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

Abstract

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

Technical Field

[0001] The invention belongs to the technical field of organic compounds, in particular to the technical field of polyolefins, and provides an application of a metallocene catalyst composition as a catalyst in the preparation of poly-alpha-olefin wax. Background Art

[0002] Polyolefin wax refers to a waxy substance at room temperature, which has the advantages of being non-toxic, non-corrosive, wear-resistant, heat-resistant, chemical-resistant, and having good dispersibility and fluidity. Among them, polyolefin wax can be used directly in polyolefin processing as a multifunctional additive. It can increase the gloss and processing performance of the product. In particular, polyolefin wax has good compatibility with polyolefin resins, etc., can disperse pigments in masterbatches, act as a release agent in plastic processing, and can be used as an ink wear-resistant agent. It has become an indispensable and important chemical raw material in the plastic, rubber, ink, paint, metal casting and other industries. Polyolefin wax usually includes polyethylene wax obtained by homopolymerization of ethylene or propylene, polypropylene wax, and polyolefin wax obtained by copolymerization of ethylene and alpha olefins. The branching degree of this part of polyolefin wax is limited, and the side chains are randomly arranged. The side chain density is not high enough, and the dispersibility of pigments or fillers still needs to be improved.

[0003] Polyalphaolefin refers to hydrocarbons with appropriate relative molecular weight that are polymerized from raw alpha olefins under the action of catalysts. Polyalphaolefin synthetic oils prepared from raw alpha olefins of C6, C8, and C10 have high viscosity index, low volatility, and excellent oxidation stability, and are usually used as lubricant base oils. Long-chain alpha olefins above C10 can be used as raw materials to synthesize polyalphaolefin waxes. For example, Zhang Jianyu et al. (Zhang Jianyu; Chen Sheng; Li Huihui; Zheng Yihong, Synthesis of Polyalphaolefin Wax, Petroleum Refining and Chemical Industry, 2009-01-12) used hexadecene and octadecene as raw materials, and used Ziegler-Natta supported catalysts and triethylaluminum as cocatalysts to prepare low-isotactic polyalphaolefin waxes under normal pressure through bulk polymerization. However, Ziegler-Natta is a multi-active site catalyst. During the polymerization process, due to the presence of multiple catalytic active sites, there are also side reactions such as double bond isomerization and carbon chain rearrangement. The resulting polyalphaolefin molecules have a high degree of isomerization, which is specifically manifested in that the polyalphaolefin molecules extend side chains of varying lengths in a disordered manner on the main chain. This type of product is more difficult to form polyalphaolefin wax crystals due to the low regularity of the molecular structure. Summary of the invention

[0004] In view of the above-mentioned shortcomings of the prior art, the purpose of the present invention is to provide a use of a metallocene catalyst composition as a catalyst in the preparation of polyalphaolefin wax. The technical solution of the present invention proposes for the first time that the catalyst composition described in the present application can be used for catalytic preparation of polyalphaolefin wax.

[0005] The first aspect of the present invention discloses the 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. The main catalyst is a metallocene compound, and the co-catalyst is an alkyl aluminum and / or an organic compound containing a boron element.

[0006] The general structural formula of the metallocene compound is shown in Formula I:

[0007]

[0008] The M is a metal element of Group IVB in the periodic table.

[0009] The X1 and X2 are halogens, such as F, Cl, Br, and I.

[0010] The E n The bridging group limits the free rotation of the cyclopentadienyl around the metal center M, making the catalyst structure rigid, and allowing the bulky linear α-olefin monomer with a carbon number greater than or equal to 8 to be more fully close to the active center, facilitating its coordination and insertion.

[0011] The R1 and R2 are each independently selected from one of hydrogen, a saturated or unsaturated C1 to C20 hydrocarbon group, a saturated or unsaturated C1 to C20 halogenated hydrocarbon group, a saturated or unsaturated C1 to C20 hydrocarbonoxy group, a saturated or unsaturated C3 to C20 cycloalkyl group, a C6 to C20 aryl group or a C5 to C20 heteroaryl group.

[0012] The R3, R4, R5 and R6 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.

[0013] R7, R8, R9, R 10 , R 11 With R 12 Each is independently selected from one of hydrogen, halogen, and a saturated or unsaturated C1 to C20 hydrocarbon group.

[0014] Preferably, M is selected from one of Ti, Zr and Hf. More preferably, M is Zr.

[0015] Preferably, X1 is Cl or Br.

[0016] Preferably, X2 is Cl or Br. In a specific embodiment, X1 and X2 are both chlorine atoms.

[0017] Preferably, the E nThe atoms playing a bridging role include but are not limited to C, Si, Ge or Sn, and the number of the atoms playing a bridging role is one or more.

[0018] In one or more specific embodiments, the E n It is a single carbon bridge, a double carbon bridge or a silicon bridge.

[0019] More preferably, said R1 and R2 are the same and are selected from hydrogen or methyl.

[0020] More preferably, R3, R4 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.

[0021] More preferably, the R5, R6 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;

[0022] The combination of the cyclopentadienyl ring between R3 and R4 and / or between R5 and R6 with a benzene ring, an aromatic heterocycle or other complex aromatic condensed ring increases the steric hindrance near the metal active center and masks its axial coordination ability, thereby extending the chain termination time during the polymerization reaction, increasing the molecular weight of the polyalphaolefin and catalyzing the polymerization activity of the polyalphaolefin.

[0023] More preferably, said R8, R9, R 10 , R 11 There is at least one pair of two carbon atoms connected to the indene ring, which together form a new aromatic ring, an alkyl-substituted aromatic ring, an aromatic heterocycle or other aromatic condensed ring.

[0024] More preferably, R7, R8, R9, R 10 , R 11 With R 12 All are hydrogen.

[0025] Preferably, the general structural formula of the main catalyst described above is shown in Formula II, Formula III, and Formula IV:

[0026]

[0027] In one or more embodiments, the main catalyst is selected from one or more of the following structural formulas:

[0028]

[0029]

[0030] Preferably, for E n The main catalyst for the silicon bridge is prepared by the following steps:

[0031] 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:

[0032]

[0033] 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:

[0034]

[0035] For E n The main catalyst is a single carbon bridge or a double carbon bridge, and R3, R4 and two carbon atoms on the cyclopentadienyl group together form a new benzene ring, which is prepared by the following steps:

[0036] 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:

[0037] n is 1 or 2;

[0038] b2) reacting dibenzylmagnesium chloride with (tetrasubstituted cyclopentadienyl)-1-methyl acetate or (tetrasubstituted cyclopentadienyl)-1-methyl propionate as raw materials, the reaction route is:

[0039] n is 1 or 2;

[0040] 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:

[0041] n is 1 or 2;

[0042] 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:

[0043] n is 1 or 2;

[0044] Preferably, in b2), X is a halogen, such as F, Cl, Br, or I. Further preferably, X is Cl or Br.

[0045] For E nThe main catalyst is a single carbon bridge or a double carbon bridge, and R3, R4 and R5, R6 together with the two carbon atoms on the cyclopentadienyl group form a new aromatic ring or aromatic heterocycle, which is prepared by the following steps:

[0046] c1) using tetrasubstituted cyclopentadiene, a hydrogen extraction agent and methyl haloacetate or methyl halopropionate as raw materials to react, thereby preparing (tetrasubstituted cyclopentadienyl)-1-methyl acetate or (tetrasubstituted cyclopentadienyl)-1-methyl propionate, the reaction route is:

[0047] n is 1 or 2;

[0048] 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:

[0049] n is 1 or 2;

[0050] 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:

[0051] n is 1 or 2;

[0052] 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:

[0053] n is 1 or 2;

[0054] Preferably, the hydrogen withdrawal agent is an organic lithium base ROLi.

[0055] More preferably, the R0 is a linear or branched alkyl, cycloalkyl or aryl group having 1 to 12 carbon atoms. Further preferably, the organic lithium base is n-butyl lithium n-BuLi or tert-butyl lithium t-BuLi.

[0056] Preferably, in step c2), X is a halogen. Further preferably, X is Cl or Br.

[0057] Preferably, the structural formula of the alkyl aluminum in the co-catalyst includes: AlR3, AlR m H (3-m) or AlR m X (3-m) .

[0058] More preferably, m is an integer of 0 to 3, such as 0, 1, 2, or 3.

[0059] More preferably, the alkyl group R in the structural formula is one or more combinations of a straight-chain alkyl group having 1 to 12 carbon atoms, a branched non-cyclic alkyl group, a cyclic alkyl group without a side chain, or a cyclic alkyl group with a side chain.

