CN118221849B

CN118221849B - Use of a metallocene catalyst composition as a catalyst in the preparation of polyalphaolefin wax

Info

Publication number: CN118221849B
Application number: CN202410320629.8A
Authority: CN
Inventors: 魏东初; 叶健
Original assignee: Apexene Technology Shanghai Co ltd
Current assignee: Apexene Technology Shanghai Co ltd
Priority date: 2024-03-20
Filing date: 2024-03-20
Publication date: 2024-12-13
Anticipated expiration: 2044-03-20
Also published as: CN118221849A

Abstract

本发明公开一种茂金属催化剂组合物在聚α烯烃蜡制备中作为催化剂的用途。所述催化剂组合物包括主催化剂和助催化剂，所述主催化剂为茂金属化合物，所述助催化剂为烷基铝和/或含硼元素的有机化合物。本发明技术方案中首次提出采用如本申请中所述催化剂组合物催化制备聚α烯烃蜡。The present invention discloses a use of a metallocene catalyst composition as a catalyst in the preparation of polyalphaolefin wax. The catalyst composition comprises a main catalyst and a co-catalyst, wherein the main catalyst is a metallocene compound, and the co-catalyst is an alkyl aluminum and/or an organic compound containing a boron element. The technical solution of the present invention proposes for the first time to use the catalyst composition as described in the present application to catalyze the preparation of polyalphaolefin wax.

Description

Application of metallocene catalyst composition as catalyst in preparation of poly alpha olefin wax

Technical Field

The invention belongs to the technical field of organic compounds, in particular to the technical field of polyolefin, and provides an application of a metallocene catalyst composition as a catalyst in the preparation of poly alpha olefin wax.

Background

Polyolefin wax is wax-like at normal temperature, and has the advantages of no toxicity, no corrosiveness, abrasion resistance, heat resistance, chemical resistance, good dispersibility and fluidity, etc. The polyolefin wax can be directly used in polyolefin processing as a multifunctional additive, can increase the gloss and processing performance of products, has good compatibility with polyolefin resin and the like, can disperse pigment in color master batches, can serve as a release agent in plastic processing, can serve as an ink wear-resistant agent, and becomes an indispensable important chemical raw material in industries such as plastics, rubber, ink, paint, metal casting and the like. Polyolefin waxes generally include polyethylene waxes obtained by homopolymerization of ethylene or propylene, polypropylene waxes, polyolefin waxes obtained by copolymerization of ethylene and an alpha olefin, which have a limited degree of branching and have side chains arranged randomly, and the density of the side chains is not high enough, and the dispersibility for pigments or fillers has yet to be improved.

The poly alpha olefin is hydrocarbon with proper relative molecular mass prepared by polymerizing raw material alpha olefin under the action of catalyst, and the poly alpha olefin synthetic oil prepared by the raw material alpha olefin of C6, C8 and C10 has high viscosity index, low volatility and excellent oxidation stability and is generally used as lubricating oil base oil. The long chain alpha olefin above C10 can be used as raw materials to synthesize poly alpha olefin wax, such as Zhang Jianyu and the like (Zhang Jianyu; chen Cheng; li Huihui; zheng Yigong, synthesis of poly alpha olefin wax, petroleum refining and chemical industry, 2009-01-12), hexadecene and octadecene are used as raw materials, and a Ziegler-Natta supported catalyst and triethylaluminum cocatalyst are adopted to prepare the poly alpha olefin wax with low isotacticity under normal pressure by a bulk polymerization method. However, ziegler-Natta belongs to a multi-active-center catalyst, and due to the existence of various catalytic active centers in the polymerization reaction process and side reactions such as double bond isomerization and carbon chain rearrangement, the isomerization degree of the obtained poly-alpha-olefin molecules is high, and the poly-alpha-olefin molecules are particularly shown to stretch out side chains with different lengths on a main chain in a disordered way, so that the poly-alpha-olefin wax crystals are more difficult to form due to low molecular structure regularity of the products.

Disclosure of Invention

In view of the above-described drawbacks of the prior art, it is an object of the present application to provide the use of a metallocene catalyst composition as a catalyst in the preparation of polyalphaolefin waxes. The technical scheme of the application firstly proposes that the catalyst composition disclosed by the application can be used for preparing the polyalphaolefin wax in a catalysis way.

The invention discloses a use of a metallocene catalyst composition as a catalyst in the preparation of poly alpha olefin wax, wherein the catalyst composition comprises a main catalyst and a cocatalyst, the main catalyst is a metallocene compound, and the cocatalyst is an aluminum alkyl and/or boron-containing organic compound.

The structural general formula of the metallocene compound is shown in formula I:

M is a metal element of group IVB of the periodic Table.

The X ₁、X₂ is halogen, for example F, cl, br, I.

The E _n is a bridging group. The bridging group limits the free rotation of the metallocene around the metal center M, so that the catalyst structure has rigidity, and the large-volume linear alpha olefin monomer with carbon number more than or equal to 8 can be more sufficiently close to the active center, thereby facilitating the coordination and insertion of the catalyst.

The R ₁、R₂ groups are each independently selected from one of hydrogen, saturated or unsaturated C1 to C20 hydrocarbyl, saturated or unsaturated C1 to C20 halocarbyl, saturated or unsaturated C1 to C20 hydrocarbyloxy, saturated or unsaturated C3 to C20 cycloalkyl, C6 to C20 aryl, or C5 to C20 heteroaryl.

The R ₃、R₄、R₅、R₆ groups are each independently selected from one of hydrogen, halogen, saturated or unsaturated C1 to C20 hydrocarbyl, saturated or unsaturated C1 to C20 halocarbyl, saturated or unsaturated C1 to C20 hydrocarbyloxy, saturated or unsaturated C3 to C20 cyclic hydrocarbyl, C6 to C20 aryl, or C5 to C20 heteroaryl.

Each of the R ₇、R₈、R₉、R₁₀、R₁₁ and R ₁₂ is independently selected from one of hydrogen, halogen, saturated or unsaturated C1 to C20 hydrocarbyl.

Preferably, M is selected from one of Ti, zr and Hf. More preferably, M is Zr.

Preferably, X ₁ is Cl or Br.

Preferably, X ₂ is Cl or Br. In one embodiment, X ₁、X₂ is also a chlorine atom.

Preferably, the bridging atoms in E _n include, but are not limited to, C, si, ge, or Sn, and the number of bridging atoms is one or more.

In one or more specific embodiments, the E _n is a single carbon bridge, a dual carbon bridge, or a silicon bridge.

More preferably, the R ₁ is the same as R ₂ and is selected from hydrogen or methyl.

More preferably, R ₃、R₄ together with the 2 carbon atoms attached to the metallocene ring form a new aromatic ring, alkyl-substituted aromatic ring, aromatic heterocyclic ring or other complex aromatic condensed ring.

More preferably, R ₅、R₆ and 2 carbon atoms attached to the metallocene ring together form a new aromatic ring, alkyl-substituted aromatic ring, aromatic heterocyclic ring or other complex aromatic condensed ring;

The combination of the metallocene rings between R ₃、R₄ and/or R ₅、R₆ with benzene rings, aromatic heterocycles or other complex aromatic condensed rings increases steric hindrance near the active center of the metal and masks the axial coordination ability of the metal, thereby prolonging the chain termination time in the polymerization process, improving the molecular weight of the poly-alpha-olefin and catalyzing the polymerization activity of the poly-alpha-olefin.

More preferably, at least one pair of R ₈、R₉、R₁₀、R₁₁'s 2 carbon atoms attached to the indene ring together form a new aromatic ring, alkyl-substituted aromatic ring, aromatic heterocyclic ring, or other aromatic fused ring.

More preferably, both R ₇、R₈、R₉、R₁₀、R₁₁ and R ₁₂ are hydrogen.

Preferably, the structural general formula of the main catalyst is shown in formula II, formula III and formula IV:

in one or more embodiments, the procatalyst described above is selected from one or more of the following formulas:

Preferably, for a procatalyst in which E _n is a silicon bridge, it is prepared by comprising the steps of:

a1 The tetra-substituted cyclopentadiene, the hydrogen extracting agent and the 2- (dimethyl chlorosilane-based) indene are used as raw materials to prepare the corresponding dimethyl silicon bridge ligand through reaction, and the reaction route is as follows:

a2 The preparation method comprises the steps of) taking a dimethylsilyl bridge ligand, a hydrogen drawing agent and zirconium tetrachloride as raw materials to react to prepare a corresponding main catalyst, wherein the reaction route is as follows:

For a procatalyst wherein E _n is a single carbon bridge or a double carbon bridge and R ₃、R₄ together with the two carbon atoms on the cyclopentadienyl group form a novel benzene ring, the preparation is carried out by the steps comprising:

b1 Using tetra-substituted dihydro cyclopentadienone, sodium hydride and 3- (diethoxyphosphoryl) methyl acetate or 3- (diethoxyphosphoryl) methyl propionate as raw materials to carry out horner-wadsworth-emmons reaction, thereby preparing (tetra-substituted cyclopentadienyl) -1-methyl acetate or (tetra-substituted cyclopentadienyl) -1-methyl propionate, wherein the reaction route is as follows:

n is 1or 2;

b2 The dibenzyl magnesium chloride reacts with (tetra-substituted cyclopentadienyl) -1-methyl acetate or (tetra-substituted cyclopentadienyl) -1-methyl propionate as raw materials, and the reaction route is as follows:

n is 1or 2;

b3 Taking the reaction product of the step b 2) as a raw material, and preparing a corresponding ligand with a single carbon bridge or a double carbon bridge through dehydration reaction under the catalysis of the methylbenzenesulfonic acid TsOH, wherein the reaction route is as follows:

n is 1or 2;

b4 Corresponding single-carbon bridge or double-carbon bridge ligand, hydrogen drawing agent and zirconium tetrachloride are used as raw materials to prepare corresponding main catalyst by reaction, and the reaction route is as follows:

n is 1or 2;

Preferably, in b 2), X is halogen, for example F, cl, br, I may be present. Further preferably, the X is Cl or Br.

For a procatalyst wherein E _n is a single carbon bridge or a double carbon bridge and R ₃、R₄ and R ₅、R₆ both together with the two carbon atoms on the cyclopentadienyl group form a novel aromatic or heteroaromatic ring, prepared by comprising the steps of:

c1 The tetra-substituted cyclopentadiene, the hydrogen drawing agent and the halogenated methyl acetate or the halogenated methyl propionate are used as raw materials for reaction, so that the (tetra-substituted cyclopentadienyl) -1-methyl acetate or the (tetra-substituted cyclopentadienyl) -1-methyl propionate is prepared, and the reaction route is as follows:

n is 1or 2;

c2 The reaction is carried out by taking dibenzyl magnesium chloride and (tetra-substituted cyclopentadienyl) -1-methyl acetate or (tetra-substituted cyclopentadienyl) -1-methyl propionate as raw materials, and the reaction route is as follows:

n is 1or 2;

c3 Taking the reaction product of the step c 2) as a raw material, and preparing a corresponding ligand with a single carbon bridge or a double carbon bridge through dehydration reaction under the catalysis of the methylbenzenesulfonic acid TsOH, wherein the reaction route is as follows:

n is 1or 2;

c4 Corresponding single-carbon bridge or double-carbon bridge ligand, hydrogen drawing agent and zirconium tetrachloride are used as raw materials to react to prepare corresponding main catalyst, and the reaction route is as follows:

n is 1or 2;

Preferably, the hydrogen extracting agent is organic lithium alkali R ₀ Li.

