propyl, allyl group, butenyl, pentenyl, hexenyl or benzyl.

The CpZrCl that uses among the present invention ₃DME, expression formula are CpMCl ₃The cyclopentadiene muriate of (M is a rare earth element) can be bought, and also can adopt the known method preparation.Wherein expression formula is CpMCl ₃The cyclopentadiene muriate the present invention of (M is a rare earth element) recommends to use that Chemical Industry Press publishes that " the Organometallic Chemistry method of synthesize in the handbook (1986) (Chen Shoushan just opens it, Wang Xukun, Liu Yiyin, Zhang Zengyou compiles) prepares.CpZrCl ₃DME recommends to use document Lund E C, Livinghouse T.Rapid and efficient procedures for the synthesis of mono-cyclopentadienyl complexes of hafnium and zirconium[J] .Organometallics, 1990, the method preparation among the 9:2426-2427.

The present invention also provides a kind of ethene polymerization method, comprise that compound of the present invention is Primary Catalysts, is promotor with the alkylaluminoxane, under polymerizing condition, make vinyl polymerization, wherein in the promotor in Al and the Primary Catalysts mol ratio of metal be 250～1500: 1.Preferably, promotor is a methylaluminoxane, during polyreaction, in the promotor in Al and the Primary Catalysts mol ratio of metal be 250～1000: 1.Polymerizing condition is 30～80 ℃, 0.1～0.8MPa.

Embodiment

If no special instructions, each reaction of the present invention all needs to carry out under inert atmosphere, and rare gas element is argon gas or nitrogen.

Compound provided by the invention is as C ₂～C ₁₀The alpha-olefin homopolymerization or the Primary Catalysts of copolymerization.Also need add alkylaluminoxane during polymerization is promotor.Preferred promotor is a methylaluminoxane, during polyreaction, in the promotor in Al and the Primary Catalysts mol ratio of metal be 250～1500: 1, preferred 250～1000: 1.Polymerizing condition is 30～80 ℃, 0.1～0.8MPa.Be used for homopolymerization or copolymerization and get alkene optimal ethylene, propylene, butylene, hexene or octene.Polymerization process can adopt mass polymerization or solution polymerization.

Analytical procedure: NMR:Jeol JNM-EX 270E, Bruker ARX 250 and Bruker DRX 500 nmr determinations; Sample dissolves in 25 ℃ CDCl under argon shield ₃Mass spectrum: Varian MAT CH7 mass spectrograph (70eV); GC/MS uses Varian 3700 gas-chromatographies and Varian MAT 312 mass spectrum logotypes.

Polymkeric substance is described: dsc (DSC): Perkin-Elmer DSC-7 calorimeter is used for the thermal properties of characterize polymers, before the measurement, and the vacuum-drying of polymkeric substance elder generation.

Following examples are to further specify of the present invention, but the present invention is not limited thereto.

Embodiment 1: metallocene catalyst A's is synthetic

Step 1: part synthetic

10mmol 1-allyl group indenes is dissolved in the 60ml sherwood oil, be cooled to-78 ℃, 6.25ml n-Butyl Lithium (1.6M hexane solution) slowly adds in the 60ml petroleum ether solution of 10mmol 1-allyl group indenes, adds 6ml HMPT again, slowly rise to 20 ℃, stir 5h down at 20 ℃.

Slowly be cooled to-78 ℃, 2.73g (10mmol) 1-bromo-2-(9-fluorenes) ethane is added drop-wise in the above-mentioned solution, and compound of reaction stirred 40 hours at 30 ℃.Mixture 50ml water hydrolysis, organic layer anhydrous sodium sulfate drying, solvent removed in vacuo.Resistates is dissolved in pentane and purifies with silicagel column, and the oil reservoir that removes after desolvating can be directly used in synthetic compound.Productive rate 79%.Product is 1-(9-fluorenes)-2-[1-(3-allyl group) indenes] ethane; GC 2820s; MS:m/e 348 (M ⁺);

¹H NMR(CDCl3，25℃)：7.74(d，J＝7.6Hz，2H)，7.48-7.15(10H)，6.14(d，J＝2.0Hz，1H，CH _ind)，6.10(m，1H，＝CH)，5.15(m，1H，CH ₂)，5.15(m，1H，＝CH ₂)，3.96(t，J＝5.5Hz，1H，CH)，3.29-3.26(m，3H，CH，CH ₂)，2.12(m，1H，CH ₂)，1.95(m，1H，CH ₂)，1.70(m，1H，CH ₂)，1.38(m，1H，CH ₂)，