[0060] More preferably, X in the structural formula is halogen.

[0061] Further preferably, the structure of the alkyl aluminum is AlR3. In a specific embodiment, the alkyl aluminum is triisobutyl aluminum.

[0062] Preferably, the organic compound containing boron in the co-catalyst is an organic boric acid ester and / or an organic boric acid salt.

[0063] Preferably, the organic part 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 group and / or an alkylaryl group, an aralkyl group or a haloaryl group of 6 to 20 carbon atoms, such as any one or more of boron compounds such as boroxine, triethylborane, triphenylborane, trifluorophenylborane, triphenylborane ammonia complex, tributyl borate, triisopropyl borate, tri(pentafluorophenyl)borane, trityltetrakis(pentafluorophenyl)borate, tri(p-octylbenzene)methyltetrakis(pentafluorophenyl)borate, dimethylphenylammoniumtetrakis(pentafluorophenyl)borate, diethylphenylammoniumtetrakis(pentafluorophenyl)borate, methyldiphenylammoniumtetrakis(pentafluorophenyl)borate, ethyldiphenylammoniumtetrakis(pentafluorophenyl)borate, methyldi(octadecyl)ammoniumtetrakis(pentafluorophenyl)borate, and trioctylammoniumtetrakis(pentafluorophenyl)borate.

[0064] Further preferably, the boron-containing organic compound is trityltetrakis(pentafluorophenyl)borate [Ph3C] + [B(C6F5)4] － and / or dimethylphenylammonium tetrakis(pentafluorophenyl)borate [Me2NHPh] + [B(C6F5)4] － .

[0065] The second aspect of the present invention discloses a method for preparing poly-alpha olefin wax, which comprises the following steps: C6-C20 linear alpha olefins are polymerized under the action of a metallocene catalyst composition.

[0066] Preferably, the linear alpha olefin is selected from one or more of C8 and / or C9 and / or C10 linear alpha olefins.

[0067] Preferably, the linear alpha olefin is selected from one or more of C12 to C20 linear alpha olefins.

[0068] The third aspect of the present invention discloses a poly-alpha-olefin wax prepared according to the above preparation method.

[0069] Preferably, the number average molecular weight M of the poly-alpha olefin wax is n ≥15000. Further preferably, the number average molecular weight of the poly-alpha olefin wax is 15000≤M n ≤60000.

[0070] Preferably, the molecular weight distribution M of the poly-alpha olefin wax is w / M n ≤1.5. As described, the molecular weight distribution is 1.1, 1.2, 1.3, 1.4, 1.5.

[0071] Preferably, the poly-alpha-olefin wax has a melting point of 40 to 90°C.

[0072] More preferably, the melting point of the polyalphaolefin wax is 50 to 90°C. Further preferably, the melting point of the polyalphaolefin wax is 60 to 90°C.

[0073] The present invention has the following beneficial effects:

[0074] (1) The metallocene main catalyst proposed in the present invention limits the free rotation of the metallocene ring around the metal center through the bridging group, so that the catalyst structure has rigidity, and the ligand at one end is a 2-indenyl group with relatively low steric hindrance, so that the large-volume linear α-olefin monomer can be more fully close to the active center, and has high catalytic activity for linear α-olefins with different carbon numbers, and can achieve a high conversion rate of α-olefins at a low catalyst dosage, reducing production costs, especially at a reaction temperature of 30°C and for the coordination polymerization reaction of long-chain linear α-olefins with a carbon number greater than or equal to 12. The catalyst composition formed by the metallocene main catalyst, alkyl aluminum, and boron-containing organic compounds can catalyze the synthesis of high molecular weight and narrow molecular weight distribution polyalphaolefins.

[0075] (2) From the perspective of the preparation method of the metallocene main catalyst, the bridging group of the main catalyst is constructed by the Horner-Wadsworth-Emmons reaction, and an ester bond is introduced at the same time, with a yield of 80-90%, which is significantly improved compared to the method of directly reacting a halogenated acid ester with a tetrasubstituted cyclopentadiene. A di-Grignard reagent is also used to react with the ester bond to construct the 2-indenyl ligand in the main catalyst, with fewer reaction steps and higher yield.

[0076] (3) Two methods for preparing polyalphaolefin wax. One method is to use low-cost C8 / 9 / 10 low-carbon linear alpha olefins as raw materials, and to obtain high molecular weight, narrow molecular weight distribution polyalphaolefins through polymerization reaction with a catalyst composition, and then slowly cool down to crystallize, and separate the light yellow liquid polyalphaolefins through solid-liquid separation for use as lubricants, drag reducers, etc., and the remaining 10-40wt% is white solid polyalphaolefin wax. This method has low raw material cost but cannot obtain high yield of polyalphaolefin wax. The second method is to use high-cost C12 or above long-chain linear alpha olefins as raw materials. More than 80wt% of the polyalphaolefins prepared in this way can be crystallized into polyalphaolefin wax. This method has high raw material cost but relatively higher yield of polyalphaolefin wax. BRIEF DESCRIPTION OF THE DRAWINGS

[0077] Figure 1 It is a graph of the DSC test results of Examples 18, 20, 27, 34-1, 34-2 and Comparative Example 4.

[0078] Figure 2 It is the C13 H NMR spectrum of Examples 20 and 34-2. DETAILED DESCRIPTION

[0079] The following describes the embodiments of the present invention through specific examples, and those skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and the details in this specification can also be modified or changed in various ways based on different viewpoints and applications without departing from the spirit of the present invention.

[0080] In addition, it should be understood that one or more method steps mentioned in the present invention do not exclude the presence of other method steps before and after the combination step or the insertion of other method steps between these explicitly mentioned steps, unless otherwise specified. Moreover, unless otherwise specified, the numbering of each method step is only a convenient tool for identifying each method step, and is not intended to limit the order of arrangement of each method step or to limit the scope of the present invention. The change or adjustment of their relative relationship, without substantial change in the technical content, should also be regarded as the scope of the present invention. If the specific experimental conditions are not specified in the examples, they are usually in accordance with conventional conditions or the conditions recommended by the sales company; the materials, reagents, etc. used in the examples, unless otherwise specified, can be purchased through commercial channels.

[0081] Example 1

[0082] This embodiment is a method for preparing a specific main catalyst having the structural formula shown below.

[0083]

[0084] The specific preparation method is as follows:

[0085] d1) Using 1-indanone as starting material, sodium hydride and methyl 3-(diethoxyphosphoryl)acetate, a Horner-Wadsworth-Emmons reaction is carried out.

[0086] First, 0.25 mol NaH was added to 150 mL toluene to prepare a suspension, and the suspension was cooled in an ice bath. Subsequently, 0.25 mol of methyl 3-(diethoxyphosphoryl)acetate was added to the NaH toluene suspension cooled to 0°C in an ice bath under nitrogen protection. After the addition, the cooling was removed, and the temperature was naturally raised to room temperature. The mixture was stirred at room temperature for 30 min until the liquid in the reaction bottle became clear and transparent. 0.2 mol of 1-indanone and 50 mL toluene were prepared into a solution and added to the reaction bottle. The mixture was kept at 95-105°C for reaction for 24 hours. h later, water was added to separate the water layer and the oil layer, the water layer was re-extracted with ethyl acetate 3 times, the oil layer was evaporated under reduced pressure to remove the solvent and dried to obtain an amber crude product, the crude product was purified by flash chromatography using a mixed solution of hexane and ethyl acetate in a volume ratio of 9:1 as eluent, and then a rotary evaporator was used to remove the solvent under reduced pressure at a vacuum of 0.8 torr to obtain 0.174 mol of reddish oily liquid (1-indenyl)-1-acetic acid methyl ester, with a yield of 86.9%, which is the mass ratio of the actual amount of the target product produced to the theoretical amount of the target product produced.

[0087] Structure confirmation of (1-indenyl)-1-acetic acid methyl ester:

[0088] 1 H 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).