More preferably, R ₀ is a straight-chain or branched-chain alkyl, cycloalkyl or aryl group with 1-12 carbon atoms. Further preferably, the organolithium base is n-butyllithium n-BuLi or t-butyllithium t-BuLi.

Preferably, in the step c 2), the X is halogen. Further preferably, the X is Cl or Br.

Preferably, the structural formula of the aluminum alkyl in the cocatalyst comprises AlR ₃、AlR_mH_(3-m) or AlR _mX_(3-m).

More preferably, m is an integer of 0 to 3, for example, 0,1, 2, and 3 may be used.

More preferably, the alkyl R in the structural formula is one or more of a straight-chain alkyl, a branched non-cyclic alkyl, a non-side-chain cyclic alkyl or a cyclic alkyl with a side chain with 1-12 carbon atoms.

More preferably, X in the formula is halogen.

Further preferably, the aluminum alkyl has the structure AlR ₃. In a specific embodiment, the aluminum alkyl is triisobutylaluminum.

Preferably, the organic compound containing boron in the cocatalyst is organic borate and/or organic borate.

Preferably, the organic moiety includes an alkyl group of 1 to 12 carbon atoms and/or an oxyalkyl group of 1 to 12 carbon atoms and/or a haloalkyl group of 1 to 12 carbon atoms and/or an aryl and/or alkylaryl group of 6 to 20 carbon atoms, an aralkyl group or a haloaryl group, and may be any one or more of boron compounds such as boroxine, triethylborane, triphenylborane, trifluorophenylborane, triphenylborane ammonia complex, tributyl borate, triisopropyl borate, tris (pentafluorophenyl) borane, trityltetra (pentafluorophenyl) borate, tris (p-n-octylphenyl) methyltetra (pentafluorophenyl) borate, dimethylphenylammonium tetrakis (pentafluorophenyl) borate, diethylphenylammonium tetrakis (pentafluorophenyl) borate, methyldiphenylammonium tetrakis (pentafluorophenyl) borate, ethyldiphenylammonium tetrakis (pentafluorophenyl) borate, methyldioctadecylammonium tetrakis (pentafluorophenyl) borate, trioctylammonium tetrakis (pentafluorophenyl) borate, and the like.

Further preferably, the boron-containing organic compound is trityl tetrakis (pentafluorophenyl) borate [ Ph ₃C]⁺[B(C₆F₅)₄]^－ and/or dimethylphenyl ammonium tetrakis (pentafluorophenyl) borate [ Me ₂NHPh]⁺[B(C₆F₅)₄]^－ ].

The invention discloses a preparation method of poly alpha olefin wax, which comprises the following steps of carrying out polymerization reaction on C6-C20 linear alpha olefin under the action of a metallocene catalyst composition.

Preferably, the linear alpha olefin is selected from one or more of C8 and/or C9 and/or C10 linear alpha olefins.

Preferably, the linear alpha olefin is selected from one or more of C12-C20 linear alpha olefins.

In a third aspect, the invention discloses a polyalphaolefin wax prepared according to the above-described preparation method.

Preferably, the number average molecular weight M _n of the poly alpha olefin wax is greater than or equal to 15000. Further preferably, the number average molecular weight of the polyalphaolefin wax is 15000-M _n -60000.

Preferably, the molecular weight distribution M _w/M_n of the poly alpha olefin wax is less than or equal to 1.5. The molecular weight distribution is 1.1, 1.2, 1.3, 1.4, 1.5.

Preferably, the melting point of the poly alpha olefin wax is 40-90 ℃.

More preferably, the melting point of the poly-alpha-olefin wax is 50-90 ℃. Further preferably, the melting point of the poly-alpha-olefin wax is 60-90 ℃.

The invention has the following beneficial effects:

(1) The metallocene main catalyst limits the free rotation of the metallocene around the metal center through the bridging group, so that the catalyst structure has rigidity, one end of the ligand is 2-indenyl with relatively low steric hindrance, so that a large volume of linear alpha olefin monomers are more fully close to the active center, the catalyst has high catalytic activity on linear alpha olefins with different carbon numbers, the high conversion rate of the alpha olefins can be realized under the condition of low catalyst dosage, the production cost is reduced, and particularly, the catalyst has high catalytic activity when the reaction temperature is 30 ℃ or more and the long-chain linear alpha olefins with carbon numbers of 12 or more are subjected to coordination polymerization. The catalyst composition formed by the metallocene main catalyst, alkyl aluminum and boron-containing organic compound can catalyze and synthesize polyalphaolefin with high molecular weight and narrow molecular weight distribution.

(2) From the preparation method of the metallocene main catalyst, the bridged group of the main catalyst is constructed through the Horner-Wadsworth-Emmons reaction, the ester bond is introduced, the yield is 80-90%, the yield is obviously improved compared with the method of directly reacting halogenated acid ester with tetra-substituted cyclopentadiene, and the 2-indenyl ligand in the main catalyst is constructed through the reaction of double Grignard reagent and the ester bond, so that the reaction steps are fewer, and the yield is high.

(3) The method is characterized in that low-cost C8/9/10 low-carbon number linear alpha olefin is used as a raw material, high-molecular weight and narrow-molecular weight distribution poly alpha olefin is obtained through polymerization reaction of a catalyst composition, then slow cooling crystallization is carried out, pale yellow liquid poly alpha olefin is separated through solid-liquid separation to be used as lubricating oil, drag reducer and the like, and the rest 10-40 wt% is white solid poly alpha olefin wax.

Drawings

FIG. 1 is a graph showing DSC test results of examples 18, 20, 27, 34-1, 34-2 and comparative example 4.

FIG. 2 is a C13 NMR hydrogen spectra of examples 20 and 34-2.

Detailed Description

Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.

Furthermore, it is to be understood that the reference to one or more method steps in this disclosure does not exclude the presence of other method steps before or after the combination step or the insertion of other method steps between these explicitly mentioned steps, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the method steps is merely a convenient tool for identifying the method steps and is not intended to limit the order of arrangement of the method steps or to limit the scope of the invention in which the invention may be practiced, as such changes or modifications in their relative relationships may be regarded as within the scope of the invention without substantial modification to the technical matter. Materials, reagents and the like used in the examples were commercially available unless otherwise specified, and were generally obtained in accordance with conventional conditions or recommended by the marketing company.

Example 1

This example is a preparation method of a specific main catalyst with the following structural formula.

The preparation method comprises the following steps:

d1 1-indanone, sodium hydride and methyl 3- (diethoxyphosphoryl) acetate are used as initial raw materials to carry out Horner-Wadsworth-Emmons reaction.

Firstly, adding 0.25molNaH to 150mL of toluene to prepare suspension, cooling the suspension by ice bath, then adding 0.25mol of 3- (diethoxyphosphoryl) methyl acetate to the toluene suspension of NaH cooled to 0 ℃ by ice bath under the protection of nitrogen, removing the cooling after the addition, naturally heating to room temperature, stirring for 30min at room temperature until the liquid in a reaction bottle becomes clear and transparent, preparing 0.2mol of 1-indanone and 50mL of toluene into solution, adding the solution into the reaction bottle, placing the mixture into 95-105 ℃ for heat preservation reaction for 24h, adding water layer and oil layer, extracting the water layer with ethyl acetate for 3 times again, evaporating the oil layer under reduced pressure, drying to obtain an amber crude product, purifying the crude product by using a mixed solution of hexane and ethyl acetate with the volume ratio of 9:1 as eluent by using a rotary evaporator under the vacuum of 0.8 r, and removing the solvent under reduced pressure to obtain the reddish oily liquid (1-indenyl) -1-methyl acetate with the yield of 0.174% of the target mass ratio to the actual product of 0.9% of the target mass ratio.

Structural confirmation of (1-indenyl) -1-acetic acid methyl ester:

¹H NMR(400MHz,CDCl₃):δ3.19(s,2H),3.32(dd,J＝11.3,1.7Hz,2H),3.65(s,3H),5.81(t,J＝1.7Hz,1H),7.10(ddd,J＝8.1,7.7,2.2Hz,1H),7.18(ddd,J＝7.9,7.7,1.0Hz,1H),7.22(ddd,J＝7.9,2.2,0.6Hz,1H),7.34(ddd,J＝8.1,1.0,0.6Hz,1H).

d2 O-dichlorobenzyl grignard reagent) 0.6mol of 50 mesh magnesium powder was placed in a three-necked round bottom flask, heated to 110 ℃ under vacuum at 10torr and dried overnight, followed by flushing the magnesium powder with dry nitrogen and cooling to ambient temperature. 120mL of anhydrous THF and 0.025mol of 2-dibromoethane were added, gas evolution occurred after 2min, the flask was cooled to room temperature, and all volatiles were removed under vacuum at 0.8 torr. 0.15mol of o-dichlorobenzyl was dissolved in 150mL of anhydrous THF and transferred to an addition funnel. The THF solution of o-dichlorobenzyl was added dropwise to the THF suspension of magnesium over 3h, and the reaction mixture was stirred for reaction for 12h and then was stationary. After the excess magnesium had settled, it was filtered, and the pale yellow filtrate obtained by filtration, i.e. the grignard solution of o-dichlorobenzene, was retained.

0.1Mol of methyl (1-indenyl) -1-acetate was dissolved in 100mL of THF and transferred to a dropping funnel. The ester solution was added dropwise to the o-dichlorobenzene solution over 3h at-78 ℃. After the completion of the dropwise addition, the temperature was slowly raised to room temperature and stirred for 12 hours overnight. After quenching the reaction mixture with water, the solvent was removed under reduced pressure at 0.8 torr. Diethyl ether was added and the mixture was neutralized with 1mol/L HCl, the ether phase was separated and the aqueous phase was extracted twice more with diethyl ether. After drying the combined organic phases over anhydrous magnesium sulfate and filtering off all solids, the solvent was removed under reduced pressure using a rotary evaporator under vacuum at 0.8torr to give the crude product, which was purified by flash chromatography using a mixture of hexane and diethyl ether as eluent, followed by removal of the solvent under reduced pressure using a rotary evaporator under vacuum at 0.8torr to give 66.7mmol of ((1-indenyl) -methyl) -2-indanol as an off-white solid in 66.7% yield.

Structural confirmation of the((1-indenyl) -methyl) -2-indanol:

¹H NMR(400MHz,CDCl₃):δ3.00(d,J＝15.6Hz,4H),3.34(dd,J＝13.3,1.9Hz,2H),3.38(s,2H),5.77(t,J＝1.9Hz,1H),7.10(td,J＝7.7,2.1Hz,1H),7.18(ddd,J＝7.9,7.7,1.1Hz,1H),7.22(ddd,J＝7.9,2.1,0.5Hz,1H),7.22(ddd,J＝7.8,2.1,0.5Hz,2H),7.24(ddd,J＝7.8,7.6,2.1Hz,2H),7.34(ddd,J＝7.7,1.1,0.5Hz,1H).

d3 10mmol of p-toluenesulfonic acid monohydrate and 66.7mmol of ((1-indenyl) -methyl) -2-indanol were placed in a three-necked round bottom flask, and 100mL of reagent grade toluene was then added to the flask to form a suspension. The flask was heated to 110-120 ℃ and refluxed for 2h, then cooled to room temperature. Distilled water was added to the flask until the solids in the suspension dissolved to become a solution, then the liquid in the flask was transferred to a separating funnel to separate a toluene layer, the aqueous layer was washed twice with diethyl ether, the combined organic layers were dried over anhydrous magnesium sulfate and the solvent was removed under reduced pressure under a vacuum of 0.8torr to give a crude product, which was purified by flash chromatography using a mixed solution of hexane and diethyl ether as an eluent. The solvent was then removed under reduced pressure using a rotary evaporator under vacuum at 0.8torr to give 63.0mmol of (2-indenyl) - (1-indenyl) -methane as a pale yellow solid in 94.5% yield. FTIR analysis of the pale yellow solid showed no significant absorption peak at 3200-3600cm ^-1, and it was considered that all the hydroxyl groups had undergone a dehydration rearrangement reaction.

