Metallocene compounds, methods of preparation and uses

Abstract

The present application provides a metallocene compound, its preparation method and use. The metallocene compound of the present application has a structure shown in formula a, in which Ar is selected from substituted or unsubstituted C6-C30 aryl, Cp' is selected from substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl, X is selected from at least one of halogen, substituted or unsubstituted C1-C30 alkyl, alkoxy, substituted or unsubstituted C2-C30 dialkylamino, alkenyl, or substituted or unsubstituted C6-C30 aryl, and M is a transition metal element. The metallocene compound is applicable to catalyzing C6-C30 long linear α-olefin feedstock and mixed long branched internal olefin feedstock, and further, the metallocene compound can obtain a polymerization product with a target molecular weight as required.

Description

[Technical Field]

[0001] TECHNICAL FIELD This application relates to the field of metallocene catalyst technology, and in particular to metallocene compounds and their methods of preparation and use. [Background technology]

[0002] The preparation of metallocene compounds and their catalytic activity in olefin polymerization reactions have traditionally been one of the hot spots in chemical research.

[0003] In 1990, U.S. Pat. No. 6,548,686 described a method for preparing transition metal compounds with restricted geometric structures and Its uses are disclosed, and the structure of the compound is shown in Formula 1. Compounds of this type can be used to catalyze the polymerization or copolymerization of ethylene and short chain olefins such as propylene, butene, butadiene, and 1-hexene.

[0004] Marks designed and synthesized two phenoxy-side-chain-containing, geometrically restricted metallocene catalysts (see Formulas 2 and 3) using a "one-pot synthesis" method in 1997. This type of catalyst is primarily used to catalyze the polymerization of ethylene and propylene.

[0005] In 1998, Bart Hessen designed and synthesized 1-(tetramethylcyclopentadienyl)-propoxy-titanium dichloride (see Formula 4), which was then reacted with an appropriate alkyllithium or Grignard reagent to obtain a type of metallocene catalyst with a restricted geometry containing a propoxy side chain half metallocene (see Formula 5, where R is one selected from H, Ph, SiMe3, and CMe3). This type of catalyst is mainly used to catalyze propylene polymerization.

[0006] In 2007, Professor Mu Ying disclosed in China Patent Publication No. 101130467 a metallocene catalyst (see Formula 6) containing phenoxy side chains and with restricted geometric structure. This catalyst employs alkylaluminum and boron compounds as cocatalysts to catalyze C6-C20 linear α-olefins to obtain a colorless, transparent oil. The product has high viscosity, a high viscosity index, and a low pour point, making it suitable for use as a lubricating base oil. However, the coordination environment of the active center of this catalyst is too open, resulting in a low molecular weight polymer.

[0007] In 2008, Mu Ying's research team also reported the development of metallocene catalysts with restricted geometries containing single carbon atom bridging aryloxy groups (see Formula 7, where R1 is H(1), Me(2), or t Bu(3,4), and R2 is H(2,3) or t The catalyst can be used to catalyze the preparation of medium molecular weight polyethylene by ethylene polymerization or the preparation of medium molecular weight copolymerization products of ethylene and 1-hexene by copolymerization of ethylene and 1-hexene.

[0008] In 2009, Hidenori Hanaoka reported a series of novel titanium metal catalysts with restricted geometric structures (see Equations 8 to 11). In Equation 8, R represents Me and Et, respectively; in Equation 9, R represents Me and Et, respectively; and in Equation 10, R represents Me and Et. 1 is selected from H or Me, and R 2 is selected from Me and Et, and in formula 11, R is Me and H, respectively. This catalyst is mainly used for the copolymerization of ethylene and 1-hexene, and can effectively improve the polymerization activity, produce high molecular weight copolymers, and ensure a high insertion rate of 1-hexene.

[0009] Based on this, Hidenori Hanaoka et al. introduced fluorenyl into the phenoxy-metal system to produce a new metallocene catalyst (see Equation 12, where M is selected from Ti, Zr, or Hf, and R 1 is H or t Selected from Bu, R 2 is selected from Me or Et, and X is selected from NMe2 or Cl) was prepared. This metallocene catalyst can maximize the activity of copolymerization of ethylene and 1-hexene.