[0089]

[0090] d2) Preparation of o-dichlorobenzyl Grignard reagent: 0.6 mol of 50-mesh magnesium powder is placed in a three-necked round-bottom flask, heated to 110°C under a vacuum of 10 torr and dried overnight, then the magnesium powder is flushed with dry nitrogen and cooled to ambient temperature. 120 mL of anhydrous THF and 0.025 mol of 2-dibromoethane are added, and gas evolution occurs after 2 minutes. The flask is cooled to room temperature and all volatiles are removed under a vacuum of 0.8 torr. 0.15 mol of o-dichlorobenzyl is dissolved in 150 mL of anhydrous THF and transferred to a charging funnel. The THF solution of o-dichlorobenzyl is added dropwise to the THF suspension of magnesium within 3 hours, and the reaction mixture is stirred for 12 hours and then left to stand. After the excess magnesium settles, it is filtered, and the light yellow filtrate obtained by filtration is retained, i.e., the Grignard solution of o-dichlorobenzyl.

[0091] Dissolve 0.1 mol of (1-indenyl)-1-acetic acid methyl ester in 100 mL of THF and transfer it to a dropping funnel. Add the ester solution dropwise to the Grignard solution of o-dichlorobenzyl at -78°C over 3 hours. After the addition is complete, slowly warm to room temperature and stir for 12 hours overnight. After quenching the reaction mixture with water, remove the solvent under reduced pressure at a vacuum of 0.8 torr. Add ether, neutralize the mixture with 1 mol / L HCl, separate the ether phase, and extract the aqueous phase twice more with ether. After drying the combined organic phases over anhydrous magnesium sulfate and filtering out all solids, the solvent was removed under reduced pressure using a rotary evaporator at a vacuum of 0.8 torr to obtain a crude product. The crude product was purified by flash chromatography using a mixed solution of hexane and ether as an eluent, and then the solvent was removed under reduced pressure using a rotary evaporator at a vacuum of 0.8 torr to obtain 66.7 mmol of an off-white solid ((1-indenyl)-methyl)-2-indanol with a yield of 66.7%.

[0092] Structure confirmation of ((1-indenyl)-methyl)-2-indanol:

[0093] 1 H 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).

[0094]

[0095] d3) 10 mmol of p-toluenesulfonic acid monohydrate and 66.7 mmol of ((1-indenyl)-methyl)-2-indanol were placed in a three-necked round-bottom flask, and then 100 mL of reagent-grade toluene was added to the flask to form a suspension. The flask was heated to 110-120° C., refluxed for 2 h, and then cooled to room temperature. Distilled water was added to the flask until the solid in the suspension dissolved into a solution, and then the liquid in the flask was transferred to a separatory funnel to separate the toluene layer, and the water layer was washed twice with ether to form a combined organic layer. The combined organic layer was dried over anhydrous magnesium sulfate and the solvent was removed under reduced pressure at a vacuum of 0.8 torr to obtain a crude product, which was purified by flash chromatography using a mixed solution of hexane and ether as an eluent. Subsequently, a rotary evaporator was used to remove the solvent under reduced pressure at a vacuum of 0.8 torr to obtain 63.0 mmol of a light yellow solid (2-indenyl)-(1-indenyl)-methane, with a yield of 94.5%. The obtained light yellow solid was subjected to FTIR analysis, and the -1 There is no obvious absorption peak, which indicates that all hydroxyl groups have undergone dehydration rearrangement reaction.

[0096]

[0097] d4) In a glove box under nitrogen atmosphere, 93.7 mmol of n-butyl lithium n-BuLi was added with 60 mL of hexane to prepare a hexane solution of n-BuLi, 63.0 mmol of [(2-indenyl)-(1-indenyl)]-methane was placed in a round-bottom flask, 60 mL of hexane was added to dissolve it, and the mixture was stirred in an ice bath and cooled to -20°C, and then the prepared hexane solution of n-BuLi was added, and the mixture was naturally heated to room temperature and stirred at room temperature for 5 hours to obtain (2-indenyl)-(1-indenyl)- methane lithium salt solution; then in a glove box, 90.1mmol of ZrCl4 was dissolved in 80mL of hexane, and the above lithium salt solution was added to the hexane solution of ZrCl4 in an ice bath with stirring, and then the temperature was raised to room temperature, and the reaction was stirred at room temperature for 20h. After the reaction was completed, the obtained suspension was filtered to remove LiCl, and all solvents were removed by distillation under reduced pressure to obtain 41.3mmol of light yellow solid main catalyst bis((2-indenyl)-(1-indenyl)-methane)zirconium dichloride, with a yield of 65.6%.

[0098] The structure of bis((2-indenyl)-(1-indenyl)-methane)zirconium dichloride is confirmed:

[0099] 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).

[0100] 13 C 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.

[0101]

[0102] Example 2

[0103] This embodiment is a method for preparing a specific main catalyst having the structural formula shown below.

[0104]

[0105] The specific preparation method is as follows:

[0106] e1) is different from step d1) described in Example 1 in that 0.25 mol of methyl 3-(diethoxyphosphoryl)propionate is used instead of methyl 3-(diethoxyphosphoryl)acetate to carry out the Horner-Wadsworth-Emmons reaction, thereby preparing 0.175 mol of slightly red oily liquid (1-indenyl)-1-propionic acid methyl ester with a yield of 87.5%.

[0107] Structure confirmation of methyl (1-indenyl)-1-propionate:

[0108] 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).

[0109]

[0110] e2) is different from step d2) described in Example 1 in that 0.1 mol of (1-indenyl)-1-propionic acid methyl ester replaces the (1-indenyl)-1-acetic acid methyl ester in step d2) to finally obtain 65.5 mmol of off-white solid ((1-indenyl)-ethyl)-2-indanol with a yield of 65.5%.

[0111] Structure confirmation of ((1-indenyl)-ethyl)-2-indanol:

[0112] 1 H 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).

[0113]

[0114] e3) is different from step d3) in Example 1 in that 65.5 mmol of ((1-indenyl)-ethyl)-2-indanol is reacted with 10 mmol of p-toluenesulfonic acid monohydrate to finally obtain 60.4 mmol of light yellow solid (2-indenyl)-(1-indenyl)-ethane with a yield of 92.2%. The obtained light yellow solid is subjected to FTIR analysis, and the wavelength of the FTIR spectrum at 3200-3600 cm -1There is no obvious absorption peak, which indicates that all hydroxyl groups have undergone dehydration rearrangement reaction.

[0115]

[0116] e4) is different from step d4) described in Example 1 in that 93.7 mmol of n-butyl lithium n-BuLi is added to 60 mL of hexane to prepare a hexane solution of n-BuLi, 60.4 mmol of (2-indenyl)-(1-indenyl)-ethane is first reacted with the hexane solution of n-BuLi to obtain a lithium salt solution of (2-indenyl)-(1-indenyl)-ethane, and then reacted with 80 mL of a hexane solution containing 90.1 mmol of ZrCl4 to obtain 36.6 mmol of light yellow solid main catalyst bis((2-indenyl)-(1-indenyl)-ethane)zirconium dichloride in a yield of 60.6%.

[0117] The structure of bis((2-indenyl)-(1-indenyl)-ethane)zirconium dichloride is confirmed:

[0118] 1 H 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).

[0119] 13 C NMR (100MHz, CDCl3): δ28.2,31.7,99.6,104.6,112.1,114.5,121.7,121.8,1 23.5,125.2,126.0,126.3,126.9,127.5,128.0,129.5,130.4,140.7,145.6.

[0120]

[0121] Example 3

[0122] This embodiment is a method for preparing a specific main catalyst having the structural formula shown below.

[0123]

[0124] The specific preparation method is as follows:

[0125] f1) is different from step d1) described in Example 1 in that 0.2 mol of 2-phenyl-1-indanone is used instead of 1-indanone in step d1) as the starting material to carry out the Horner-Wadsworth-Emmons reaction, thereby preparing 0.161 mol of slightly red oily liquid (2-phenyl-1-indenyl)-1-acetic acid methyl ester with a yield of 80.6%.

[0126] Structure confirmation of methyl (2-phenyl-1-indenyl)-1-acetate:

[0127] 1 H 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).

[0128]

[0129] f2) is different from step d2) described in Example 1 in that 0.1 mol of (2-phenyl-1-indenyl)-1-methyl acetate replaces the (1-indenyl)-1-methyl acetate in step d2) to finally obtain 65.0 mmol of off-white solid ((2-phenyl-1-indenyl)-methyl)-2-indanol with a yield of 65.0%.

[0130] Structure confirmation of ((2-phenyl-1-indenyl)-methyl)-2-indanol:

[0131] 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(dddd,J=8.5,1.0,0.5Hz,1H).