D4 93.7mmol of n-butyllithium n-BuLi was added with 60mL of hexane to prepare n-BuLi hexane solution in a glove box under nitrogen atmosphere, 63.0mmol of [ (2-indenyl) - (1-indenyl) ] -methane was put into a round bottom flask, 60mL of hexane was added to dissolve the n-BuLi solution, the ice bath was stirred and cooled to-20 ℃, then the prepared n-BuLi hexane solution was added, naturally warmed to room temperature and then stirred and reacted at room temperature for 5 hours to prepare (2-indenyl) - (1-indenyl) -methane lithium salt solution, then 90.1mmol of ZrCl ₄ was dissolved with 80mL of hexane in the glove box, the above lithium salt solution was added to ZrCl ₄ in ice bath and stirred and then warmed to room temperature, stirred and reacted at room temperature for 20 hours, liCl was removed by suction filtration from the obtained suspension after the end of the reaction, and all solvents were removed by distillation under reduced pressure to obtain 41.3mmol of light yellow solid bis ((2-indenyl) - (1-indenyl) -methane) zirconium dichloride, yield 65.6%.

Structural confirmation of bis ((2-indenyl) - (1-indenyl) -methane) zirconium dichloride:

¹H NMR(400MHz,CDCl₃):δ3.59(d,J＝13.7Hz,1H),3.72(d,J＝13.7Hz,1H),6.07(dd,J＝2.1,0.7Hz,1H),6.30(dd,J＝2.1,0.7Hz,1H),6.59(d,J＝3.4Hz,1H),6.81(d,J＝3.4Hz,1H),7.06-7.38(m,5H),7.47-7.50(m,2H),7.59-7.62(m,1H).

¹³C NMR(101MHz,CDCl₃):δ27.0,89.5,98.6,103.4,112.0,112.9,121.7,122.5,124.9,125.2,126.4,126.6,127.2,128.5,129.1,129.9,140.3,143.1.

Example 2

The preparation method comprises the following steps:

e1 Unlike step d 1) described in example 1), horner-wadsworth-emmons was conducted using 0.25mol of methyl 3- (diethoxyphosphoryl) propionate instead of methyl 3- (diethoxyphosphoryl) acetate, whereby 0.175mol of methyl (1-indenyl) -1-propionate was produced as a reddish oily liquid, with a yield of 87.5%.

Structural confirmation of methyl (1-indenyl) -1-propionate:

¹H NMR(400MHz,CDCl₃):δ2.39-2.51(m,4H),3.33(dd,J＝13.3,1.9Hz,2H),3.64(s,3H),5.72(t,J＝1.9Hz,1H),7.10(td,J＝7.7,2.1Hz,1H),7.18(ddd,J＝7.9,7.7,1.1Hz,1H),7.22(ddd,J＝7.9,2.1,0.5Hz,1H),7.34(ddd,J＝7.7,1.1,0.5Hz,1H).

e2 (1-indenyl) -2-indanol was obtained in 65.5mmol of off-white solid ((1-indenyl) -ethyl) -2-indanol in 65.5% yield by substituting 0.1mol of methyl (1-indenyl) -1-propionate for the methyl (1-indenyl) -1-acetate in step d 2) described in example 1).

Structural confirmation of the((1-indenyl) -ethyl) -2-indanol:

¹H NMR(400MHz,CDCl₃):δ1.63(t,J＝9.4Hz,2H),2.16(t,J＝9.4Hz,2H),3.00(d,J＝15.6Hz,4H),3.31(dd,J＝13.2,1.9Hz,2H),5.67(t,J＝1.9Hz,1H),7.10(td,J＝7.7,2.1Hz,1H),7.18(ddd,J＝7.9,7.7,1.1Hz,1H),7.22(ddd,J＝7.9,2.1,0.5Hz,1H),7.22(ddd,J＝7.8,2.1,0.5Hz,2H),7.24(ddd,J＝7.8,7.6,2.1Hz,2H),7.34(ddd,J＝7.7,1.1,0.5Hz,1H).

e3 Step d 3) described in example 1), except that 65.5mmol of ((1-indenyl) -ethyl) -2-indanol was used to react with 10mmol of p-toluenesulfonic acid monohydrate, 60.4mmol of (2-indenyl) - (1-indenyl) -ethane was finally obtained as a pale yellow solid in 92.2%. FTIR analysis of the pale yellow solid showed no significant absorption peak at 3200-3600cm ^-1, and it was considered that all the hydroxyl groups had undergone a dehydration rearrangement reaction.

E4 (2-indenyl) - (1-indenyl) -ethane was prepared by reacting 93.7mmol of n-butyllithium n-BuLi with 60mL of hexane to prepare n-BuLi in hexane solution, 60.4mmol of (2-indenyl) - (1-indenyl) -ethane with n-BuLi in hexane solution to prepare a lithium salt solution of (2-indenyl) - (1-indenyl) -ethane, and then reacting with 80mL of hexane solution containing 90.1mmol of ZrCl ₄ to obtain 36.6mmol of bis ((2-indenyl) - (1-indenyl) -ethane) zirconium dichloride as a pale yellow solid, the yield being 60.6%.

Structural confirmation of bis ((2-indenyl) - (1-indenyl) -ethane) zirconium dichloride:

¹H NMR(400MHz,CDCl₃):δ3.39-3.56(m,3H),3.68-3.77(m,1H),6.13(d,J＝2.5Hz,1H),6.37(d,J＝2.7Hz,1H),6.53(d,J＝3.4Hz,1H),6.78(d,J＝3.4Hz,1H),7.13-7.33(m,5H),7.47-7.56(m,2H),7.65-7.68(m,1H).

¹³C NMR(100MHz,CDCl₃):δ28.2,31.7,99.6,104.6,112.1,114.5,121.7,121.8,123.5,125.2,126.0,126.3,126.9,127.5,128.0,129.5,130.4,140.7,145.6.

Example 3

The preparation method comprises the following steps:

f1 Unlike step d 1) described in example 1), the reaction of horner-wadsworth-emmons was performed using 0.2mol of 2-phenyl-1-indanone as an initial starting material instead of 1-indanone in step d 1), thereby preparing 0.161mol of methyl (2-phenyl-1-indenyl) -1-acetate as a reddish oily liquid in a yield of 80.6%.

Structural confirmation of (2-phenyl-1-indenyl) -1-acetic acid methyl ester:

¹H NMR(400MHz,CDCl₃):δ3.27(s,2H),3.42(d,J＝13.6Hz,2H),3.63(s,3H),7.08(ddd,J＝8.3,8.2,2.6Hz,1H),7.16(td,J＝8.1,1.0Hz,1H),7.17(ddd,J＝8.1,2.6,0.4Hz,1H),7.25(tt,J＝7.5,1.3Hz,1H),7.31(ddd,J＝8.3,1.0,0.4Hz,1H),7.33(dddd,J＝7.9,2.1,1.3,0.5Hz,2H),7.37(dddd,J＝7.9,7.5,1.7,0.5Hz,2H).

f2 (1-indenyl) -1-acetic acid methyl ester in step d 2) was replaced with 0.1mol of (2-phenyl-1-indenyl) -1-acetic acid methyl ester in example 1), and 65.0mmol of ((2-phenyl-1-indenyl) -methyl) -2-indanol was finally obtained in a yield of 65.0%.

Structural confirmation of the((2-phenyl-1-indenyl) -methyl) -2-indanol:

¹H NMR(400MHz,CDCl₃):δ2.94-3.08(m,4H),3.40(s,2H),3.44(d,J＝13.6Hz,2H),7.09(ddd,J＝8.5,8.1,2.7Hz,1H),7.11(ddd,J＝7.8,2.1,0.5Hz,2H),7.16(td,J＝8.1,1.0Hz,1H),7.17(ddd,J＝8.1,2.7,0.5Hz,1H),7.24(ddd,J＝7.8,7.6,2.1Hz,2H),7.25(tt,J＝7.5,1.3Hz,1H),7.34(dddd,J＝7.9,7.5,1.7,0.5Hz,2H),7.36(dddd,J＝7.9,2.0,1.3,0.5Hz,2H),7.37(ddd,J＝8.5,1.0,0.5Hz,1H).

f3 Step d 3) described in example 1), except that 65.0mmol of ((2-phenyl-1-indenyl) -methyl) -2-indanol was used to react with 10mmol of p-toluenesulfonic acid monohydrate, 61.2mmol of (2-indenyl) - (2-phenyl-1-indenyl) -methane was finally obtained as a pale yellow solid in 94.1% yield. FTIR analysis of the pale yellow solid showed no significant absorption peak at 3200-3600cm ^-1, and it was considered that all the hydroxyl groups had undergone a dehydration rearrangement reaction.

F4 (2-indenyl) - (2-phenyl-1-indenyl) -methane was prepared by reacting 61.2mmol of (2-indenyl) - (2-phenyl-1-indenyl) -methane with n-BuLi in hexane by adding 93.7mmol of n-butyllithium n-BuLi to 60mL of hexane to prepare n-BuLi in hexane, followed by reacting with 80mL of hexane solution containing 90.1mmol of ZrCl ₄ to obtain 30.8mmol of zirconium dichloride as a pale yellow solid as a main catalyst in 50.4% yield.

Structural confirmation of bis ((2-indenyl) - (2-phenyl-1-indenyl) -methane) zirconium dichloride:

¹H NMR(400MHz,CDCl₃):δ4.54(d,J＝13.7Hz,1H),5.05(d,J＝13.7Hz,1H),5.08(dd,J＝2.1,0.7Hz,1H),5.83(dd,J＝2.1,0.7Hz,1H),6.95(s,1H),7.16-7.63(m,11H),7.87-7.90(m,2H).

¹³C NMR(101MHz,CDCl₃):δ25.6,88.0,97.8,98.2,100.4,111.0,112.6,121.7,122.5,124.9,125.2,125.8,126.3,126.4,126.9,127.2,128.4,128.7,129.4,129.9,132.3,133.5.

Example 4

The preparation method comprises the following steps:

g1 Unlike step d 1) described in example 1), the reaction of horner-wadsworth-emmons was conducted using 0.2mol of 2-phenyl-1-indanone as an initial starting material in step d 1), whereby 0.163mol of methyl (2-phenyl-1-indenyl) -1-propionate was produced as a reddish oily liquid in a yield of 81.2%.

Structural confirmation of methyl (2-phenyl-1-indenyl) -1-propanoate:

¹H NMR(400MHz,CDCl₃):δ2.52-2.65(m,4H),3.41(d,J＝13.6Hz,2H),3.66(s,3H),7.08(ddd,J＝8.1,7.8,2.7Hz,1H),7.16(td,J＝8.1,1.0Hz,1H),7.17(ddd,J＝8.1,2.7,0.4Hz,1H),7.25(tt,J＝7.5,1.3Hz,1H),7.32-7.38(m,4H).

g2 (1-indenyl) -1-acetic acid methyl ester in step d 2) was replaced with 0.1mol of (2-phenyl-1-indenyl) -1-propionic acid methyl ester in step d 2), and 55.9mmol of an off-white solid ((2-phenyl-1-indenyl) -ethyl) -2-indanol was finally obtained in 55.9%.