[0010] [ka]

[0011] However, metallocene compounds having the above structural formula have limitations in terms of either raw materials or products. For example, they are only applicable to catalyzing the polymerization reaction of linear olefins having 6 or fewer carbon atoms, and cannot be applied to catalyzing the polymerization reaction of linear olefins having more than 6 carbon atoms, nor can they be applied to catalyzing the polymerization reaction of branched olefins having 6 or more carbon atoms. In addition, when metallocene compounds having the above structural formula are used to catalyze the polymerization reaction of linear olefins having 6 or more carbon atoms, it is not possible to prepare a high molecular weight polymerization product. Summary of the Invention [Problem to be solved by the invention]

[0012] The present application provides a metallocene compound that can catalyze long linear α-olefin feedstocks and mixed long branched internal olefin feedstocks with high efficiency, and further, can produce polymerization products having target molecular weights as required.

[0013] The present application provides a method for preparing a metallocene compound, which can be used to prepare a metallocene compound that is applicable to highly efficient catalysis of long linear α-olefin feedstocks and mixed long branched internal olefin feedstocks, and can also produce a polymerization product of the metallocene compound having a target molecular weight as required.

[0014] The present application provides a catalyst system that can be applied to catalyze C6-C30 long linear α-olefin feedstocks and mixed long branched internal olefin feedstocks, and can also produce polymerization products with target molecular weights as required. [Means for solving the problem]

[0015] The present application provides a metallocene compound, wherein the metallocene compound has the structure shown in formula a: [ka] During the ceremony, Ar is selected from substituted or unsubstituted C6-C30 aryl; Cp' is selected from substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl; X is a halogen atom, a substituted or unsubstituted C1-C30 alkyl group, an alkoxy group, a substituted or unsubstituted C2-C30 dialkylamino group, an alkenyl group, and selected from at least one of substituted or unsubstituted C6-C30 aryl; M is a transition metal element.

[0016] For the metallocene compounds as described above, where in Ar, the C6-C30 aryl substituents are methyl, ethyl, methylene, isopropyl, vinyl, propenyl, and butenyl. At least one selected from .

[0017] For the metallocene compounds as described above, the substituents of cyclopentadienyl, indenyl, or fluorenyl in Cp' are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and phenyl. At least one of the following is selected from .

[0018] For the metallocene compounds as described above, the substituents of C1-C30 alkyl, C1-C30 alkoxy, C2-C30 dialkylamino, C2-C30 alkenyl, or C6-C30 aryl in X are methyl, ethyl, methylene, isopropyl, vinyl, propenyl, and butenyl. At least one of the following is selected from .

[0019] For the metallocene compounds as described above, the structural formula of the metallocene compounds includes the following: [ka]

[0020] The present application further provides a method for preparing a metallocene compound as described above, wherein the method comprises: reacting a diarylmethanol with a dihydropyran in the presence of p-toluenesulfonic acid to form a first compound; reacting the first compound with n-butyllithium, and then adding dichlorodimethylsilane to the system to obtain a second compound; reacting the second compound with a third compound to obtain a fourth compound, and reacting the fourth compound with hydrochloric acid to obtain a ligand; reacting the ligand with a strong base compound to obtain a ligand salt; reacting the ligand salt with MX4 to obtain the metallocene compound; wherein the third compound is obtained by reacting the fifth compound with n-butyllithium; The fifth compound may be a substituted or unsubstituted cyclopentadiene, indene, and Fluorene At least one of the following is selected from .

[0021] Regarding the above-mentioned preparation method, the strong base compound is n-butyllithium, methyllithium, methylmagnesium chloride, and Benzylmagnesium chloride At least one selected from .

[0022] Regarding the above-mentioned preparation method, wherein during the preparation of the second compound, a diarylmethanol, a dihydropyran, and n- butyllithium has a molar ratio of (29.5-30.5):(59.5-60.5):(29.7-35.1), and / or During the preparation of the ligand, the second compound, the fifth compound, n-butyllithium, and hydrochloric acid are mixed in a molar ratio of (4.3-5.2):(4.2-4.8):(4.5-5.2):(9.8-10.4).

[0023] In the above preparation method, the ligand, the strong basic compound, and MX4 are present in a molar ratio of (3.8-4.4):(8.0-9.2):(3.9-4.5).

[0024] The present application further provides a catalyst system, wherein the catalyst system comprises the metallocene compound described above. [Effects of the Invention]

[0025] The metallocene compound of the present invention has the structure shown in formula (a), which is a silicon-carbon-oxygen bridged heteroatom compound with a restricted geometry. The metal center of the metallocene compound contains a five-membered chelate ring, and two large, sterically hindering aromatic groups are attached to the bridging carbon atom. As a result, the coordination space environment is more crowded, which greatly improves the thermal stability of the metallocene compound. It exhibits exceptionally high catalytic activity under high temperature conditions, high tolerance to impurities, and a long catalyst life. Therefore, the metallocene compound can be used to catalyze C6-C30 long-chain linear α-olefin feedstocks and mixed long-branched internal olefin feedstocks, and can produce polymerization products with target molecular weights as needed.