[0132]

[0133] f3) is different from step d3) described in Example 1 in that 65.0 mmol of ((2-phenyl-1-indenyl)-methyl)-2-indanol is reacted with 10 mmol of p-toluenesulfonic acid monohydrate to finally obtain 61.2 mmol of light yellow solid (2-indenyl)-(2-phenyl-1-indenyl)-methane with a yield of 94.1%. The obtained light yellow solid is subjected to FTIR analysis, and the wavelength of FTIR at 3200-3600 cm -1 There is no obvious absorption peak, which indicates that all hydroxyl groups have undergone dehydration rearrangement reaction.

[0134]

[0135] f4) is different from step d4) described in Example 1 in that 93.7 mmol of n-butyl lithium n-BuLi is added to 60 mL of hexane to prepare a hexane solution of n-BuLi, 61.2 mmol of (2-indenyl)-(2-phenyl-1-indenyl)-methane is first reacted with the hexane solution of n-BuLi to obtain a lithium salt solution of (2-indenyl)-(2-phenyl-1-indenyl)-methane, and then reacted with 80 mL of a hexane solution containing 90.1 mmol of ZrCl4 to obtain 30.8 mmol of a light yellow solid main catalyst bis((2-indenyl)-(2-phenyl-1-indenyl)-methane) zirconium dichloride in a yield of 50.4%.

[0136] The structure of bis((2-indenyl)-(2-phenyl-1-indenyl)-methane)zirconium dichloride is confirmed:

[0137] 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).

[0138] 13 C 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.

[0139]

[0140] Example 4

[0141] This embodiment is a method for preparing a specific main catalyst having the structural formula shown below.

[0142]

[0143] The specific preparation method is as follows:

[0144] g1) is different from step d1) described in Example 1 in that 0.2 mol of 2-phenyl-1-indanone is used as the starting material for the Horner-Wadsworth-Emmons reaction to prepare 0.163 mol of reddish oily liquid (2-phenyl-1-indenyl)-1-methyl propionate in a yield of 81.2%.

[0145] Structure confirmation of methyl (2-phenyl-1-indenyl)-1-propionate:

[0146] 1 H 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).

[0147]

[0148] g2) is different from step d2) described in Example 1 in that 0.1 mol of (2-phenyl-1-indenyl)-1-propionic acid methyl replaces the (1-indenyl)-1-acetic acid methyl ester in step d2) to finally obtain 55.9 mmol of off-white solid ((2-phenyl-1-indenyl)-ethyl)-2-indanol with a yield of 55.9%.

[0149] Structure confirmation of ((2-phenyl-1-indenyl)-ethyl)-2-indanol:

[0150] 1 H 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(ddd d, 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 (dddd, J=7.8, 1.0, 0.5Hz, 1H).

[0151]

[0152] g3) is different from step d3) described in Example 1 in that 55.9 mmol of ((2-phenyl-1-indenyl)-ethyl)-2-indanol is reacted with 10 mmol of p-toluenesulfonic acid monohydrate to finally obtain 50.8 mmol of light yellow solid (2-indenyl)-(2-phenyl-1-indenyl)-ethane with a yield of 90.9%. The obtained light yellow solid was subjected to FTIR analysis, and the peak values ​​at 3200-3600 cm -1 There is no obvious absorption peak, which indicates that all hydroxyl groups have undergone dehydration rearrangement reaction.

[0153]

[0154] g4) is different from step d4) described in Example 1 in that 93.7 mmol of n-butyl lithium n-BuLi is added to 60 mL of hexane to prepare a hexane solution of n-BuLi, 50.8 mmol of (2-indenyl)-(2-phenyl-1-indenyl)-ethane is first reacted with the hexane solution of n-BuLi to obtain a lithium salt solution of (2-indenyl)-(2-phenyl-1-indenyl)-ethane, and then reacted with 80 mL of hexane solution containing 90.1 mmol of ZrCl4 to obtain 26.7 mmol of light yellow solid main catalyst bis((2-indenyl)-(2-phenyl-1-indenyl)-ethane)zirconium dichloride, with a yield of 52.5%.

[0155] The structure of bis((2-indenyl)-(2-phenyl-1-indenyl)-ethane)zirconium dichloride is confirmed:

[0156] 1 H 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).

[0157] 13 C 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.

[0158]

[0159] Example 5

[0160] This embodiment is a method for preparing a specific main catalyst having the structural formula shown below.

[0161]

[0162] The specific preparation method is as follows:

[0163] h1) Using 4H-cyclopentane [2,1-b:3,4-b'] dithiophene, referred to as 4H-dithienocyclopentadiene as the initial raw material, first dissolve 0.25 mol of 4H-dithienocyclopentadiene in 250 mL of THF, stir in an ice bath and cool to -20°C, then drop 0.26 mol of n-butyl lithium into the THF solution of 4H-dithienocyclopentadiene, naturally warm the reaction mixture to room temperature and stir for 2 hours, then cool to -78°C, drop 0.25 mol of methyl bromoacetate at this temperature, and after 30 minutes of dripping, naturally warm the reaction mixture to room temperature and stir for 12 hours to terminate the reaction. Quench the reaction with water, remove the solvent and other volatiles by distillation under reduced pressure, and dissolve the crude product in ether and water. Separate the organic layer, and wash the aqueous phase twice with ether. After drying the combined organic layer with magnesium sulfate, distill under reduced pressure to remove the solvent. An amber crude product was obtained, which was purified by flash chromatography using a mixture of hexane and diethyl ether as an eluent to obtain 0.139 mol of brown oily liquid (4-dithienocyclopentadienyl)-1-acetic acid methyl ester in a yield of 55.6%.

[0164] 1 H 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).

[0165]

[0166] h2) is different from step d2) described in Example 1 in that 0.1 mol of (4-dithienocyclopentadienyl)-1-methyl acetate is used to replace the (1-indenyl)-1-methyl acetate in step d2), and the (4-dithienocyclopentadienyl)-1-methyl acetate solution is added dropwise to the Grignard solution of o-dibenzyl chloride to react, ultimately obtaining 52.7 mmol of a brown solid ((4-dithienocyclopentadienyl)-methyl)-2-indanol with a yield of 52.7%.

[0167] 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).

[0168] 1H NMR (400MHz, CDCl3): δ3.01 (d, J = 15.6 Hz, 4H), 3.08 (d, J = 6.1 Hz, 2H), 4.01 (t, J = 6.1 Hz, 1H), 7.00 (d, J = 4.9 Hz, 2H), 7.18-7.33 (m, 6H).

[0169]

[0170] h3) is different from step d3) described in Example 1 in that 52.7 mmol of ((4-dithienocyclopentadienyl)-methyl)-2-indanol is reacted with 10 mmol of p-toluenesulfonic acid monohydrate to finally obtain 50.6 mmol of brownish yellow solid (2-indenyl)-(4-dithienocyclopentadienyl)-methane with a yield of 96.0%. The obtained brownish yellow solid was subjected to FTIR analysis, and the peaks at 3200-3600 cm -1 There is no obvious absorption peak, which indicates that all hydroxyl groups have undergone dehydration rearrangement reaction.

[0171]

[0172] h4) is different from step d4) described in Example 1 in that (2-indenyl)-(4-dithienocyclopentadienyl)-methane is first reacted with a hexane solution of n-BuLi to obtain a lithium salt solution of (2-indenyl)-(4-dithienocyclopentadienyl)-methane, which is then reacted with 80 mL of a hexane solution containing 90.1 mmol ZrCl4 to obtain 27.3 mmol of an orange-yellow solid main catalyst, bis((2-indenyl)-(4-dithienocyclopentadienyl)-methane)zirconium dichloride, with a yield of 54.0%.

[0173] 1 H 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).

[0174] 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.

[0175]

[0176] Example 6

[0177] This embodiment is a method for preparing a specific main catalyst having the structural formula shown below.

[0178]

[0179] The specific preparation method is as follows:

[0180] The difference between step i1) and step h1) in Example 5 is that 0.25 mol of methyl bromopropionate is used as methyl bromoacetate in step h1), thereby preparing 0.150 mol of reddish oily liquid (4-dithienocyclopentadienyl)-1-propionic acid methyl ester with a yield of 60.1%.

[0181] 1 H NMR (400MHz, CDCl3): δ2.25 (dt, J=8.0, 7.4Hz, 2H), 2.35 (t, J=7.4Hz, 2H), 3.6 5(s,3H),4.10(t,J=8.0Hz,1H),7.00(d,J=4.9Hz,2H),7.31(d,J=4.9Hz,2H).