¹³C NMR(CDCl3，25℃)：148.0，147.0，146.9，141.5，141.2(Cq)，135.5(＝CH)，133.7，126.9，126.8，126.2，124.7，124.2，122.7，119.7，119.7，119.1(CH)，116.2(＝CH ₂)，48.8，47.3(CH)，32.2，29.6，26.7(CH ₂)；

Step 2: catalyst intermediate synthetic:

0.0266mol part is dissolved in the 80ml normal hexane, ice-water bath drips the n-Butyl Lithium of 0.0532mol down, dropwises the recession deicing and bathes, and rises to room temperature naturally, and reaction is spent the night.Remove by filter solvent, vacuum is drained, and gets the part lithium salts;

Add 150ml toluene in above-mentioned part lithium salts, obtain white opacity liquid, room temperature adds 9.36 gram cyclopentadiene tri-chlorination zirconium glycol dimethyl ether (CpZrCl ₃DME), 25 ℃ of stirring reactions 24 hours, centrifugation, resistates merges centrifugate and extraction liquid with 50ml dichloromethane extraction 2 times, is concentrated into solid and occurs, and-20 ℃ left standstill 24 hours, must faint yellow needle-like crystal, be the title complex intermediate, productive rate 39.2%.

Step 3: metallocene catalyst A's is synthetic

Under the argon shield, with title complex intermediate 1.35mmol and 1.35mmol CpYCl ₃Put into the Schlenk bottle that prolong is housed, add 80ml toluene, be heated to 145 ℃ of reflux temperatures, along with the rising of temperature of reaction, reaction solution changes into orange red by yellow gradually.Stirring reaction is 20 hours under reflux state, stops to stir, and reduces to room temperature.1/3 ,-20 ℃ that after the filtration filtrate are concentrated into original volume left standstill 20 hours, the silver gray crystal, its structure is shown below.Productive rate 42.5%.

Because the Sm ion has unpaired electron, so have paramagnetism.So ¹Active change in displacement is big and be generally bigger broad peak on the H NMR spectrum, and spectrum is read in influence.Relevant spectral data is as follows:

¹H NMR(CDCl3，25℃)：7.46-7.40(C ₅H ₅)，7.28-7.20(C ₉H ₆)，6.87-6.72(C ₉H ₆)，6.48-6.58(C ₉H ₆)，6.35-6.40(C ₁₃H ₉)，6.15-6.19(C ₁₃H ₉)，5.56-5.32(＝CH-)，5.01-4.99(＝CH ₂)，3.38-3.78(THF)，1.29-1.87(CH ₂)，1.02-1.10(CH ₂)；

Embodiment 2: metallocene catalyst B's is synthetic

Other are with embodiment 1, and different is with CpSmCl ₃Replaced C pYCl ₃, be heated to 155 ℃ of reflux temperatures, along with the rising of temperature of reaction, reaction solution changes into orange red by yellow gradually.Stirring reaction is 22 hours under reflux state, stops to stir, and reduces to room temperature.1/3 ,-20 ℃ that after the filtration filtrate are concentrated into original volume left standstill 20 hours, the silver gray crystal, its structure is shown below.Productive rate 47.2%.

Because the Sm ion has unpaired electron, so have paramagnetism.So ¹Active change in displacement is big and be generally bigger broad peak on the H NMR spectrum, and spectrum is read in influence.Relevant spectral data is as follows:

¹H NMR(CDCl3，25℃)：7.58-7.46(C ₅H ₅)，7.38-7.26(C ₉H ₆)，6.88-6.71(C ₉H ₆)，6.49-6.56(C ₉H ₆)，6.41-6.45(C ₁₃H ₉)，6.18-6.22(C ₁₃H ₉)，5.57-5.38(＝CH-)，5.04-4.98(＝CH ₂)，3.37-3.72(THF)，1.49-1.77(CH ₂)，1.01-1.14(CH ₂)；

Embodiment 3: metallocene catalyst C's is synthetic

Other are with embodiment 1, and different is with CpNdCl ₃Replaced C pYCl ₃, be heated to 160 ℃ of reflux temperatures, along with the rising of temperature of reaction, reaction solution changes into orange red by yellow gradually.Stirring reaction is 18 hours under reflux state, stops to stir, and reduces to room temperature.1/3 ,-20 ℃ that after the filtration filtrate are concentrated into original volume left standstill 20 hours, the silver gray crystal, its structure is shown below.Productive rate 48%.