Structural confirmation of the((2-phenyl-1-indenyl) -ethyl) -2-indanol:

¹H NMR(400MHz,CDCl₃):δ1.80(t,J＝9.4Hz,2H),2.19(t,J＝9.4Hz,2H),2.94-3.08(m,4H),3.43(d,J＝13.6Hz,2H),7.08(ddd,J＝8.2,7.8,2.7Hz,1H),7.16(td,J＝8.1,1.0Hz,1H),7.17(ddd,J＝8.1,2.7,0.5Hz,1H),7.22(ddd,J＝7.8,2.1,0.5Hz,2H),7.24(ddd,J＝7.8,7.6,2.1Hz,2H),7.25(tt,J＝7.5,1.3Hz,1H),7.34(dddd,J＝7.9,7.5,1.7,0.5Hz,2H),7.36(dddd,J＝7.9,1.9,1.3,0.5Hz,2H),7.37(ddd,J＝7.8,1.0,0.5Hz,1H).

g3 Step d 3) described in example 1), except that 55.9mmol of ((2-phenyl-1-indenyl) -ethyl) -2-indanol was used to react with 10mmol of p-toluenesulfonic acid monohydrate, 50.8mmol of (2-indenyl) - (2-phenyl-1-indenyl) -ethane was finally obtained as a pale yellow solid in a yield of 90.9%. FTIR analysis of the pale yellow solid showed no significant absorption peak at 3200-3600cm ^-1, and it was considered that all the hydroxyl groups had undergone a dehydration rearrangement reaction.

G4 (2-indenyl) - (2-phenyl-1-indenyl) -ethane was prepared by reacting 50.8mmol of (2-indenyl) - (2-phenyl-1-indenyl) -ethane with a hexane solution of n-BuLi, followed by a reaction with 80mL of hexane solution containing 90.1mmol of ZrCl ₄ to give 26.7mmol of zirconium dichloride as a pale yellow solid main catalyst, which was 26.7mmol, with the addition of 60mL of hexane to prepare an n-BuLi hexane solution, with the exception of step d 4) described in example 1.

Structural confirmation of bis ((2-indenyl) - (2-phenyl-1-indenyl) -ethane) zirconium dichloride:

¹H NMR(400MHz,CDCl₃):δ3.18-3.36(m,2H),3.77-3.95(m,2H),5.74(d,J＝2.5Hz,1H),6.19(d,J＝2.5Hz,1H),6.87(s,1H),7.13-7.34(m,5H),7.42-7.48(m,3H),7.55-7.58(m,2H),7.66-7.69(m,1H),7.84-7.87(m,2H).

¹³C NMR(101MHz,CDCl₃):δ27.1,30.6,100.9,103.7,112.9,117.3,122.2,125.1,125.4,125.7,125.9,126.5,127.0,127.3,128.6,128.9,129.3,129.5,132.6,134.5,141.7.

Example 5

The preparation method comprises the following steps:

h1 Taking 4H-cyclopenta [2,1-b:3,4-b' ] dithiophene, namely 4H-dithiophene as an initial raw material, firstly dissolving 0.25mol of 4H-dithiophene in 250mL of THF, dropwise adding 0.26mol of n-butyllithium into the THF solution of the 4H-dithiophene after cooling to-20 ℃ by stirring in an ice bath, naturally heating the reaction mixture to room temperature and stirring for reaction for 2H, subsequently cooling to-78 ℃, dropwise adding 0.25mol of methyl bromoacetate at the temperature, naturally heating the reaction mixture to room temperature after 30min, stirring for reaction for 12H, and ending the reaction. The reaction was quenched with water, volatiles such as solvent were removed by distillation under reduced pressure, and the crude product was dissolved in diethyl ether and water. The organic layer was separated and the aqueous phase was washed twice with diethyl ether. After drying the combined organic layers over magnesium sulfate, the solvent was distilled off under reduced pressure. The crude product was obtained as an amber color and purified by flash chromatography using a mixture of hexane and diethyl ether as eluent, whereby 0.139mol of methyl (4-dithienocyclopentadienyl) -1-acetate was obtained as a brown oily liquid in a yield of 55.6%.

¹H NMR(400MHz,CDCl₃):δ2.68(d,J＝3.7Hz,2H),3.71(s,3H),4.31(t,J＝3.7Hz,1H),7.03(d,J＝5.0Hz,2H),7.32(d,J＝5.0Hz,2H).

H2 (4-dithienocyclopentadienyl) -1-methyl acetate was replaced with 0.1mol of methyl (4-dithienocyclopentadienyl) -1-acetate in the step d 2) described in example 1, and the (4-dithienocyclopentadienyl) -1-methyl acetate solution was added dropwise to the Grignard solution of o-dichlorobenzene for reaction, whereby a tan solid ((4-dithienocyclopentadienyl) -methyl) -2-indanol was obtained in a yield of 52.7 mmol.

1H NMR(400MHz,CDCl₃):δ3.01(d,J＝15.6Hz,4H),3.08(d,J＝6.1Hz,2H),4.01(t,J＝6.1Hz,1H),7.00(d,J＝4.9Hz,2H),7.18-7.33(m,6H).

¹H NMR(400MHz,CDCl₃):δ3.01(d,J＝15.6Hz,4H),3.08(d,J＝6.1Hz,2H),4.01(t,J＝6.1Hz,1H),7.00(d,J＝4.9Hz,2H),7.18-7.33(m,6H).

H3 Step d 3) described in example 1), except that 52.7mmol of ((4-dithienocyclopentadienyl) -methyl) -2-indanol was used to react with 10mmol of p-toluenesulfonic acid monohydrate, 50.6mmol of (2-indenyl) - (4-dithienocyclopentadienyl) -methane was finally obtained as a tan solid in a yield of 96.0%. FTIR analysis of the resulting brown-yellow solid showed no significant absorption peak at 3200-3600cm ^-1, which suggests that all hydroxyl groups had undergone a dehydration rearrangement reaction.

H4 (2-indenyl) - (4-dithienocyclopentadienyl) -methane was reacted with a hexane solution of n-BuLi to obtain a lithium salt solution of (2-indenyl) - (4-dithienocyclopentadienyl) -methane, followed by reaction with 80mL of a hexane solution containing 90.1mmol of ZrCl4 to obtain 27.3mmol of zirconium dichloride as a yellow-orange solid main catalyst, bis ((2-indenyl) - (4-dithienocyclopentadienyl) -methane) in a yield of 54.0%.

¹H NMR(400MHz,CDCl₃):δ2.81(d,J＝13.8Hz,1H),2.93(d,J＝13.8Hz,1H),4.83(s,1H),6.73(s,1H),7.02(ddd,J＝7.9,1.4,0.5Hz,1H),7.06(td,J＝7.7,1.4Hz,1H),7.08(d,J＝4.9Hz,2H),7.18(ddd,J＝7.9,7.8,1.1Hz,1H),7.31(ddd,J＝7.7,1.1,0.5Hz,1H),7.40(d,J＝4.9Hz,2H).

¹³C NMR(101MHz,CDCl₃):δ29.2,47.9,54.7,120.5,125.2,125.4,126.7,127.0,127.2,127.3,127.8,128.1,128.3,128.7,128.9,131.0,131.8,143.6.

Example 6

The preparation method comprises the following steps:

i1 Unlike step h 1) described in example 5), methyl bromoacetate in step h 1) was used with 0.25mol of methyl bromopropionate, whereby 0.150mol of methyl (4-dithienocyclopentadienyl) -1-propionate was produced as a reddish oily liquid in a yield of 60.1%.

¹H NMR(400MHz,CDCl₃):δ2.25(dt,J＝8.0,7.4Hz,2H),2.35(t,J＝7.4Hz,2H),3.65(s,3H),4.10(t,J＝8.0Hz,1H),7.00(d,J＝4.9Hz,2H),7.31(d,J＝4.9Hz,2H).

I2 (1-dithienocyclopentadienyl) -1-acetic acid methyl ester in the step h 2) was replaced with 0.1 mol) of methyl (4-dithienocyclopentadienyl) -1-propanoate as described in the step h 2), and 57.9mmol of tan solid ((4-dithienocyclopentadienyl) -ethyl) -2-indanol was finally obtained in a yield of 57.9%.

¹H NMR(400MHz,CDCl₃):δ1.46(t,J＝2.7Hz,2H),2.28(dt,J＝6.0,2.7Hz,2H),3.07(d,J＝15.6Hz,4H),4.08(t,J＝6.0Hz,1H),6.99(d,J＝4.9Hz,2H),7.15-7.37(m,6H).

I3 (2-indenyl) - (4-dithienocyclopentadienyl) -ethane 55.8mmol, 96.4% yield, was obtained as a tan solid, which was obtained by reacting 57.9mmol of ((4-dithienocyclopentadienyl) -ethyl) -2-indanol with 10mmol of p-toluenesulfonic acid monohydrate, as a difference from step h 3) described in example 5. FTIR analysis of the resulting brown-yellow solid showed no significant absorption peak at 3200-3600cm ^-1, which suggests that all hydroxyl groups had undergone a dehydration rearrangement reaction.

I4 (2-indenyl) - (4-dithienocyclopentadienyl) -ethane was reacted with a hexane solution of n-BuLi to obtain a lithium salt solution of (2-indenyl) - (4-dithienocyclopentadienyl) -ethane, followed by reaction with 80mL of a hexane solution containing 90.1mmol of ZrCl4 to obtain 30.9mmol of zirconium dichloride as a orange solid as a main catalyst (2-indenyl) - (4-dithienocyclopentadienyl) -ethane) in a yield of 55.3%.

¹H NMR(400MHz,CDCl₃):δ2.05(ddd,J＝14.2,10.3,2.7Hz,1H),2.19(ddd,J＝14.6,2.8,2.7Hz,1H),2.22(dt,J＝14.2,2.8Hz,1H),2.23(ddd,J＝14.6,10.3,2.8Hz,1H),4.78(s,1H),6.69(s,1H),7.05(ddd,J＝9.6,8.2,1.1Hz,1H),7.07(d,J＝4.9Hz,1H),7.11(ddd,J＝8.2,1.3,0.5Hz,1H),7.14(ddd,J＝9.6,7.9,1.3Hz,1H),7.17(d,J＝4.9Hz,1H),7.28(ddd,J＝7.9,1.1,0.5Hz,1H),7.40(d,J＝4.9Hz,2H).

¹³C NMR(101MHz,CDCl₃):δ30.4,33.0,47.9,54.7,120.2,125.4,125.5,127.2,127.3,127.5,127.6,127.8,128.0,128.3,128.5,131.6,131.9,143.7.

Example 7

The preparation method comprises the following steps:

j1 Unlike step H1) described in example 5), 4H-dithienocyclopentadiene in step H1) was replaced with 0.25mol of 9H-fluorene as an initial material, whereby 0.149mol of methyl (9-fluorenyl) -1-acetate was produced as a yellow oily liquid in a yield of 59.8%.

¹H NMR(400MHz,CDCl₃):δ3.02(d,J＝5.5Hz,2H),3.77(s,3H),4.60(t,J＝5.5Hz,1H),7.34(ddd,J＝7.9,6.9,1.1Hz,2H),7.36(ddd,J＝8.5,6.9,1.4Hz,2H),7.62(ddd,J＝7.9,1.4,0.5Hz,2H),7.83(ddd,J＝8.5,1.1,0.5Hz,2H).

J2 (9-fluorenyl) -1-acetic acid methyl ester was substituted for the (4-dithienocyclopentadienyl) -1-acetic acid methyl ester in the step h 2) by 0.1mol of (9-fluorenyl) -1-acetic acid methyl ester in the step h 2), and 59.8mmol of ((9-fluorenyl) -methyl) -2-indanol was finally obtained as a yellow solid in a yield of 63.1%.