[0182]

[0183] i2) is different from step h2) described in Example 5 in that 0.1 mol of (4-dithienocyclopentadienyl)-1-propionic acid methyl ester is used to replace the (4-dithienocyclopentadienyl)-1-acetic acid methyl ester in step h2), and finally 57.9 mmol of brown solid ((4-dithienocyclopentadienyl)-ethyl)-2-indanol is obtained, with a yield of 57.9%.

[0184] 1 H 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).

[0185]

[0186] i3) is different from step h3) described in Example 5 in that 57.9 mmol of ((4-dithienocyclopentadienyl)-ethyl)-2-indanol reacts with 10 mmol of p-toluenesulfonic acid monohydrate to finally obtain 55.8 mmol of brownish yellow solid (2-indenyl)-(4-dithienocyclopentadienyl)-ethane in a yield of 96.4%. The obtained brownish yellow solid was subjected to FTIR analysis, and the FTIR wavelength was 3200-3600 cm -1 There is no obvious absorption peak, which indicates that all hydroxyl groups have undergone dehydration rearrangement reaction.

[0187]

[0188] i4) is different from step h4) described in Example 5 in that (2-indenyl)-(4-dithienocyclopentadienyl)-ethane is first reacted with a hexane solution of n-BuLi to obtain a lithium salt solution of (2-indenyl)-(4-dithienocyclopentadienyl)-ethane, which is then reacted with 80 mL of a hexane solution containing 90.1 mmol ZrCl4 to obtain 30.9 mmol of an orange-yellow solid main catalyst bis((2-indenyl)-(4-dithienocyclopentadienyl)-ethane)zirconium dichloride in a yield of 55.3%.

[0189] 1 H 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(dd d,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).

[0190] 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.

[0191]

[0192] Example 7

[0193] This embodiment is a method for preparing a specific main catalyst having the structural formula shown below.

[0194]

[0195] The specific preparation method is as follows:

[0196] j1) is different from step h1) in Example 5 in that 0.25 mol of 9H-fluorene is used as the initial raw material to replace 4H-dithienocyclopentadiene in step h1), thereby preparing 0.149 mol of yellow oily liquid (9-fluorenyl)-1-acetic acid methyl ester with a yield of 59.8%.

[0197] 1 H 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).

[0198]

[0199] j2) is different from step h2) described in Example 5 in that 0.1 mol of (9-fluorenyl)-1-methyl acetate replaces the (4-dithienocyclopentadienyl)-1-methyl acetate in step h2) to finally obtain 59.8 mmol of yellow solid ((9-fluorenyl)-methyl)-2-indanol with a yield of 63.1%.

[0200] 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).

[0201]

[0202] j3) is different from step h3) in Example 5 in that 59.8 mmol of ((9-fluorenyl)-methyl)-2-indanol reacts with 10 mmol of p-toluenesulfonic acid monohydrate to finally obtain 58.3 mmol of brownish yellow solid (2-indenyl)-(9-fluorenyl)-methane with a yield of 97.6%. The obtained brownish yellow solid was subjected to FTIR analysis, and the peak wavelength was 3200-3600 cm -1 There is no obvious absorption peak, which indicates that all hydroxyl groups have undergone dehydration rearrangement reaction.

[0203]

[0204] j4) is different from step h4) described in Example 5 in that (2-indenyl)-(9-fluorenyl)-methane is first reacted with a hexane solution of n-BuLi to obtain a lithium salt solution of (2-indenyl)-(9-fluorenyl)-methane, which is then reacted with a hexane solution of ZrCl4 to obtain 34.0 mmol of orange-yellow solid main catalyst bis((2-indenyl)-(9-fluorenyl)-methane)zirconium dichloride in a yield of 58.2%.

[0205] The structure of bis((2-indenyl)-(9-fluorenyl)-methane)zirconium dichloride is confirmed:

[0206] 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).

[0207] 13 C NMR (101MHz, CDCl3): δ29.2,47.9,54.7,119.9,120.0,120.4,127.0,127.3,1 27.5,127.8,127.9,128.1,128.4,128.8,129.0,129.6,140.2,140.8,143.7.

[0208]

[0209] Example 8

[0210] This embodiment is a method for preparing a specific main catalyst having the structural formula shown below.

[0211]

[0212] The specific preparation method is as follows:

[0213] k1) is different from step j1) in Example 7 in that 0.25 mol of methyl bromopropionate is used to replace methyl bromoacetate in step j1), thereby preparing 0.143 mol of yellow oily liquid (9-fluorenyl)-1-propionic acid methyl ester with a yield of 57.2%.

[0214] 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).

[0215]

[0216] k2) is different from step j2) described in Example 7 in that 0.1 mol of (9-fluorenyl)-1-methyl propionate replaces the (9-fluorenyl)-1-methyl acetate in step j2) to finally obtain 59.4 mmol of yellow solid ((9-fluorenyl)-ethyl)-2-indanol with a yield of 59.4%.

[0217] 1 H 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(d dd,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).

[0218]

[0219] k3) is different from step j3) described in Example 7 in that 59.4 mmol of ((9-fluorenyl)-ethyl)-2-indanol reacts with 10 mmol of p-toluenesulfonic acid monohydrate to finally obtain 57.3 mmol of brownish yellow solid (2-indenyl)-(9-fluorenyl)-ethane with a yield of 96.5%. The obtained brownish yellow solid was subjected to FTIR analysis, and the wavelength of FTIR at 3200-3600 cm -1 There is no obvious absorption peak, which indicates that all hydroxyl groups have undergone dehydration rearrangement reaction.

[0220]

[0221] k4) is different from step j4) described in Example 7 in that (2-indenyl)-(9-fluorenyl)-ethane is first reacted with a hexane solution of n-BuLi to obtain a lithium salt solution of (2-indenyl)-(9-fluorenyl)-ethane, which is then reacted with a hexane solution of ZrCl4 to obtain 30.2 mmol of an orange-yellow solid main catalyst bis((2-indenyl)-(9-fluorenyl)-ethane)zirconium dichloride in a yield of 52.7%.

[0222] Structure Confirmation of Bis((2-Indenyl)-(9-Fluorenyl)-Ethane)Zirconium Dichloride

[0223] 1 H 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).

[0224] 13 C 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.

[0225]

[0226] Example 9

[0227] This embodiment is a method for preparing a specific main catalyst having the structural formula shown below.

[0228]

[0229] The specific preparation method is as follows:

[0230] l1) Indene and 2-(dimethylchlorosilyl)indene were used as raw materials. At 0°C, 0.875 mol of n-butyl lithium dissolved in 120 mL of THF was added dropwise to 86.2 mmol of indene dissolved in 50 mL of THF. The addition time was 20 min. After the addition was completed, the reaction mixture was naturally warmed to room temperature and stirred for 3 h to obtain a lithium salt solution of indene, which was transferred to a dropping funnel. 50 mL of THF was added to 93.4 mmol of chloro-2-indenylsilane to prepare a solution, and then the above-mentioned lithium salt solution of indene was added dropwise thereto. After the addition was completed, the reaction was stirred at room temperature for 12 h, and the reaction was quenched with 50 mL of distilled water. Subsequently, the solvent THF was removed by reduced pressure distillation to obtain a crude product, and ether and saturated brine were added to the crude product. After separating the ether layer, the aqueous phase was washed twice with ether. The combined organic layer was dried over anhydrous magnesium sulfate, and then the volatiles were removed by distillation under reduced pressure. The mixture was purified by flash chromatography using hexane as a solvent to obtain a yellow oil, which spontaneously crystallized when left to stand, to finally obtain 54.4 mmol of off-white crystalline dimethyl-(1-indenyl)-(2-indenyl)silane with a yield of 63.1%.

[0231] Structure confirmation of dimethyl-(1-indenyl)-(2-indenyl)silane:

[0232] 1 H 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).

[0233]

[0234] l2) is different from step d2) described in Example 1 in that 54.4mmol of dimethyl-(1-indenyl)-(2-indenyl)silane is first reacted with a hexane solution of n-BuLi to obtain a lithium salt solution of dimethyl-(1-indenyl)-(2-indenyl)silane, and then reacted with a hexane solution of ZrCl4 to obtain 28.1mmol of an orange-yellow solid main catalyst bis(dimethyl-(1-indenyl)-(2-indenyl)silane)zirconium dichloride, with a yield of 51.6%.

[0235] The structure of bis(dimethyl-(1-indenyl)-(2-indenyl)silane)zirconium dichloride is confirmed:

[0236] 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).

[0237] 13 C 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.

[0238] 1 H 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).