Because the Sm ion has unpaired electron, so have paramagnetism.So ¹Active change in displacement is big and be generally bigger broad peak on the H NMR spectrum, and spectrum is read in influence.Relevant spectral data is as follows:

¹H NMR(CDCl3，25℃)：7.52-7.47(C ₅H ₅)，7.39-7.27(C ₉H ₆)，6.82-6.70(C ₉H ₆)，6.44-6.53(C ₉H ₆)，6.40-6.38(C ₁₃H ₉)，6.17-6.21(C ₁₃H ₉)，5.58-5.39(＝CH-)，5.02-4.94(＝CH ₂)，3.38-3.69(THF)，1.48-1.71(CH ₂)，1.00-1.12(CH ₂)；

Embodiment 4: metallocene catalyst D's is synthetic

Step 1: part synthetic:

10mmol 1-(3-butenyl) indenes is dissolved in the 60ml ether, be cooled to-60 ℃, 6.30ml n-Butyl Lithium (1.6M hexane solution) slowly adds in the 60ml diethyl ether solution of 10mmol 1-(3-butenyl) indenes, adds 6ml HMPT then, compound is warming up to 0 ℃, and stirs 3h.

Be cooled to-70 ℃, 2.73g (10mmol) 1-bromo-2-(9-fluorenes) ethane is added drop-wise in the above-mentioned solution, and compound of reaction is warming up to 10 ℃ and stirred 60 hours.Mixture 50ml water hydrolysis, organic layer anhydrous sodium sulfate drying, solvent removed in vacuo.Resistates is dissolved in pentane and purifies with silicagel column, and the oil reservoir that removes after desolvating can be directly used in synthetic compound.Productive rate 88%.Product is 1-(9-fluorenes)-2-[1-(3-fourth-3-thiazolinyl) indenes] ethane; GC 2976s; MS:m/e 362 (M ⁺);

¹H NMR(CDCl3，25℃)：7.90-7.82(，2H)，7.67(m，1H)，7.49-7.24(8H)，7.13(d，J＝6.6Hz，1H)，6.26(d，J＝1.6Hz)，6.22(d，J＝1.6Hz，1H，CH _ind)，6.01(m，1H，＝CH)，5.15(m，lH，＝CH ₂)，5.15(m，1H，＝CH ₂)，4.21(t，J＝5.0Hz，1H，CH)，4.05(d，J＝5.4Hz，1H，CH)，3.42(m，1H，CH)，2.70(m，1H，CH ₂)，2.57-2.40(3H，CH ₂)，2.20(m，1H，CH ₂)，2.15-1.94(m，1H，CH ₂)，1.78(m，1H，CH ₂)，1.62(m，2H，CH ₂)；

¹³C NMR(CDCl3，25℃)：148.5，148.1，147.1，147.1，145.1，144.8，143.4，143.0，141.4，141.3，141.3(Cq)，138.7，138.4(＝CH)，132.9，132.7，127.1，127.0，126.9，126.3，126.3，126.0，124.8，124.4，124.3，122.9，122.8，120.0，120.0，119.9，119.8，119.8，119.0，118.9，118.6(CH)，114.9，114.8(＝CH ₂)，48.8，48.4，47.4，47.3(CH)，32.1，31.8，31.3，31.0，29.6，26.8(CH ₂)；

Step 2: catalyst intermediate synthetic:

0.0266mol part is dissolved in the 80ml normal hexane, cryosel is bathed the n-Butyl Lithium that (25 ℃) drip 0.054mol down, dropwises the recession deicing and bathes, and rises to room temperature naturally, and reaction is spent the night.Remove by filter solvent, vacuum is drained, and adds 150ml toluene, obtains white opacity liquid, and room temperature adds 9.36 gram cyclopentadiene tri-chlorination zirconium glycol dimethyl ether (CpZrCl ₃DME), 20 ℃ of stirring reactions 20 hours, centrifugation, resistates merges centrifugate and extraction liquid with 50ml dichloromethane extraction 2 times, is concentrated into solid and occurs, and-15 ℃ left standstill 24 hours, must faint yellow needle-like crystal, be the title complex intermediate, productive rate 33.2%.