¹H NMR(400MHz,CDCl₃):δ3.02(d,J＝15.6Hz,4H),3.37(d,J＝5.3Hz,2H),4.34(t,J＝5.3Hz,1H),7.22(ddd,J＝7.8,2.1,0.5Hz,2H),7.24(ddd,J＝7.8,7.6,2.1Hz,2H),7.33(ddd,J＝7.6,6.9,1.1Hz,2H),7.36(ddd,J＝8.5,6.9,1.4Hz,2H),7.58(ddd,J＝7.6,1.4,0.5Hz,2H),7.83(ddd,J＝8.5,1.1,0.5Hz,2H).

J3 59.8mmol of ((9-fluorenyl) -methyl) -2-indanol is reacted with 10mmol of p-toluenesulfonic acid monohydrate, which is different from step h 3) described in example 5, to finally yield 58.3mmol of (2-indenyl) - (9-fluorenyl) -methane as a tan solid in 97.6%. FTIR analysis of the resulting brown-yellow solid showed no significant absorption peak at 3200-3600cm ^-1, which suggests that all hydroxyl groups had undergone a dehydration rearrangement reaction.

J4 (2-indenyl) - (9-fluorenyl) -methane was reacted with a hexane solution of n-BuLi to obtain a lithium salt solution of (2-indenyl) - (9-fluorenyl) -methane, followed by reaction with a hexane solution of ZrCl ₄ to obtain 34.0mmol of zirconium dichloride as a main catalyst in the form of an orange yellow solid ((2-indenyl) - (9-fluorenyl) -methane) in a yield of 58.2%.

Structural confirmation of bis ((2-indenyl) - (9-fluorenyl) -methane) zirconium dichloride:

¹H NMR(400MHz,CDCl₃):δ2.95(d,J＝14.2Hz,1H),3.04(d,J＝14.2Hz,1H),4.92(s,1H),6.73(s,1H),7.02(ddd,J＝7.9,1.4,0.5Hz,1H),7.06(td,J＝7.7,1.4Hz,1H),7.18(ddd,J＝7.9,7.8,1.1Hz,1H),7.31(ddd,J＝7.7,1.1,0.5Hz,1H),7.38(ddd,J＝8.5,6.9,1.4Hz,2H),7.39(ddd,J＝7.7,6.9,1.5Hz,2H),7.67(ddd,J＝7.7,1.4,0.5Hz,2H),7.85(ddd,J＝8.5,1.5,0.5Hz,2H).

¹³C NMR(101MHz,CDCl₃):δ29.2,47.9,54.7,119.9,120.0,120.4,127.0,127.3,127.5,127.8,127.9,128.1,128.4,128.8,129.0,129.6,140.2,140.8,143.7.

Example 8

The preparation method comprises the following steps:

k1 (9-fluorenyl) -1-propionic acid methyl ester was prepared as a yellow oily liquid in a yield of 57.2% by substituting 0.25mol of methyl bromopropionate for methyl bromoacetate in the step j 1) described in example 7, with the difference that step j 1) described in example 7.

¹H NMR(400MHz,CDCl₃):δ2.35(t,J＝7.4Hz,2H),2.36(td,J＝7.4,3.9Hz,2H),3.65(s,3H),4.32(t,J＝3.9Hz,1H),7.33(ddd,J＝8.5,6.9,1.4Hz,2H),7.37(ddd,J＝7.6,6.9,1.1Hz,2H),7.57(ddd,J＝7.6,1.4,0.5Hz,2H),7.80(ddd,J＝8.5,1.1,0.5Hz,2H).

K2 (9-fluorenyl) -1-indanol is obtained in 59.4mmol of yellow solid ((9-fluorenyl) -ethyl) -2-indanol in 59.4% yield) which differs from step j 2) described in example 7 in that 0.1mol of methyl (9-fluorenyl) -1-propionate is substituted for methyl (9-fluorenyl) -1-acetate in step j 2).

¹H NMR(400MHz,CDCl₃):δ1.46(t,J＝10.1Hz,2H),2.23(td,J＝10.1,5.2Hz,2H),3.01(d,J＝15.6Hz,4H),4.21(t,J＝5.2Hz,1H),7.22(ddd,J＝7.8,2.1,0.5Hz,2H),7.24(ddd,J＝7.8,7.6,2.1Hz,2H),7.36(ddd,J＝8.5,6.9,1.4Hz,2H),7.37(ddd,J＝7.6,6.9,1.1Hz,2H),7.577＝J(ddd,.6,1.4,0.5Hz,2H),7.83(ddd,J＝8.5,1.1,0.5Hz,2H).

K3 (9-fluorenyl) -ethyl) -2-indanol, 59.4mmol, and p-toluenesulfonic acid monohydrate, were reacted to give 57.3mmol of (2-indenyl) - (9-fluorenyl) -ethane as a tan solid in 96.5% yield. FTIR analysis of the resulting brown-yellow solid showed no significant absorption peak at 3200-3600cm ^-1, which suggests that all hydroxyl groups had undergone a dehydration rearrangement reaction.

K4 (2-indenyl) - (9-fluorenyl) -ethane was reacted with a hexane solution of n-BuLi to obtain a lithium salt solution of (2-indenyl) - (9-fluorenyl) -ethane, followed by reaction with a hexane solution of ZrCl ₄ to obtain 30.2mmol of zirconium dichloride as a orange solid main catalyst, bis ((2-indenyl) - (9-fluorenyl) -ethane) in a yield of 52.7%.

Structural confirmation of bis ((2-indenyl) - (9-fluorenyl) -ethane) zirconium dichloride

¹H NMR(400MHz,CDCl₃):δ2.07(ddd,J＝14.3,10.3,2.7Hz,1H),2.17(dt,J＝14.3,2.8Hz,1H),2.42(ddd,J＝14.0,2.9,2.7Hz,1H),2.48(ddd,J＝14.0,10.3,2.8Hz,1H),4.81(s,1H),6.69(s,1H),7.05-7.14(m,2H),7.19(ddd,J＝9.6,8.2,1.1Hz,1H),7.28(ddd,J＝7.9,1.1,0.5Hz,1H),7.39-7.65(m,6H),7.68-7.81(m,2H).

¹³C NMR(101MHz,CDCl₃):δ30.2,33.0,47.9,54.7,119.8,120.0,120.5,127.2,127.3,127.6,127.8,127.9,128.0,128.3,128.8,129.2,129.9,140.7,140.9,143.8.

Example 9

The preparation method comprises the following steps:

l 1) starting from indene and 2- (dimethylchlorosilane) indene, 0.875mol of n-butyllithium dissolved in 120mL of THF are added dropwise to 86.2mmol of indene dissolved in 50mL of THF at 0℃for 20min, the reaction mixture is naturally warmed to room temperature after the addition is completed, stirred for 3h to give a lithium salt solution of indene, which is transferred to a dropping funnel. To 93.4mmol of chloro-2-indenyl silane was added 50mL of THF to prepare a solution, and then a lithium salt solution of the above indene was added dropwise thereto. After completion of the dropwise addition, the reaction was stirred at room temperature for 12 hours, and quenched with 50mL of distilled water. The solvent THF was then distilled off under reduced pressure to give a crude product, and diethyl ether and saturated brine were added to the crude product. After separation of the ether layer, the aqueous phase was washed twice with diethyl ether. The combined organic layers were dried over anhydrous magnesium sulfate, and then evaporated under reduced pressure, and purified by flash chromatography using hexane as a solvent to give a yellow oil which was automatically crystallized in a stationary state to finally give 54.4mmol of dimethyl- (1-indenyl) - (2-indenyl) silane as off-white crystals in 63.1% yield.

Structural confirmation of dimethyl- (1-indenyl) - (2-indenyl) silane:

¹H NMR(400MHz,CDCl₃):δ0.29(s,6H),3.43(d,J＝14.2Hz,2H),3.67(d,J＝3.0Hz,1H),5.88(dd,J＝5.3,3.0Hz,1H),6.55(s,1H),6.77(d,J＝5.3Hz,1H),6.96(ddd,J＝7.8,2.0,0.5Hz,1H),7.06-7.32(m,7H).

l 2) differs from step d 2) described in example 1 in that 54.4mmol of dimethyl- (1-indenyl) - (2-indenyl) silane was reacted first with n-BuLi in hexane to give a lithium salt solution of dimethyl- (1-indenyl) - (2-indenyl) silane, which was subsequently reacted with ZrCl ₄ in hexane to give 28.1mmol of zirconium dichloride as a yellow solid as a main catalyst, bis (dimethyl- (1-indenyl) - (2-indenyl) silane) in a yield of 51.6%.

Structural confirmation of bis (dimethyl- (1-indenyl) - (2-indenyl) silane) zirconium dichloride:

¹H NMR(400MHz,CDCl₃):δ0.51(s,3H),1.03(s,3H),5.18(s,1H),6.05(d,J＝8.5Hz,1H),6.68(s,1H),6.92(d,J＝8.5Hz,1H),7.02-7.38(m,8H).

¹³C NMR(101MHz,CDCl₃):δ-1.0,-0.3,47.9,71.7,120.0,120.3,123.2,123.9,127.4,127.6,127.8,128.3,128.6,128.8,129.5,132.1,143.0,143.9.

Example 10

The preparation method comprises the following steps:

m 1) differs from step l 1) described in example 9 in that 84.8mmol of 2-phenyl-indene are used as starting material and are reacted with 93.4mmol of chloro-2-indenyl silane to give 49.4mmol of dimethyl- (2-phenyl-1-indenyl) - (2-indenyl) silane as off-white crystals in a yield of 58.2%.

¹ H-NMR (400 MHz, solvent ：CDCl₃):δ0.18(s,6H),3.44(d,J＝14.4Hz,2H),3.80(s,1H),6.55(s,1H),6.96(ddd,J＝7.8,2.0,0.5Hz,1H),7.03-7.46(13H,m).

M 2) differs from step l 2) described in example 9 in that 49.4mmol of dimethyl- (2-phenyl-1-indenyl) - (2-indenyl) silane was reacted first with a hexane solution of n-BuLi to give a lithium salt solution of dimethyl- (2-phenyl-1-indenyl) - (2-indenyl) silane and then with a hexane solution of ZrCl ₄ to give 24.2mmol of zirconium dichloride as an orange solid as main catalyst, 24.2mmol of dimethyl- (2-phenyl-1-indenyl) - (2-indenyl) silane, in a yield of 49.0%.

Structural confirmation of bis (dimethyl- (2-phenyl-1-indenyl) - (2-indenyl) silane) zirconium dichloride:

¹H NMR(400MHz,CDCl₃):δ0.55(s,3H),1.10(s,3H),5.66(dd,J＝2.5,0.9Hz,1H),6.12(dd,J＝2.5,0.9Hz,1H),7.06(d,J＝0.7Hz,1H),7.14-7.22(m,2H),7.28-7.38(m,2H),7.40-7.58(m,5H),7.59-7.72(m,4H).

¹³C NMR(101MHz,CDCl₃):δ-0.3,1.3,87.8,104.5,108.6,112.3,120.8,125.0,125.3,125.6,126.3,126.7,127.2,127.3,127.5,128.4,128.8,129.1,130.8,131.4,132.6,134.5,135.9,140.7.

Example 11

The preparation method comprises the following steps:

n 1) differs from step l 1) described in example 9 in that 82.4mmol of 4H-dithienocyclopentadiene are used as starting material and reacted with 93.4mmol of chloro-2-indenyl silane to give finally 55.3mmol of dimethyl- (4H-dithienocyclopentadienyl) - (2-indenyl) silane as light brown crystals in 67.2% yield.