[0239] 13 C 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.

[0240]

[0241] Example 10

[0242] This embodiment is a method for preparing a specific main catalyst having the structural formula shown below.

[0243]

[0244] The specific preparation method is as follows:

[0245] m1) is different from step l1) described in Example 9 in that 84.8 mmol of 2-phenyl-indene is used as a raw material to react with 93.4 mmol of chloro-2-indenylsilane to finally obtain 49.4 mmol of off-white crystals of dimethyl-(2-phenyl-1-indenyl)-(2-indenyl)silane with a yield of 58.2%.

[0246] 1H-NMR (400 MHz, solvent: CDCl3): δ0.18 (s, 6H), 3.44 (d, J = 14.4 Hz, 2H), 3.80 (s, 1H), 6.55 (s, 1H), 6.96 (ddd, J = 7.8, 2.0, 0.5 Hz, 1H), 7.03-7.46 (13H, m).

[0247]

[0248] m2) is different from step l2) described in Example 9 in that 49.4 mmol of dimethyl-(2-phenyl-1-indenyl)-(2-indenyl) silane is first reacted with a hexane solution of n-BuLi to obtain a lithium salt solution of dimethyl-(2-phenyl-1-indenyl)-(2-indenyl) silane, and then reacted with a hexane solution of ZrCl4 to obtain 24.2 mmol of an orange-yellow solid main catalyst bis(dimethyl-(2-phenyl-1-indenyl)-(2-indenyl) silane) zirconium dichloride, with a yield of 49.0%.

[0249] The structure of bis(dimethyl-(2-phenyl-1-indenyl)-(2-indenyl)silane)zirconium dichloride is confirmed:

[0250] 1 H 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,1 H),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).

[0251] 13 C 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.

[0252]

[0253] Embodiment 11

[0254] This embodiment is a method for preparing a specific main catalyst having the structural formula shown below.

[0255]

[0256] The specific preparation method is as follows:

[0257] n1) is different from step l1) described in Example 9 in that 82.4 mmol of 4H-dithienocyclopentadiene is used as a raw material to react with 93.4 mmol of chloro-2-indenylsilane to finally obtain 55.3 mmol of light brown crystalline dimethyl-(4H-dithienocyclopentadienyl)-(2-indenyl)silane with a yield of 67.2%.

[0258] Structure confirmation of dimethyl-(4H-dithienocyclopentadienyl)-(2-indenyl)silane:

[0259] 1 H 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).

[0260]

[0261] n2) is different from step l2) described in Example 9 in that 55.3 mmol of dimethyl-(4H-dithienocyclopentadienyl)-(2-indenyl)silane is first reacted with a hexane solution of n-BuLi to obtain a lithium salt solution of dimethyl-(4H-dithienocyclopentadienyl)-(2-indenyl)silane, and then reacted with a hexane solution of ZrCl4 to obtain 28.0 mmol of an orange-yellow solid main catalyst bis(dimethyl-(4H-dithienocyclopentadienyl)-(2-indenyl)silane)zirconium dichloride in a yield of 50.7%.

[0262] The structure of bis(dimethyl-(4H-dithienocyclopentadienyl)-(2-indenyl)silane)zirconium dichloride is confirmed:

[0263] 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,1 H), 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).

[0264] 13 C 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.

[0265]

[0266] Example 12

[0267] This embodiment is a method for preparing a specific main catalyst having the structural formula shown below.

[0268]

[0269] The specific preparation method is as follows:

[0270] o1) is different from step l1) described in Example 9 in that 84.2 mmol 9H-fluorene is used as a raw material to react with 93.4 mmol chloro-2-indenylsilane to finally obtain 54.1 mmol of light yellow crystalline dimethyl-(9H-fluorenyl)-(2-indenyl)silane with a yield of 64.2%.

[0271] Structure confirmation of dimethyl-(9H-fluorenyl)-(2-indenyl)silane:

[0272] 1H NMR (400MHz, CDCl3): δ0.21 (s, 6H), 3.43 (d, J = 14.4Hz, 2H), 4.44 (s, 1H), 6.5 5(s,1H),6.96(ddd,J=7.8,2.0,0.5Hz,1H),7.09(td,J=7.7,2.0Hz,1H),7.2 0(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).

[0273]

[0274] o2) is different from step l2) described in Example 9 in that 54.1 mmol of dimethyl-(9H-fluorenyl)-(2-indenyl)silane is first reacted with a hexane solution of n-BuLi to obtain a lithium salt solution of dimethyl-(9H-fluorenyl)-(2-indenyl)silane, and then reacted with a hexane solution of ZrCl4 to obtain 27.9 mmol of an orange-yellow solid main catalyst bis(dimethyl-(9H-fluorenyl)-(2-indenyl)silane)zirconium dichloride, with a yield of 51.5%.

[0275] The structure of bis(dimethyl-(9H-fluorenyl)-(2-indenyl)silane)zirconium dichloride is confirmed:

[0276] 1 H 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).

[0277] 13 C NMR (101MHz, CDCl3): δ-1.0,-0.1,47.8,71.5,119.4,120.0,120.2,123.8,1 27.4,127.7,127.8,128.0,128.2,128.4,128.7,128.9,140.1,140.7,143.6.

[0278]

[0279] Embodiment 13

[0280] This embodiment is a method for preparing a specific main catalyst having the structural formula shown below.

[0281]

[0282] The specific preparation method is as follows:

[0283] p1) is different from step l1) described in Example 9 in that 84.6 mmol of dihydroindeno[1,2-b]benzothiophene (10H-indenobenzothiophene for short) is used as a raw material to react with 93.4 mmol of chloro-2-indenylsilane to finally obtain 55.0 mmol of light brown crystalline dimethyl-(10H-indenobenzothiophene)-(2-indenyl)silane with a yield of 65.0%.

[0284] Structure confirmation of dimethyl-(10H-indenobenzothiophene)-(2-indenyl)silane:

[0285] 1 H 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=7.7,1.1,0.5 Hz,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).

[0286]

[0287] p2) is different from step l2) described in Example 9 in that 55.0 mmol of dimethyl-(10H-indenobenzothiophene)-(2-indenyl)silane is first reacted with a hexane solution of n-BuLi to obtain a lithium salt solution of dimethyl-(10H-indenobenzothiophene)-(2-indenyl)silane, and then reacted with a hexane solution of ZrCl4 to obtain 29.2 mmol of an orange-yellow solid main catalyst bis(dimethyl-(10H-indenobenzothiophene)-(2-indenyl)silane)zirconium dichloride, with a yield of 53.1%.

[0288] The structure of bis(dimethyl-(10H-indenobenzothiophene)-(2-indenyl)silane)zirconium dichloride is confirmed:

[0289] 1 H 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).

[0290] 13 C 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.

[0291]

[0292] Embodiment 14

[0293] This embodiment is a method for preparing a specific main catalyst having the structural formula shown below.

[0294]

[0295] The specific preparation method is as follows:

[0296] q1) is different from step l1) described in Example 9 in that 84.0 mmol of N-methyl-dihydroindeno[1,2-b]indole, referred to as N-methyl-10H-indenoindole, is used as a raw material to react with 93.4 mmol of chloro-2-indenylsilane to finally obtain 57.7 mmol of light yellow crystalline dimethyl-(N-methyl-10H-indenoindole)-(2-indenyl)silane with a yield of 68.7%.

[0297] Structure confirmation of dimethyl-(N-methyl-10H-indenoindole)-(2-indenyl)silane:

[0298] 1 H 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=7.8,2.0,0.5H z,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).

[0299]

[0300] q2) is different from step l2) described in Example 9 in that 57.7 mmol of dimethyl-(N-methyl-10H-indenoindole)-(2-indenyl)silane is first reacted with a hexane solution of n-BuLi to obtain a lithium salt solution of dimethyl-(N-methyl-10H-indenoindole)-(2-indenyl)silane, and then reacted with a hexane solution of ZrCl4 to obtain 31.9 mmol of an orange-yellow solid main catalyst bis(dimethyl-(N-methyl-10H-indenoindole)-(2-indenyl)silane)zirconium dichloride, with a yield of 55.3%.

[0301] The structure of bis(dimethyl-(N-methyl-10H-indenoindole)-(2-indenyl)silane)zirconium dichloride is confirmed:

[0302] 1 H 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).

[0303] 13 C NMR (101MHz, CDCl3): δ-1.0,-0.3,31.1,47.6,71.9,112.0,118.7,120.2,120.6,123.8,12 7.3,127.5,127.8,128.0,128.2,128.3,128.7,128.9,129.2,133.7,137.0,139.3,144.2.