Step 3: metallocene catalyst D's is synthetic

Under the argon shield, with title complex intermediate 1.35mmol and 1.35mmol CpYCl ₃Put into the Schlenk bottle that prolong is housed, add 80ml toluene, be heated to 150 ℃ of reflux temperatures, along with the rising of temperature of reaction, reaction solution changes into orange red by yellow gradually.Stirring reaction is 15 hours under reflux state, stops to stir, and reduces to room temperature.80 ℃ of filtrations, resistates is incorporated filtrate into the extraction of 60ml toluene, filtrate is concentrated into 1/3 ,-20 ℃ of original volume left standstill 20 hours, the silver gray solid.Solid gets the silver gray crystal with 50ml toluene recrystallization, and its structure is shown below.Productive rate 43.8%.

Because the Sm ion has unpaired electron, so have paramagnetism.So ¹Active change in displacement is big and be generally bigger broad peak on the H NMR spectrum, and spectrum is read in influence.Relevant spectral data is as follows:

¹H NMR(CDCl3，25℃)：7.55-7.48(C ₅H ₅)，7.38-7.26(C ₉H ₆)，6.85-6.70(C ₉H ₆)，6.43-6.53(C ₉H ₆)，6.39-6.36(C ₁₃H ₉)，6.18-6.22(C ₁₃H ₉)，5.59-5.38(＝CH-)，5.01-4.93(＝CH ₂)，3.44-3.79(THF)，1.55-1.78(CH ₂)，1.22-1.41(CH ₂)；

Embodiment 5: metallocene catalyst E's is synthetic

Other are with embodiment 4, and different is with CpNdCl ₃Replaced C pYCl ₃, be heated to 165 ℃ of reflux temperatures, along with the rising of temperature of reaction, reaction solution changes into orange red by yellow gradually.Stirring reaction is 16 hours under reflux state, stops to stir, and reduces to room temperature.1/3 ,-20 ℃ that after the filtration filtrate are concentrated into original volume left standstill 22 hours, the silver gray crystal.Productive rate 44.9%.

Embodiment 6: metallocene catalyst F's is synthetic

10mmol 1-(4-pentenyl) indenes is dissolved in the 70ml methyl ether, be cooled to-80 ℃, 6.20ml n-Butyl Lithium (1.6M hexane solution) slowly adds in the 60ml methyl ether solution of 10mmol 1-(4-pentenyl) indenes, adds 6ml HMPT then, is warming up to 30 ℃ and stir 8h at 30 ℃.

Be cooled to-80 ℃, 2.73g (10mmol) 1-bromo-2-(9-fluorenes) ethane is added drop-wise in the above-mentioned solution, is warming up to 30 ℃ and stirred 40 hours down at 30 ℃.Mixture 50ml water hydrolysis, organic layer anhydrous sodium sulfate drying, solvent removed in vacuo.Resistates is dissolved in pentane and purifies with silicagel column, and the oil reservoir that removes after desolvating can be directly used in synthetic compound.Productive rate 70%.Product is 1-(9-fluorenes)-2-[1-(3-penta-4-thiazolinyl) indenes] ethane; GC 3061s; MS:m/e 376 (M ⁺);

¹H NMR(CDCl3，25℃)：7.94-7.86(2H)，7.66(m，1H)，7.53-7.12(8H)，7.05(m，1H)，6.23(d，J＝1.9Hz)，6.17(d，J＝1.9Hz，CH _ind)，5.89(m，1H，＝CH)，5.08(m，1H，＝CH ₂)，5.09(m，1H，＝CH ₂)，4.18(t，J＝5.5Hz)，4.02(t，J＝5.5Hz，1H)，3.37(m，1H，CH)，2.62-2.36(3H，CH ₂)，2.23-2.11(m，3H，CH ₂)，1.89-1.77(m，2H，CH ₂)，1.57-1.34(2H，CH ₂)；

¹³C NMR(CDCl3，25℃)：148.6，148.1，147.1，147.0，145.1，144.8，143.4，143.1，141.3，141.3，141.2(Cq)，138.8，138.7(＝CH)，133.0，132.8，132.7，127.0，126.9，126.2，124.6，124.3，122.8，119.8，119.8，119.8，118.9(CH)，114.8，114.6(＝CH ₂)，48.9，48.7，47.5，47.3，47.2(CH)，34.1，33.6，31.3，27.2，27.0，26.9，23.3，18.3(CH ₂)；