Structural confirmation of dimethyl- (4H-dithienocyclopentadienyl) - (2-indenyl) silane:

¹H NMR(400MHz,CDCl₃):δ0.24(s,6H),3.43(d,J＝14.4Hz,2H),3.83(s,1H),6.55(s,1H),6.96(ddd,J＝7.8,2.0,0.5Hz,1H),7.00(d,J＝4.9Hz,2H),7.09(td,J＝7.7,2.0Hz,1H),7.20(ddd,J＝7.8,7.7,1.1Hz,1H),7.26(ddd,J＝7.7,1.1,0.5Hz,1H),7.32(d,J＝4.9Hz,2H).

n 2) differs from step l 2) described in example 9 in that 55.3mmol of dimethyl- (4H-dithienocyclopentadienyl) - (2-indenyl) silane was reacted first with a hexane solution of n-BuLi to give a lithium salt solution of dimethyl- (4H-dithienocyclopentadienyl) - (2-indenyl) silane, which was then reacted with a hexane solution of ZrCl ₄ to give 28.0mmol of zirconium dichloride as a yellow solid procatalyst bis (dimethyl- (4H-dithienocyclopentadienyl) - (2-indenyl) silane in a yield of 50.7%.

Structural confirmation of bis (dimethyl- (4H-dithienocyclopentadienyl) - (2-indenyl) silane) zirconium dichloride:

¹H NMR(400MHz,CDCl₃):δ0.52(s,3H),1.06(s,3H),5.13(s,1H),6.68(s,1H),7.09(d,J＝4.9Hz,2H),7.13(ddd,J＝7.7,7.5,1.2Hz,1H),7.16(ddd,J＝7.9,1.2,0.5Hz,1H),7.18(ddd,J＝7.9,7.5,1.1Hz,1H),7.30(ddd,J＝7.7,1.1,0.5Hz,1H),7.40(d,J＝4.9Hz,2H).

¹³C NMR(101MHz,CDCl₃):δ-0.9,-0.3,47.8,71.6,120.3,123.8,125.1,125.4,127.3,127.6,127.8,128.1,128.5,131.5,131.8,142.7.

Example 12

The preparation method comprises the following steps:

o 1) differs from step l 1) described in example 9 in that 84.2mmol of 9H-fluorene was used as a starting material and reacted with 93.4mmol of chloro-2-indenyl silane to finally obtain 54.1mmol of dimethyl- (9H-fluorenyl) - (2-indenyl) silane as pale yellow crystals in a yield of 64.2%.

Structural confirmation of dimethyl- (9H-fluorenyl) - (2-indenyl) silane:

¹H NMR(400MHz,CDCl₃):δ0.21(s,6H),3.43(d,J＝14.4Hz,2H),4.44(s,1H),6.55(s,1H),6.96(ddd,J＝7.8,2.0,0.5Hz,1H),7.09(td,J＝7.7,2.0Hz,1H),7.20(ddd,J＝7.8,7.7,1.1Hz,1H),7.26(ddd,J＝7.7,1.1,0.5Hz,1H),7.30-7.37(m,4H),7.59(ddd,J＝7.6,1.4,0.5Hz,2H),7.80(ddd,J＝8.5,1.1,0.5Hz,2H).

o 2) differs from step l 2) described in example 9 in that 54.1mmol of dimethyl- (9H-fluorenyl) - (2-indenyl) silane was reacted with a hexane solution of n-BuLi to obtain a lithium salt solution of dimethyl- (9H-fluorenyl) - (2-indenyl) silane, which was subsequently reacted with a hexane solution of ZrCl ₄ to obtain 27.9mmol of zirconium dichloride as a yellow-orange solid procatalyst bis (dimethyl- (9H-fluorenyl) - (2-indenyl) silane) in a yield of 51.5%.

Structural confirmation of bis (dimethyl- (9H-fluorenyl) - (2-indenyl) silane) zirconium dichloride:

¹H NMR(400MHz,CDCl₃):δ0.54(s,3H),1.10(s,3H),5.23(s,1H),6.68(s,1H),7.15-7.19(m,3H),7.30(ddd,J＝7.7,1.1,0.5Hz,1H),7.36-7.41(m,4H),7.61(ddd,J＝7.8,1.4,0.5Hz,1H),7.65(ddd,J＝7.8,1.4,0.5Hz,1H),7.80(ddd,J＝8.5,1.6,0.5Hz,1H),7.84(ddd,J＝8.5,1.6,0.5Hz,1H).

¹³C NMR(101MHz,CDCl₃):δ-1.0,-0.1,47.8,71.5,119.4,120.0,120.2,123.8,127.4,127.7,127.8,128.0,128.2,128.4,128.7,128.9,140.1,140.7,143.6.

Example 13

The preparation method comprises the following steps:

p 1) differs from step l 1) described in example 9 in that 84.6mmol of indano [1,2-b ] benzothiophene (abbreviated as 10H-indeno-benzothiophene) are used as starting material and reacted with 93.4mmol of chloro-2-indenyl silane to give 55.0mmol of dimethyl- (10H-indeno-benzothiophene) - (2-indenyl) silane as light brown crystals in a yield of 65.0%.

Structural confirmation of dimethyl- (10H-indenobenzothiene) - (2-indenyl) silane:

¹H NMR(400MHz,CDCl₃):δ0.25(s,6H),3.43(d,J＝14.5Hz,2H),4.93(s,1H),6.55(s,1H),6.96(ddd,J＝7.8,2.0,0.5Hz,1H),7.09(td,J＝7.7,2.0Hz,1H),7.12(ddd,J＝7.8,7.7,1.1Hz,1H),7.21(ddd,J＝8.5,7.7,1.8Hz,1H),7.26(ddd,J＝7.7,1.1,0.5Hz,1H),7.38(ddd,J＝8.5,8.2,1.3Hz,1H),7.44(ddd,J＝8.5,7.7,1.5Hz,1H),7.49(td,J＝8.5,1.4Hz,1H),7.53(ddd,J＝8.2,1.4,0.5Hz,1H),7.84(ddd,J＝8.5,1.8,0.5Hz,1H),7.86(ddd,J＝8.5,1.3,0.5Hz,1H),7.96(ddd,J＝8.5,1.5,0.5Hz,1H).

p 2) differs from step l 2) described in example 9 in that 55.0mmol of dimethyl- (10H-indenobenzothiene) - (2-indenyl) silane was reacted with a hexane solution of n-BuLi to give a lithium salt solution of dimethyl- (10H-indenobenzothiene) - (2-indenyl) silane, which was then reacted with a hexane solution of ZrCl ₄ to give 29.2mmol of zirconium dichloride as a yellow solid as a main catalyst, 29.2mmol of dimethyl- (10H-indenobenzothiene) - (2-indenyl) silane, in 53.1% yield.

Structural confirmation of bis (dimethyl- (10H-indeno benzothiophene) - (2-indenyl) silane) zirconium dichloride:

¹H NMR(400MHz,CDCl₃):δ0.51(s,3H),1.04(s,3H),5.21(s,1H),6.68(s,1H),7.09-7.36(m,5H),7.42(ddd,J＝8.5,8.2,1.2Hz,1H),7.46(ddd,J＝8.5,7.7,1.4Hz,1H),7.53(td,J＝8.5,1.5Hz,1H),7.75(ddd,J＝8.2,1.5,0.4Hz,1H),7.87(ddd,J＝8.5,1.2,0.4Hz,1H),7.98(ddd,J＝8.4,1.4,0.5Hz,1H),8.12(ddd,J＝8.5,1.5,0.5Hz,1H).

¹³C NMR(101MHz,CDCl₃):δ-0.9,-0.3,47.6,71.3,120.2,122.5,123.1,123.8,127.0,127.4,127.6,127.8,127.9,128.0,128.2,128.4,128.7,128.9,131.7,138.5,139.3,143.9.

Example 14

The preparation method comprises the following steps:

q 1) differs from step l 1) described in example 9 in that 84.0mmol of N-methyl-indano [1,2-b ] indole, abbreviated as N-methyl-10H-indenoindole, are used as starting material and reacted with 93.4mmol of chloro-2-indenyl silane to finally give 57.7mmol of dimethyl- (N-methyl-10H-indenoindole) - (2-indenyl) silane as pale yellow crystals in a yield of 68.7%.

Structural confirmation of dimethyl- (N-methyl-10H-indenoindole) - (2-indenyl) silane:

¹H NMR(400MHz,CDCl₃):δ0.29(s,6H),3.43(d,J＝14.5Hz,2H),3.81(s,3H),4.77(s,1H),6.55(s,1H),6.96(ddd,J＝7.8,2.0,0.5Hz,1H),7.09(td,J＝7.7,2.0Hz,1H),7.11(ddd,J＝8.3,7.1,1.3Hz,1H),7.12(ddd,J＝7.8,7.7,1.1Hz,1H),7.17(ddd,J＝8.2,7.1,1.9Hz,1H),7.26(ddd,J＝7.7,1.1,0.5Hz,1H),7.33(ddd,J＝8.2,7.5,2.0Hz,1H),7.51(ddd,J＝8.2,1.3,0.5Hz,1H),7.54(ddd,J＝8.6,7.5,1.5Hz,1H),7.62(ddd,J＝8.2,1.5,0.5Hz,1H),7.68(ddd,J＝8.3,1.9,0.5Hz,1H),7.72(ddd,J＝8.6,2.0,0.5Hz,1H).

q 2) differs from step l 2) described in example 9 in that 57.7mmol of dimethyl- (N-methyl-10H-indenoindole) - (2-indenyl) silane was reacted first with a hexane solution of N-BuLi to give a lithium salt solution of dimethyl- (N-methyl-10H-indenoindole) - (2-indenyl) silane, which was subsequently reacted with a hexane solution of ZrCl ₄ to give a solid, orange-yellow-solid, bis (dimethyl- (N-methyl-10H-indenoindole) - (2-indenyl) silane) zirconium dichloride 31.9mmol, yield 55.3%.

Structural confirmation of bis (dimethyl- (N-methyl-10H-indenoindole) - (2-indenyl) silane) zirconium dichloride:

¹H NMR(400MHz,CDCl₃):δ0.54(s,3H),1.12(s,3H),3.82(s,3H),5.24(s,1H),6.68(s,1H),7.13(ddd,J＝8.3,7.7,1.3Hz,1H),7.16(ddd,J＝7.7,7.5,1.2Hz,1H),7.17(ddd,J＝7.9,1.2,0.5Hz,1H),7.18(ddd,J＝7.9,7.5,1.1Hz,1H),7.21(ddd,J＝8.0,7.7,1.5Hz,1H),7.30(ddd,J＝7.7,1.1,0.5Hz,1H),7.32(ddd,J＝8.6,8.1,1.5Hz,1H),7.42(ddd,J＝8.3,8.1,2.0Hz,1H),7.52(ddd,J＝8.0,1.3,0.5Hz,1H),7.67(ddd,J＝8.3,1.5,0.5Hz,1H),7.74(ddd,J＝8.3,1.5,0.5Hz,1H),7.85(ddd,J＝8.6,2.0,0.5Hz,1H).

¹³C NMR(101MHz,CDCl₃):δ-1.0,-0.3,31.1,47.6,71.9,112.0,118.7,120.2,120.6,123.8,127.3,127.5,127.8,128.0,128.2,128.3,128.7,128.9,129.2,133.7,137.0,139.3,144.2.

examples 15 to 28 and comparative examples 1 to 4

Refining an alpha olefin raw material, namely adding 0.8wt% of sodium hydroxide solid into 1-nonene, stirring for 60min, then carrying out reduced pressure distillation under the vacuum degree of 0.8torr, collecting and collecting fractions at 55-85 ℃, eluting through a glass column filled with activated neutral alumina, and removing oxygen-containing impurities such as water, long-chain fatty alcohol, long-chain fatty ether and the like mixed in the alpha olefin, wherein the elution process is carried out in a nitrogen glove box or carried out under the protection of nitrogen by a Schlenk technology, and the activation method of the neutral alumina is that the neutral alumina is baked for 4h at 600 ℃ in a muffle furnace.