[0304]

[0305] Examples 15 to 28 and Comparative Examples 1 to 4

[0306] Refining of α-olefin raw materials: 0.8wt% of sodium hydroxide solid is added to 1-nonene and stirred for 60 minutes, followed by reduced pressure distillation at a vacuum degree of 0.8 torr, collecting the fraction at 55-85°C, and then eluting it through a glass column filled with activated neutral alumina, thereby removing oxygen-containing impurities such as water, long-chain fatty alcohols, and long-chain fatty ethers mixed in the α-olefins, wherein the elution process is carried out in a nitrogen glove box or under nitrogen protection by Schlenk technology, and the activation method of the neutral alumina is baking at 600°C in a muffle furnace for 4 hours.

[0307] The polymerization reaction of polyalphaolefin is carried out in a 1L polymerization reactor. First, the reactor is heated to above 100°C and vacuum-baked for 1h, during which it is replaced with high-purity nitrogen several times to remove water / oxygen impurities in the reactor. Then the reaction temperature is set to 30°C, and the temperature of the reactor is adjusted to the set reaction temperature by jacket water circulation. 440.4g of refined 1-nonene is added, and then a certain concentration of co-catalyst triisobutylaluminum Al(i-Bu)3 is added. The Al concentration of Al(i-Bu)3 in the reaction system is 60mmol / L. The stirring rate is turned on at 500rpm. After stirring for 20min, the metallocene main catalyst and the organic compound containing the boron element dissolved in an inert solvent are added to the polymerization reactor. Among them, the Zr concentration of the metallocene main catalyst in the reaction system is 0.25mmol / L, and the organic compound containing the boron element [Ph3C] + [B(C6F5)4] － The concentration of B in the reaction system was 0.25 mmol / L, the inert solvent was toluene, and the total amount was 120 mL.

[0308] After adding the catalyst composition, the nitrogen valve is opened to fill the nitrogen pressure to 0.1MPa, the reaction is terminated after 1.5h of reaction, the vent pipe is opened to release the pressure, the crude product is released from the reactor, 10mL of a mixed solution of water / ethanol / hydrochloric acid solution is added to the crude product to quench the reaction, 3wt% of white clay is added to the obtained product to adsorb and remove the catalyst residue, and then pressure filtration is performed to obtain a filtrate, and the filtrate is subjected to reduced pressure distillation at 120°C and a vacuum degree of 0.5torr to remove light components such as solvents and unreacted monomers to obtain a slightly yellow viscous and transparent liquid polyalphaolefin product, and the obtained polyalphaolefin product is naturally cooled to room temperature, and white opaque solid polyalphaolefin wax can be precipitated. It is worth noting that only part of the polyalphaolefin can produce white opaque polyalphaolefin wax, and the other part still exists in the form of a slightly yellow viscous and transparent liquid, and filtration is required to separate the two.

[0309] Among them, the co-catalyst of Comparative Example 4 does not use Al(i-Bu)3 and [Ph3C] + [B(C6F5)4] － The method is different from the above steps in that MAO and the metallocene main catalyst are dissolved in an inert solvent and then directly added to the reactor.

[0310] The test dosages and results of Examples 15 to 28 and Comparative Examples 1 to 4 are shown in Table 1.

[0311] Test method for molecular weight and molecular weight distribution of polyalphaolefins: Use high temperature gel permeation chromatography (GPC) to test the average molecular weight and molecular weight distribution, use 1,2,4-trichlorobenzene as a solvent to dissolve the polyalphaolefin sample at 150°C, use narrow molecular weight polyethylene as the test standard sample, GPC test conditions are 135°C, feed flow rate is 1.0mL / min, and molecular weight data of weight average molecular weight Mw and number average molecular weight Mn are processed by GPC software. The polydispersity index used to represent the molecular weight distribution is calculated by Mw / Mn. At the same time, the average degree of polymerization of polyalphaolefins is also calculated based on the number average molecular weight Mn.

[0312] Thermal properties test of polyalphaolefin: Differential scanning calorimeter measurement, test temperature -20 ~ 140 ° C, by cooling the sample from room temperature to -20 ° C at a rate of 5 ° C / min in a nitrogen atmosphere, keeping it at -20 ° C for 5 minutes, and then raising its temperature to 140 ° C at a rate of 10 ° C / min. Record the DSC curve from -20 ° C to 140 ° C.

[0313] Chemical structure characterization of polyalphaolefins: 13 C-NMR was measured at room temperature, and the solvent was CDCl3.

[0314] As shown in Table 1, "-" indicates that it does not appear. The structures of the metallocene procatalysts of Comparative Examples 1-3 are:

[0315] rac-Et(Ind)2ZrCl2

[0316] Me2C(Cp(9-Flu))ZrCl2

[0317] rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2

[0318] As shown in Table 1, the metallocene main catalyst and the cocatalyst Al(i-Bu)3 and [Ph3C] + [B(C6F5)4] －By using them in combination, a series of high molecular weight and narrow molecular weight distribution polyalphaolefins can be prepared. Compared with comparative example 4 using MAO as a co-catalyst, embodiments 15 to 28 have better polymerization uniformity, higher molecular weight and narrower molecular weight distribution. This is because the organic compound containing the boron element has a stronger stabilizing ability on the cationic active center of the metallocene main catalyst. MAO is a low molecular weight polymer obtained by partial hydrolysis of trimethylaluminum, and its catalytic activity in combination with the metallocene main catalyst is significantly higher. Trimethylaluminum residues are inevitably present in MAO, and trimethylaluminum has strong chain transfer activity, resulting in high alpha olefin conversion rate and catalytic activity in comparative example 4, but low molecular weight and wider molecular weight distribution of the obtained polyalphaolefin.

[0319] Comparative Examples 1 to 3 and Examples 15 to 28 use the same co-catalyst, the difference being that the structure of the metallocene main catalyst is different. Comparative Example 1 has significantly lower catalytic activity than Examples 15 to 28, and the resulting poly-alpha-olefin has a low molecular weight and a wide molecular weight distribution.

[0320] The catalytic activity of Comparative Example 2 is significantly lower than that of Examples 15 to 28, and the molecular weights of the obtained poly-alpha-olefins are similar and the molecular weight distribution is wide.

[0321] Compared with Examples 15 to 28, Comparative Example 3 has similar catalytic activity, and the molecular weights of the obtained poly-α-olefins are similar and the molecular weight distribution is broad.

[0322] When C9 is used as a raw material for preparing polyalphaolefins, the obtained polyalphaolefins can only form polyalphaolefin waxes under conditions of higher average polymerization degree and molecular weight. This is because the polyalphaolefin side chains prepared from C9 are relatively shorter, and the regular arrangement is not enough to form crystals. Only local chain segments can crystallize, and then white waxy products are precipitated from the liquid polyalphaolefins. Only under conditions of higher polymerization degree can polyalphaolefin molecules be more easily arranged closely to form crystalline regions.

[0323] From the data in Table 1, it can be seen that white waxy products begin to appear only when the average degree of polymerization is ≥150, wherein the white waxy products account for 10-40wt% of the entire poly-alpha olefin product. The higher the average degree of polymerization, the higher the proportion of the white waxy products. Poly-alpha olefins with a low average degree of polymerization are difficult to crystallize to form poly-alpha olefin wax products.

[0324] Table 1

[0325]

[0326] Table 1

[0327] Examples 29 to 42 and Comparative Examples 5 to 8

[0328] Refining of α-olefin raw materials: 0.8wt% of sodium hydroxide solid is added to 1-hexadecene and stirred for 60 minutes, followed by reduced pressure distillation at a vacuum degree of 0.8 torr, collecting the fraction at 150-180°C, and then eluting it through a glass column filled with activated neutral alumina, thereby removing oxygen-containing impurities such as water, long-chain fatty alcohols, and long-chain fatty ethers mixed in the α-olefins, wherein the elution process is carried out in a nitrogen glove box or under nitrogen protection by Schlenk technology, and the activation method of the neutral alumina is baking at 600°C in a muffle furnace for 4 hours.

[0329] Among them, the test dosages and results of Examples 29 to 42 and Comparative Examples 5 to 8 are shown in Table 1.