Step 2: catalyst intermediate synthetic:

0.0266mol part is dissolved in the 80ml normal hexane, ice-water bath drips the n-Butyl Lithium of 0.055mol down, dropwises the recession deicing and bathes, and rises to room temperature naturally, and reaction is spent the night.Remove by filter solvent, vacuum is drained, and adds 150ml toluene, obtains white opacity liquid, and room temperature adds 9.36 gram cyclopentadiene tri-chlorination zirconium glycol dimethyl ether (CpZrCl ₃DME), 25 ℃ of stirring reactions 15 hours, centrifugation, resistates merges centrifugate and extraction liquid with 50ml dichloromethane extraction 2 times, is concentrated into solid and occurs, and-20 ℃ left standstill 24 hours, must faint yellow needle-like crystal, be the title complex intermediate, productive rate 28.4%.

Step 3: metallocene catalyst F's is synthetic

Under the argon shield, with title complex intermediate 1.50mmol and 1.50mmol CpSmCl ₃Put into the Schlenk bottle that prolong is housed, add 80ml toluene, be heated to 145 ℃ of reflux temperatures, along with the rising of temperature of reaction, reaction solution changes into orange red by yellow gradually.The continuously stirring reaction is 20 hours under reflux state, stops to stir, and reduces to room temperature.1/3 ,-20 ℃ that after the filtration filtrate are concentrated into original volume left standstill 20 hours, the silver gray crystal, its structure is shown below.Productive rate is 52.5%.

Because the Sm ion has unpaired electron, so have paramagnetism.So ¹Active change in displacement is big and be generally bigger broad peak on the H NMR spectrum, and spectrum is read in influence.Relevant spectral data is as follows:

¹H NMR(CDCl3，25℃)：7.82-7.77(C ₅H ₅)，7.59-7.48(C ₉H ₆)，6.79-6.79(C ₉H ₆)，6.65-6.51(C ₉H ₆)，6.44-6.38(C ₁₃H ₉)，6.31-6.26(C ₁₃H ₉)，5.60-5.44(＝CH-)，5.06-4.98(＝CH ₂)，3.44-3.73(THF)，1.55-1.78(CH ₂)，1.13-1.42(CH ₂)；

Embodiment 7: metallocene catalyst G's is synthetic:

Other are with embodiment 6, and different is with CpNdCl ₃Replaced C pSmCl ₃, be heated to 150 ℃ of reflux temperatures, along with the rising of temperature of reaction, reaction solution changes into orange red by yellow gradually.Stirring reaction is 24 hours under reflux state, stops to stir, and reduces to room temperature.1/3 ,-20 ℃ that after the filtration filtrate are concentrated into original volume left standstill 20 hours, the silver gray crystal.Productive rate 51.5%.

Embodiment 8: metallocene catalyst H's is synthetic:

10mmol1-(5-hexenyl) indenes is dissolved in the 50ml ether, be cooled to-78 ℃, 6.28ml n-Butyl Lithium (1.6M pentane solution) slowly adds in the 50ml diethyl ether solution of 10mmol 1-(5-hexenyl) indenes, adds 6ml HMPT again, is warming up to 10 ℃ and stir down 2h at 10 ℃.

Be cooled to-78 ℃, 2.73g (10mmol) 1-bromo-2-(9-fluorenes) ethane is added drop-wise in the solution, and reactant is warming up to 0 ℃ and stirred 66 hours down at 0 ℃.Mixture 50ml water hydrolysis, organic layer anhydrous sodium sulfate drying, solvent removed in vacuo.Resistates is dissolved in pentane and purifies with silicagel column, and the oil reservoir that removes after desolvating can be directly used in synthetic compound.Productive rate 86%.Product is 1-(9-fluorenes)-2-[1-(3-oneself-5-thiazolinyl) indenes] ethane; GC 3300s; MS:m/e 390 (M ⁺);

Step 2: catalyst intermediate synthetic:

0.0266mol part is dissolved in the 80ml normal hexane, cryosel is bathed the n-Butyl Lithium that (10 ℃) drip 0.0532mol down, dropwises the recession deicing and bathes, and rises to room temperature naturally, and reaction is spent the night.Remove by filter solvent, vacuum is drained, and adds 150ml toluene, obtains white opacity liquid, and room temperature adds 9.36 gram cyclopentadiene tri-chlorination zirconium glycol dimethyl ether (CpZrCl ₃DME), 25 ℃ of stirring reactions 24 hours, centrifugation, resistates merges centrifugate and extraction liquid with 50ml dichloromethane extraction 2 times, is concentrated into solid and occurs, and-20 ℃ left standstill 24 hours, must faint yellow needle-like crystal, be the title complex intermediate, productive rate 33.6%.