The polymerization of the polyalphaolefins was carried out in a 1L polymerization reactor. Firstly, heating the reaction kettle to above 100 ℃, vacuumizing and baking for 1h, and replacing the reaction kettle with high-purity nitrogen for a plurality of times to remove water/oxygen impurities in the reaction kettle. Then setting the reaction temperature to be 30 ℃, circularly adjusting the temperature of the reaction kettle to the set reaction temperature through jacket water, adding 440.4g of refined 1-nonene, adding a certain concentration of cocatalyst triisobutyl aluminum Al (i-Bu) ₃,Al(i-Bu)₃, wherein the Al concentration in the reaction system is 60mmol/L, starting stirring speed is 500rpm, stirring for 20min, adding a metallocene main catalyst dissolved by an inert solvent and an organic compound containing boron element into the polymerization kettle, wherein the Zr concentration of the metallocene main catalyst in the reaction system is 0.25mmol/L, the B concentration of the organic compound containing boron element [ Ph ₃C]⁺[B(C₆F₅)₄]^－ ] in the reaction system is 0.25mmol/L, and the inert solvent is toluene, and adding 120mL in total.

After the catalyst composition is added, a nitrogen valve is opened to charge nitrogen to 0.1MPa, the reaction is finished after 1.5 hours, a blow-down pipe is opened to relieve pressure, a crude product is discharged from a reaction kettle, 10mL of mixed liquor of water/ethanol/hydrochloric acid solution is added into the crude product to quench the reaction, 3wt% of clay is added into the obtained product to adsorb and remove catalyst residues, then the filtrate is obtained through pressure filtration, the filtrate is subjected to reduced pressure distillation at 120 ℃ and the vacuum degree of 0.5torr to remove light components such as solvent, unreacted monomers and the like, a yellowish viscous transparent liquid poly-alpha-olefin product is obtained, the obtained poly-alpha-olefin product is naturally cooled to room temperature, and white opaque solid poly-alpha-olefin wax can be separated out. Notably, only a portion of the polyalphaolefin can produce a white opaque polyalphaolefin wax, with the other portion still being present as a yellowish viscous clear liquid that requires filtration to separate the two.

Wherein the cocatalyst of comparative example 4 was not a combination of Al (i-Bu) ₃ and [ Ph ₃C]⁺[B(C₆F₅)₄]^－ ], and methylaluminoxane MAO was used alone as the cocatalyst, except that MAO and the metallocene procatalyst were dissolved in an inert solvent and then directly added to the reaction vessel.

The amounts and results of the tests of examples 15 to 28 and comparative examples 1 to 4 are shown in Table 1.

The molecular weight and molecular weight distribution of polyalphaolefins were tested using high temperature Gel Permeation Chromatography (GPC) using 1,2, 4-trichlorobenzene as solvent to dissolve polyalphaolefin samples at 150℃and narrow molecular weight polyethylene as test standard, with GPC test conditions of 135℃and feed flow of 1.0mL/min, and molecular weight data of weight average molecular weight Mw and number average molecular weight Mn processed by GPC software to represent polydispersity index of molecular weight distribution calculated by Mw/Mn. At the same time, the average degree of polymerization of the polyalphaolefins is also calculated from the number average molecular weight Mn

Thermal performance testing of polyalphaolefins, measured by differential scanning calorimeter at a temperature of-20 to 140 ℃, by cooling the sample from room temperature to-20 ℃ at a rate of 5 ℃ per minute under nitrogen atmosphere, holding at-20 ℃ for 5 minutes, and then raising the temperature to 140 ℃ at a rate of 10 ℃ per minute. DSC curves were recorded from-20 ℃ to 140 ℃.

The chemical structure of the poly-alpha-olefin is characterized by that the solvent is CDCl ₃ measured by ¹³ C-NMR at normal temperature.

As shown in Table 1, "-" indicates that no occurrence was observed, and the metallocene procatalyst structures of comparative examples 1-3 were:

rac-Et(Ind)₂ZrCl₂

Me₂C(Cp(9-Flu))ZrCl₂

rac-Me₂Si(2-Me-4-Ph-Ind)₂ZrCl₂

As shown in Table1, the combination of the metallocene procatalysts of examples 1 to 14 with the cocatalysts Al (i-Bu) ₃ and [ Ph ₃C]⁺[B(C₆F₅)₄]^－ ] can produce a series of high molecular weight, narrow molecular weight distribution polyalphaolefins, and compared with comparative example 4 using MAO as the cocatalysts, examples 15 to 28 have better polymerization uniformity, higher molecular weight and narrower molecular weight distribution, because the boron-containing organic compound has stronger stabilizing ability to the cationic active center of the metallocene procatalysts, MAO is a low molecular weight polymer obtained by partial hydrolysis of trimethylaluminum, the catalytic activity combined with the metallocene procatalysts is significantly higher, trimethylaluminum residues are unavoidable in MAO, trimethylaluminum has strong chain transfer activity, resulting in high conversion and catalytic activity of the alpha olefins of comparative example 4, but the obtained polyalphaolefins have lower molecular weight and wider molecular weight distribution.

The same cocatalysts are selected for comparative examples 1-3 and examples 15-28, except that the metallocene procatalysts are different in structure, and the catalytic activity is significantly lower in comparative example 1 than in examples 15-28, and the obtained polyalphaolefins are low in molecular weight and wide in molecular weight distribution.

Comparative example 2 has significantly lower catalytic activity than examples 15 to 28, and the obtained polyalphaolefin has a close molecular weight and a broad molecular weight distribution.

Comparative example 3 has a similar catalytic activity to that of examples 15 to 28, and the obtained polyalphaolefin has a similar molecular weight and a broad molecular weight distribution.

When C9 is used as a raw material for preparing the polyalphaolefin, the polyalphaolefin can be formed only under the condition of higher average polymerization degree and molecular weight, because the side chains of the polyalphaolefin prepared by C9 are relatively shorter, the ordered arrangement degree is insufficient for forming crystallization, only partial chain segments can be crystallized, white waxy products are separated from liquid polyalphaolefin, and the polyalphaolefin molecules are more easily and tightly arranged to form crystallization areas only under the condition of higher polymerization degree.

As can be seen from the data in Table 1, only when the average degree of polymerization is greater than or equal to 150, the white waxy product is present in an amount of 10 to 40wt% based on the total polyalphaolefin product, and the higher the average degree of polymerization, the higher the proportion of white waxy product is, and the lower the average degree of polymerization, the more difficult it is to crystallize the polyalphaolefin to form the polyalphaolefin wax product.

TABLE 1

Examples 29 to 42 and comparative examples 5 to 8

Refining an alpha olefin raw material, namely adding 0.8wt% of sodium hydroxide solid into 1-hexadecene, stirring for 60min, then carrying out reduced pressure distillation under the vacuum degree of 0.8torr, collecting and collecting fractions of 150-180 ℃, eluting through a glass column filled with activated neutral alumina, and removing oxygen-containing impurities such as water, long-chain fatty alcohol, long-chain fatty ether and the like mixed in the alpha olefin, wherein the elution process is carried out in a nitrogen glove box or carried out under the protection of nitrogen by a Schlenk technology, and the activation method of the neutral alumina is that the neutral alumina is baked for 4h at 600 ℃ in a muffle furnace.

The amounts and results of the tests of examples 29 to 42 and comparative examples 5 to 8 are shown in Table 1.

The polymerization of the polyalphaolefin was the same as described above except that 1-hexadecene 469.8g of the purified alpha olefin raw material was added, the concentration of Al in the reaction system was 120mmol/L for the cocatalyst Al (i-Bu) ₃, 0.5mmol/L for the metallocene procatalyst, and 0.5mmol/L for the organic compound [ Me ₂NHPh]⁺[B(C₆F₅)₄]^－ ] containing boron element for the cocatalyst, B in the reaction system.

Wherein the cocatalyst of comparative example 8 was not a combination of Al (i-Bu) ₃ and [ Me ₂NHPh]⁺[B(C₆F₅)₄]^－ ], and methylaluminoxane MAO was used alone as the cocatalyst, unlike the above procedure in that MAO and the metallocene procatalyst were dissolved in an inert solvent and then directly added to the reaction vessel.

When the reaction temperature was set at 70 ℃, the concentration of Al in the reaction system was 60mmol/L for the cocatalyst Al (i-Bu) ₃, 0.25mmol/L for the metallocene procatalyst, and 0.25mmol/L for the organic compound [ Me ₂NHPh]⁺[B(C₆F₅)₄]^－ ] containing boron element for the cocatalyst, B in the reaction system.

As shown in Table 2, "-1" indicates that the reaction temperature was set to 30℃and "-2" indicates that the reaction temperature was set to 70 ℃.

As shown in Table 2, when C16 is used as a raw material for preparing polyalphaolefin, the obtained polyalphaolefin can crystallize to separate out more white waxy products, because after the chain length of the alpha olefin is increased to a certain degree, the synthesized polyalphaolefin side chains can form crystals, the polyalphaolefin products can be obtained without high polymerization degree, the proportion of the polyalphaolefin wax in the polyalphaolefin overall products is obviously improved, the proportion of the polyalphaolefin wax in examples 29-42 and comparative examples 5-8 is generally not lower than 85wt%, which indicates that in order to obtain the polyalphaolefin wax with higher proportion in the products, the polyalphaolefin wax synthesized by adopting alpha olefin with longer carbon chain should be selected as the raw material, but the cost of the alpha olefin raw material with more than 10 carbon atoms is higher, and the economy of the product with lower proportion of the alpha olefin synthesized by selecting the alpha olefin wax with less than 10 carbon atoms is better.

From the point of view of polymerization temperature, compared with the reaction temperature of 70 ℃, the average polymerization degree of the poly-alpha-olefin at 30 ℃ is higher, the corresponding poly-alpha-olefin wax accounts for a little higher proportion, because the high temperature is favorable for the activation of the metallocene main catalyst, the high temperature is favorable for the formation of active centers, the larger the proportion of the active centers with the rise of the temperature is, and meanwhile, the chain transfer rate of a reaction system is increased at the high temperature, so that the high temperature promotes the alpha-olefin monomer to form a polymerization product with lower molecular weight, the activity of the main catalyst is obviously improved at 70 ℃, and the corresponding alpha-olefin conversion rate is relatively higher.

From the viewpoint of the activity of the main catalyst, the catalytic activity of examples 29 to 42 on 1-hexadecene is generally higher, the activity is not lower than 450 Kg.mol ^-1(Zr)·h^-1 at 30 ℃ and the activity is not lower than 1000 Kg.mol ^-1(Zr)·h^-1 at 70 ℃, and compared with examples 1 to 14, the catalytic activity of examples 29 to 42 using the same metallocene main catalyst on alpha-olefins is generally lower because the carbon chain of the C16 alpha-olefin monomer is longer, the steric hindrance is relatively higher, and the coordination ability with the active center is weaker due to the steric hindrance effect, particularly at the reaction temperature of 30 ℃, so the catalytic activity of the main catalyst is generally lower than that of 1-nonene.