[0330] The polymerization reaction of poly-alpha olefin is the same as above, except that 469.8 g of the refined alpha olefin raw material 1-hexadecene is added, the concentration of Al(i-Bu)3 in the reaction system is 120 mmol / L, the concentration of Zr in the metallocene main catalyst in the reaction system is 0.5 mmol / L, and the organic compound containing boron element [Me2NHPh] + [B(C6F5)4] － The concentration of B in the reaction system was 0.5 mmol / L.

[0331] Among them, the co-catalyst of Comparative Example 8 does not use Al(i-Bu)3 and [Me2NHPh] + [B(C6F5)4] － The method is different from the above steps in that MAO and the metallocene main catalyst are dissolved in an inert solvent and then directly added to the reactor.

[0332] When the reaction temperature is set to 70°C, the concentration of Al(i-Bu)3 in the reaction system is 60mmol / L, the concentration of Zr in the metallocene main catalyst is 0.25mmol / L, and the organic compound containing boron element [Me2NHPh] + [B(C6F5)4] － The concentration of B in the reaction system was 0.25 mmol / L.

[0333] As shown in Table 2, "-1" indicates that the reaction temperature was set to 30°C, and "-2" indicates that the reaction temperature was set to 70°C.

[0334] As shown in Table 2, when C16 is used as a raw material for preparing polyalphaolefin, the obtained polyalphaolefin can crystallize and precipitate more white waxy products. This is because after the chain length of the alpha olefin increases to a certain extent, the synthesized polyalphaolefin side chain will form crystals, and a high degree of polymerization is not required to obtain the polyalphaolefin product. In addition, the proportion of polyalphaolefin wax in the overall polyalphaolefin product is significantly improved. The proportion of polyalphaolefin wax in Examples 29 to 42 and Comparative Examples 5 to 8 is generally not less than 85wt%. This shows that in order to obtain a higher proportion of polyalphaolefin wax in the product, alpha olefins with longer carbon chains should be selected as raw materials to synthesize polyalphaolefin wax, but the cost of alpha olefins with more than 10 carbon atoms is higher, and the product with a low proportion of polyalphaolefin wax synthesized by selecting alpha olefins with less than 10 carbon atoms is more economical.

[0335] From the perspective of polymerization temperature, compared with the reaction temperature of 70°C, the average degree of polymerization of polyalphaolefins at 30°C is higher, and the corresponding proportion of polyalphaolefin wax is slightly higher. This is because high temperature is conducive to the activation of the metallocene main catalyst, and high temperature is conducive to the formation of active centers. The proportion of active centers increases with increasing temperature. At the same time, the chain transfer rate of the reaction system increases at high temperature. Therefore, high temperature prompts the alpha olefin monomer to form a polymerization product with a lower molecular weight. The activity of the main catalyst is significantly improved at 70°C, and the corresponding alpha olefin conversion rate is also relatively higher.

[0336] From the perspective of the main catalyst activity, the catalytic activity of Examples 29 to 42 for 1-hexadecene is generally high, and the activity is not less than 450 Kg·mol at 30°C. -1 (Zr)·h -1 , the activity is not less than 1000Kg·mol at 70℃ -1 (Zr)·h -1 Compared with Examples 1 to 14, Examples 29 to 42 using the same metallocene main catalyst have lower catalytic activity for α-olefins. This is because the carbon chain of the C16 α-olefin monomer is longer and the steric hindrance is relatively higher. Due to the steric hindrance effect and the weaker coordination ability of the active center, especially at a reaction temperature of 30°C, the catalytic activity of the main catalyst is generally lower than that of 1-nonene.

[0337] Compared with Comparative Examples 5-7, the molecular weight, molecular weight distribution, average degree of polymerization and proportion of polyalphaolefin wax of the polyalphaolefin products obtained by polymerization in Examples 29-42 are not much different. However, the catalytic activity of the main catalysts of Examples 29-42 at 30°C and 70°C is significantly higher than that of Comparative Examples 5-7, especially the main catalysts with structures of Me2C(Cp(9-Flu))ZrCl2 and rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2, whose catalytic activity in catalyzing the polymerization of C9 monomer is close to that of the embodiments. After the monomer is changed to C16 alpha olefin with higher steric hindrance, its catalytic activity decreases significantly. This indicates that the metallocene main catalysts synthesized in Examples 1-14 have higher catalytic activity for alpha olefins, especially long-chain alpha olefins with high steric hindrance.

[0338] Comparative Example 8: MAO is used to replace the co-catalysts Al(i-Bu)3 and [Me2NHPh] in other embodiments and comparative examples. + [B(C6F5)4] － The combination did not react at 30°C and 70°C. This is because C16 olefins contain long carbon chain oxygen-containing substances such as C16 alcohols, aldehydes, and ethers that hinder the reaction. Due to the long carbon chain structure in the molecule, the polarity is close to that of C16 olefins. It is difficult to separate them by adsorption through a neutral alumina column during the raw material refining process. If these long carbon chain oxygen-containing substances directly contact the main catalyst, the latter will be poisoned. Therefore, it is necessary to stir C16 olefins and alkyl aluminum for a period of time before adding the catalyst combination for polymerization reaction.

[0339] The DSC test results of Examples 18, 20, 27, 34-1, 34-2 and Comparative Example 4 are shown in the attached Figure 1 As shown in the attached Figure 1 It can be seen that with the increase of the polymerization degree of α-olefin monomer, the originally amorphous poly-α-olefin begins to have a melting point peak, which is due to the increase of the molecular weight of the poly-α-olefin, the more regular arrangement of the molecular chain, and the crystallization of the main side chain. Through the comparison of Examples 18, 20, 27, 34-1, and 34-2, it can be seen that with the increase of the molecular weight, the melting point also increases, and with the increase of the length of the side chain of the α-olefin monomer, the melting point of the poly-α-olefin also increases. This is because the increase of the molecular weight and the length of the side chain of the poly-α-olefin increases the resistance to the internal rotation of the polymer chain, thereby making the molecular chain more rigid, and the conformational change is small during the melting process, resulting in an increase in the melting point peak of the DSC test.

[0340] At the same time, the polyalphaolefins prepared in Example 20 and Example 34-2 were subjected to 13 C-NMR characterization, as attached Figure 2It can be seen that no spectral peaks were found in the olefin double bond region with a chemical shift of 100 to 150, indicating that the polymerization reaction was complete and there was no residual carbon-carbon double bond in the molecule, indicating that the catalyst successfully synthesized the target product by catalyzing the coordination polymerization of α-olefin monomers.

[0341] Table 2

[0342]

[0343]

[0344]

[0345] Finally, it should be noted that the above is only a preferred embodiment of the present application and is not intended to limit the scope of protection of the present application. Although the present application has been described in detail with reference to the aforementioned embodiments, for those skilled in the art, any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present application should be included in the scope of protection of the present application.

Claims

1. 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, 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 X1 and X2 are halogen; The E n is a bridging group; Said R1 and R2 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; The R3 and R4 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 the R3, R4 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 R5, R6 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; R7, R8, R9, R 10 , R 11 With R 12 Each is 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: AlR3, AlR m H (3-m) Or AlR m X (3-m) , wherein m is an integer from 0 to 3; And / or, X1 is Cl or Br; And / or, X2 is Cl or Br; and / or, the E n The bridging atom 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: Said R1 and R2 are the same and are selected from hydrogen or methyl; And / or, R7, R8, R9, R 10 , R 11 With R 12 All are 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 boron-containing organic compound is trityltetrakis(pentafluorophenyl)borate [Ph3C] + [B(C6F5)4] － and / or dimethylphenylammonium tetrakis(pentafluorophenyl)borate [Me2NHPh] + [B(C6F5)4] － .

4. The use according to claim 1, characterized in that The general structural formula of the main catalyst is shown in Formula II, Formula III, and 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 E n The main catalyst for the silicon bridge 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 E n The main catalyst is a single carbon bridge or a double carbon bridge, and R3, R4 and two carbon atoms on the cyclopentadienyl group together form a new benzene ring, which 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; For E n The main catalyst is a single carbon bridge or a double carbon bridge, and R3, R4 and R5, R6 together with the two carbon atoms on the cyclopentadienyl group form a new aromatic ring or aromatic heterocycle, which 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 ROLi.

7. The use according to claim 6, characterized in that In the organic lithium base R0Li, R0 is a straight-chain 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 preparation 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 X1 and X2 are halogen; The E n is a bridging group; Said R1 and R2 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; The R3 and R4 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 the R3, R4 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 R5, R6 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; R7, R8, R9, R 10 , R 11 With R 12 Each is independently selected from one of 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.

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