Step 3: metallocene catalyst H's is synthetic

Under the argon shield, with title complex intermediate 1.50mmol and 1.52mmol CpSmCl ₃Put into the Schlenk bottle that prolong is housed, add 80ml toluene, be heated to 175 ℃ of reflux temperatures, along with the rising of temperature of reaction, reaction solution changes into orange red by yellow gradually.Stirring reaction is 20 hours under reflux state, stops to stir, and reduces to room temperature.After the filtration filtrate is concentrated into 1/3 of original volume, left standstill 20 hours at-20 ℃, get the silver gray crystal, its structure is shown below.Productive rate 51.3%.

Because the Sm ion has unpaired electron, so have paramagnetism.So ¹Active change in displacement is big and be generally bigger broad peak on the H NMR spectrum, and spectrum is read in influence.Relevant spectral data is as follows:

¹H NMR(CDCl3，25℃)：7.66-7.57(C ₅H ₅)，7.42-7.28(C ₉H ₆)，6.89-6.77(C ₉H ₆)，6.45-6.52(C ₉H ₆)，6.38-6.35(C ₁₃H ₉)，6.22-6.29(C ₁₃H ₉)，5.61-5.42(＝CH-)，5.05-4.99(＝CH ₂)，3.45-3.72(THF)，1.58-1.77(CH ₂)，1.26-1.44(CH ₂)；

Embodiment 9: metallocene catalyst I's is synthetic:

Other are with embodiment 8, and different is with CpNdCl ₃Replaced C pSmCl ₃, be heated to 150 ℃ of reflux temperatures, along with the rising of temperature of reaction, reaction solution changes into orange red by yellow gradually.Stirring reaction is 21 hours under reflux state, stops to stir, and reduces to room temperature.1/3 ,-20 ℃ that after the filtration filtrate are concentrated into original volume left standstill 20 hours, the silver gray crystal.Productive rate 52.3%.

Embodiment 10: metallocene catalyst J's is synthetic:

10mmol 1-benzyl indenes is dissolved in the 60ml ether, is cooled to-70 ℃, and 6.30ml n-Butyl Lithium (1.6M pentane solution) slowly adds in the 60ml diethyl ether solution of 10mmol 1-benzyl indenes, adds 6ml HMPT then, is warming up to 0 ℃ and stir 4h.

Be cooled to-78 ℃, 2.73g (10mmol) 1-bromo-2-(9-fluorenes) ethane is added drop-wise in the solution, slowly rises to 10 ℃ and stirred 69 hours.Mixture 50ml water hydrolysis, organic layer anhydrous sodium sulfate drying, solvent removed in vacuo.Resistates is dissolved in pentane and purifies with silicagel column, and the oil reservoir that removes after desolvating can be directly used in synthetic compound.Productive rate 77%.

1-(9-fluorenes)-2-[1-(3-phenmethyl) indenes] ethane: GC 3341s.MS:m/e 398 (M ⁺).

¹H NMR(CDCl3，25℃)：7.94-7.83(3H)，7.58-7.31(13H)，7.14(m，1H)，6.67(d，J＝5.5Hz，2H)，6.27(d，J＝5.5Hz，1H)，6.23(m)，6.18(m)，6.15(m，1H，CH _ind)，4.03(m，2H)，3.97(s，1H，CH)，3.44(s，1H，CH)，2.44(2H，CH ₂)，2.23(m，1H，CH ₂)，2.05(m，1H，CH ₂)；

Step 2: catalyst intermediate synthetic:

0.0266mol part is dissolved in the 80ml normal hexane, ice-water bath drips the n-Butyl Lithium of 0.0532mol down, dropwises the recession deicing and bathes, and rises to room temperature naturally, and reaction is spent the night.Remove by filter solvent, vacuum is drained, and adds 150ml toluene, obtains white opacity liquid, and room temperature adds 9.36 gram cyclopentadiene tri-chlorination zirconium glycol dimethyl ether (CpZrCl ₃DME), 25 ℃ of stirring reactions 20 hours, centrifugation, resistates merges centrifugate and extraction liquid with 50ml dichloromethane extraction 2 times, is concentrated into solid and occurs, and-20 ℃ left standstill 24 hours, must faint yellow needle-like crystal, be the title complex intermediate, productive rate 48.9%.