Compared with comparative examples 5-7, the molecular weight, molecular weight distribution and average polymerization degree of the polymerized poly-alpha-olefin product are not greatly different from the ratio of poly-alpha-olefin wax, but the catalytic activity of the main catalyst of examples 29-42 is obviously higher than that of comparative examples 5-7 at 30 ℃ and 70 ℃, especially the main catalyst with the structures of Me ₂C(Cp(9-Flu))ZrCl₂ and rac-Me ₂Si(2-Me-4-Ph-Ind)₂ZrCl₂, and the catalytic activity of the main catalyst is obviously reduced after the catalytic activity of the main catalyst for catalyzing the polymerization of C9 monomers is relatively similar to that of examples, and the catalytic activity of the main catalyst of the metallocene catalyst synthesized by examples 1-14 is obviously reduced to alpha-olefin, especially high-steric long-chain alpha-olefin.

Comparative example 8 the co-catalysts Al (i-Bu) ₃ and [ Me ₂NHPh]⁺[B(C₆F₅)₄]^－ ] of the other examples and comparative examples were replaced with MAO and did not react at both 30 and 70 ℃. This is because the presence of long carbon chain oxygenates such as C16 alcohols, aldehydes, ethers, which inhibit the reaction, in the C16 olefins, is more polar than the C16 olefins due to the presence of long carbon chain structures in the molecule, and is difficult to adsorb and separate by means of a through-neutral alumina column during the refining of the feedstock, which would lead to poisoning of the latter if the long carbon chain oxygenates were in direct contact with the main catalyst. It is therefore necessary to mix the C16 olefins with the aluminum alkyl for a period of time before adding the catalyst composition to effect polymerization.

As shown in FIG. 1, the DSC test results of examples 18, 20, 27, 34-1, 34-2 and comparative example 4 show that as the polymerization degree of the alpha-olefin monomer increases, the melting point peak of the originally amorphous poly-alpha-olefin starts to appear, which is caused by the fact that the molecular weight of the poly-alpha-olefin increases, the molecular chain arrangement is more regular and the main chain is crystallized. As can be seen from a comparison of examples 18, 20, 27, 34-1, 34-2, the melting point increases with increasing molecular weight and the melting point of the polyalphaolefin increases with increasing side chain length of the alpha-olefin monomer. This is because the increase in molecular weight and side chain length of the polyalphaolefin increases the resistance of the polymer chain to internal rotation, thereby making the molecular chain stiffer, and the conformational change during melting is less, resulting in an increase in the melting point peak of the DSC test.

Meanwhile, by carrying out ¹³ C-NMR characterization on the poly-alpha-olefin prepared in the embodiment 20 and the embodiment 34-2, as shown in the attached figure 2, no spectrum peak is found in an olefin double bond region with a chemical shift of 100-150, the polymerization reaction is complete, no residual carbon-carbon double bond exists in the molecule, and the catalyst successfully synthesizes a target product by catalyzing alpha-olefin monomer to carry out coordination polymerization.

TABLE 2

Finally, it should be understood that the foregoing description is only a preferred embodiment of the present application, and is not intended to limit the scope of the present application, but rather to limit the application to the particular embodiments described, and that any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the present application will become apparent to those skilled in the art.

Claims

1. A use of a metallocene catalyst composition as a catalyst in the preparation of poly-alpha-olefin wax, characterized in that the catalyst composition comprises a main catalyst and a co-catalyst, the main catalyst is a metallocene compound, the co-catalyst is an alkyl aluminum and an organic compound containing a boron element, and the general structural formula of the metallocene compound is as shown in Formula I:

The M is a metal element of Group IVB in the periodic table;

Said X ₁ and X ₂ are halogen;

The E _n is a bridging group;

Said R ₁ and R ₂ are each independently selected from one of hydrogen, saturated or unsaturated C1 to C20 hydrocarbon group, saturated or unsaturated C1 to C20 halogenated hydrocarbon group, saturated or unsaturated C1 to C20 hydrocarbonoxy group, saturated or unsaturated C3 to C20 cycloalkyl group, C6 to C20 aryl group or C6 to C20 heteroaryl group;

Said R ₃ and R ₄ are each independently selected from one of hydrogen, halogen, saturated or unsaturated C1 to C20 hydrocarbon group, saturated or unsaturated C1 to C20 halogenated hydrocarbon group, saturated or unsaturated C1 to C20 hydrocarbonoxy group, saturated or unsaturated C3 to C20 cycloalkyl group, C6 to C20 aryl group or C5 to C20 heteroaryl group; or said R ₃ and R ₄ together with the two carbon atoms connected to the cyclopentadienyl ring form a new aromatic ring, alkyl-substituted aromatic ring, aromatic heterocycle or other complex aromatic condensed ring;

The R ₅ , R ₆ and the two carbon atoms connected to the cyclopentadienyl ring together form a new aromatic ring, an alkyl-substituted aromatic ring, an aromatic heterocycle or other complex aromatic condensed ring;

The R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently selected from one of hydrogen, halogen, and a saturated or unsaturated C1 to C20 hydrocarbon group.

2. The use according to claim 1, characterized in that the M is selected from one of Ti, Zr and Hf; the structural formula of the alkyl aluminum includes: AlR ₃ , AlR _m H _(3-m) or AlR _m X _(3-m) , wherein m is an integer of 0 to 3;

And/or, _X1 is Cl or Br;

And/or, _X2 is Cl or Br;

And/or, the bridging atom in the _En includes but is not limited to C, Si, Ge or Sn, and the number of the bridging atom is one or more;

And/or, in the preparation of the poly-alpha olefin wax, C6-C20 linear alpha olefins are used as raw materials;

And/or, the organic compound containing the boron element is an organic borate ester and/or an organic borate salt;

And/or, the organic part of the organic compound containing boron element includes alkyl group of 1 to 12 carbon atoms and/or oxyalkyl group of 1 to 12 carbon atoms and/or halogenated alkyl group of 1 to 12 carbon atoms and/or aryl group of 6 to 20 carbon atoms and/or alkylaryl group, arylalkyl group or halogenated aryl group.

3. The use according to claim 2, characterized in that R ₁ and R ₂ are the same and are selected from hydrogen or methyl;

and/or, said R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are all hydrogen;

And/or, R in the structural formula of the alkyl aluminum is an alkyl group, and the alkyl group is one or more combinations of a straight-chain alkyl group having 1 to 12 carbon atoms, a branched non-cyclic alkyl group, a side-chain-free cyclic alkyl group, or a side-chain-containing cyclic alkyl group;

and/or, X in the structural formula of the alkyl aluminum is a halogen;

And/or, the organic compound containing the boron element is trityltetrakis(pentafluorophenyl)borate [Ph ₃ C] ⁺ [B(C ₆ F ₅ ) ₄ ] ⁻ and/or dimethylphenylammoniumtetrakis(pentafluorophenyl)borate [Me ₂ NHPh] ⁺ [B(C ₆ F ₅ ) ₄ ] ⁻ .

4. The use according to claim 1, characterized in that the main catalyst has a general structural formula as shown in Formula II, Formula III, or Formula IV:

5. The use according to claim 1, characterized in that the main catalyst is selected from one or more of the following structural formulas:

6. The use according to claim 1, characterized in that:

For the main catalyst in which _En is a silicon bridge, the catalyst is prepared by the following steps:

a1) The corresponding dimethylsilyl bridged ligand is prepared by reacting tetrasubstituted cyclopentadiene, a hydrogen extraction agent and 2-(dimethylchlorosilyl)indene as raw materials. The reaction route is:

a2) Using dimethylsilyl bridge ligand, hydrogen extraction agent and zirconium tetrachloride as raw materials to react and prepare the corresponding main catalyst, the reaction route is:

For the main catalyst in which E _n is a single carbon bridge or a double carbon bridge, and R ₃ , R ₄ and two carbon atoms on the cyclopentadienyl group together form a new benzene ring, the main catalyst is prepared by the following steps:

b1) using tetrasubstituted dihydrocyclopentadienone, sodium hydride and 3-(diethoxyphosphoryl)methyl acetate or 3-(diethoxyphosphoryl)methyl propionate as raw materials to carry out Horner-Wadsworth-Emmons reaction to prepare (tetrasubstituted cyclopentadienyl)-1-methyl acetate or (tetrasubstituted cyclopentadienyl)-1-methyl propionate, the reaction route is:

n is 1 or 2;

b2) reacting dibenzylmagnesium chloride with (tetrasubstituted cyclopentadienyl)-1-methyl acetate or (tetrasubstituted cyclopentadienyl)-1-methyl propionate as raw materials, the reaction route is:

n is 1 or 2, X is Cl;

b3) Using the reaction product of step b2) as a raw material, a dehydration reaction is carried out under the catalysis of toluenesulfonic acid TsOH to prepare the corresponding single carbon bridge or double carbon bridge ligand, and the reaction route is:

n is 1 or 2;

b4) Using the corresponding single carbon bridge or double carbon bridge ligand, hydrogen extraction agent and zirconium tetrachloride as raw materials, reacting to prepare the corresponding main catalyst, the reaction route is:

n is 1 or 2;

The main catalyst in which _En is a single carbon bridge or a double carbon bridge and R ₃ , R ₄ , R ₅ , and R ₆ all form a new aromatic ring or aromatic heterocycle together with the two carbon atoms on the cyclopentadienyl group is prepared by the following steps:

c1) using tetrasubstituted cyclopentadiene, a hydrogen extraction agent and methyl bromoacetate or methyl bromopropionate as raw materials to react, thereby preparing (tetrasubstituted cyclopentadienyl)-1-methyl acetate or (tetrasubstituted cyclopentadienyl)-1-methyl propionate, the reaction route is:

n is 1 or 2;

c2) using dibenzylmagnesium chloride and (tetrasubstituted cyclopentadienyl)-1-methyl acetate or (tetrasubstituted cyclopentadienyl)-1-methyl propionate as raw materials to react, the reaction route is:

n is 1 or 2,

X is Cl;

c3) using the reaction product of step c2) as a raw material, and subjecting it to a dehydration reaction under the catalysis of toluenesulfonic acid TsOH, to prepare the corresponding single carbon bridge or double carbon bridge ligand, the reaction route is:

n is 1 or 2;

c4) using the corresponding single carbon bridge or double carbon bridge ligand, hydrogen extraction agent and zirconium tetrachloride as raw materials to react and prepare the corresponding main catalyst, the reaction route is:

n is 1 or 2;

Wherein, the hydrogen extraction agent is an organic lithium base R ₀ Li.

7 . The use according to claim 6 , characterized in that R ₀ in the organic lithium base R ₀ Li is a linear or branched alkyl, cycloalkyl or aryl group having 1 to 12 carbon atoms.

8. The use according to claim 7, characterized in that the organic lithium base is n-butyl lithium n-BuLi or tert-butyl lithium t-BuLi.

9. A method for preparing poly-alpha olefin wax, characterized in that the method comprises the following steps: polymerizing C6-C20 linear alpha olefins under the action of a metallocene catalyst composition;

The catalyst composition comprises a main catalyst and a co-catalyst, wherein the main catalyst is a metallocene compound, and the co-catalyst is an alkyl aluminum and an organic compound containing a boron element. The general structural formula of the metallocene compound is shown in Formula I:

The M is a metal element of Group IVB in the periodic table;

Said X ₁ and X ₂ are halogen;

The E _n is a bridging group;

The R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently selected from hydrogen, halogen, and a saturated or unsaturated C1 to C20 hydrocarbon group.

10. A poly-alpha olefin wax prepared according to the preparation method of claim 9, characterized in that the number average molecular weight Mn of the poly-alpha olefin wax is ≥ 15000; and/or the molecular weight distribution Mw/Mn of the poly-alpha olefin wax is ≤ 1.5; and/or the melting point of the poly-alpha olefin wax is 40-90°C.