Step 3: metallocene catalyst J's is synthetic

Under the argon shield, with title complex intermediate 1.55mmol and 1.55mmol CpNdCl ₃Put into the Schlenk bottle that prolong is housed, add 80ml toluene, be heated to 125 ℃ of reflux temperatures, along with the rising of temperature of reaction, reaction solution changes into orange red by yellow gradually.Stirring reaction is 20 hours under reflux state, stops to stir, and reduces to room temperature.80 ℃ of filtrations, resistates is incorporated filtrate into the extraction of 60ml toluene, filtrate is concentrated into 1/3 ,-20 ℃ of original volume left standstill 20 hours, red solid.Solid gets brown crystal with 50ml normal hexane recrystallization, and its structure is shown below.Productive rate 39.9%.

The R=benzyl;

Because the Sm ion has unpaired electron, so have paramagnetism.So ¹Active change in displacement is big and be generally bigger broad peak on the H NMR spectrum, and spectrum is read in influence.Relevant spectral data is as follows:

¹H NMR(CDCl3，25℃)：7.89-7.86(C ₆H ₅)，7.66-7.57(C ₅H ₅)，7.42-7.28(C ₉H ₆)，6.89-6.77(C ₉H ₆)，6.45-6.52(C ₉H ₆)，6.38-6.35(C ₁₃H ₉)，6.22-6.29(C ₁₃H ₉)，5.61-5.42(＝CH-)，5.05-4.99(＝CH ₂)，3.45-3.72(THF)，1.58-1.77(CH ₂)；

Embodiment 11: metallocene catalyst K's is synthetic:

Other are with embodiment 10, and different is with CpYCl ₃Replaced C pNdCl ₃, be heated to 155 ℃ of reflux temperatures, along with the rising of temperature of reaction, reaction solution changes into orange red by yellow gradually.Under reflux state, continue stirring reaction 18 hours, stop to stir, reduce to room temperature.1/3 ,-20 ℃ that after the filtration filtrate are concentrated into original volume left standstill 24 hours, brown crystal.Productive rate 50.6%.

Embodiment 12-21: vinyl polymerization

Catalyzer is made into toluene solution, adds 10% MAO toluene solution, catalyzer and toluene successively in the exsiccant reaction flask, the control cumulative volume is 25ml, is warming up to 60 ℃, feeds ethylene gas, and maintenance system is a normal pressure, reacts 0.5 hour.With dilute hydrochloric acid and ethanol stopped reaction, filter, product was 60 ℃ of vacuum-dryings 3 hours, and the catalyzer that adds in the reaction process and the amount of promotor, catalyst activity and polymer property see Table 1, and wherein weight-average molecular weight and molecular weight distribution mw/mn are recorded by GPC.

It should be noted that, the metallocene catalyst that has ω-alkenyl group can be used as comonomer and enters the polyolefin polymers chain, in this case, being equivalent to these metallocene catalysts is immobilized, polymer chain is as organic carrier, and the polymer chain that obtains later is that heterogeneous catalysis obtains.The catalysis data see Table 1.The polyethylene fusing point that obtains is at 131.7 to 140.0 ℃, and the fusion enthalpy difference is very big, and the polyethylene fusion enthalpy that the catalyzer of C2 bridging obtains is up to 16095Jg ^-1, corresponding degree of crystallinity is 53 to 57%, (α=40-50%) and PE-HD are (between the α=60-80%) between PE-LD.

Embodiment 22-31: ethylene homo reaction

Carry out ethene party reaction by the method for the foregoing description, different is that ethene, with dilute hydrochloric acid and ethanol stopped reaction, is filtered after 1 hour 80 ℃ of polymerizations, and product was 60 ℃ of vacuum-dryings 3 hours, and weighing gets polymer weight, calculates polymerization activity.The catalysis data see Table 1.