[0026] The catalyst system according to the present invention, which contains the above-mentioned metallocene compound, can be applied to catalyze C6-C30 long linear α-olefin feedstocks and mixed long branched internal olefin feedstocks, and can also produce polymerization products with target molecular weights as required.

[0027] In order to more clearly describe the technical solutions in the embodiments of the present application or the related art, the drawings that need to be used in the description of the embodiments of the present application or the related art will be briefly described below. Of course, the drawings described below are only some embodiments of the present application, and those skilled in the art can devise other drawings based on these drawings without any creative effort. [Brief explanation of the drawings]

[0028] [Figure 1] 1 is a nuclear magnetic resonance hydrogen spectrum ( 1 H NMR) of a polymerization product obtained by catalyzing the polymerization reaction of 1-decene using a metallocene compound according to Example 1 of the present application. DETAILED DESCRIPTION OF THE INVENTION

[0029] Hereinafter, the technical solutions of the present application will be described clearly and completely with reference to the drawings of the embodiments of the present application, and it should be understood that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments, and all other embodiments obtained by those skilled in the art without creative work based on the embodiments of the present application fall within the scope of protection of the present application.

[0030] In a first aspect, the present application provides a metallocene compound having the structure shown in formula a: [ka] During the ceremony, Ar is selected from substituted or unsubstituted C6-C30 aryl; Cp' is selected from substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl; X is a halogen atom, a substituted or unsubstituted C1-C30 alkyl group, an alkoxy group, a substituted or unsubstituted C2-C30 dialkylamino group, an alkenyl group, and selected from at least one of substituted or unsubstituted C6-C30 aryl; M is a transition metal element.

[0031] Specifically, Ar is selected from substituted or unsubstituted C6-C30 aryl (e.g., Phenyl group, biphenyl group, substituted phenyl group, or substituted biphenyl group (possibly When Cp' is selected from substituted cyclopentadienyl, substituted indenyl, or substituted fluorenyl, the substituent may be one or more, for example, the substituents may be one methyl, two methyls, or one methyl and one ethyl; X is halogen (e.g., -F, -Cl, -Br, -I), substituted or unsubstituted C1-C30 alkyl (e.g., C1-C30 straight chain alkyl, C1-C30 branched chain alkyl), alkoxy (e.g., C1-C30 branched chain alkoxy, C1-C30 straight chain alkoxy), substituted or unsubstituted C2-C30 dialkylamino (e.g., amino substituted with two C1-C15 straight chain alkyls), alkenyl (e.g., C2-C30 straight chain alkenyl), or substituted or unsubstituted C6-C30 aryl (e.g., a phenyl group, a biphenyl group, a substituted phenyl group, or a substituted biphenyl group may be M is a transition metal element (e.g., Ti, Ni, Zr, Hf).

[0032] The metallocene compound according to the present invention is a silicon-carbon-oxygen bridged heteroatom compound with a restricted geometric structure. The metal center of the metallocene compound contains a five-membered chelate ring, and two large, sterically hindering aromatic groups are attached to the bridging carbon atom. As a result, the coordination space environment is further congested. This significantly improves the thermal stability of the metallocene compound, and it exhibits exceptionally high catalytic activity under high-temperature conditions. It also has high impurity tolerance and a long catalyst life. Therefore, the metallocene compound can be used with both long linear α-olefins and long branched internal olefins, and can produce polymerization products with the desired molecular weight. For example, it can be used in the polymerization of linear olefins with more than six carbon atoms and branched olefins with six or more carbon atoms, and can produce high-molecular-weight polymers after the polymerization reaction.

[0033] Although the present application does not particularly limit the C6-C30 aryl substituents for Ar, in some embodiments, the C6-C30 aryl substituents for Ar include methyl, ethyl, methylene, isopropyl, vinyl, propenyl, and butenyl. At least one of the following is selected from .

[0034] Although the present application does not specifically limit the substituents of Cp' to cyclopentadienyl, indenyl, or fluorenyl, in some embodiments, Cp' Cyclopentadienyl, indenyl, or fluorenyl in The substituents are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and phenyl. At least one of the following is selected from Preferably, the substituents of cyclopentadienyl, indenyl, or fluorenyl in Cp' are selected from at least one of methyl, ethyl, n-propyl, isopropyl, and butyl.

[0035] In some embodiments of the present application, the C1-C30 alkyl, C1-C30 alkoxy, C2-C30 dialkylamino, C2-C30 alkenyl, or C6-C30 aryl substituents on X are methyl, ethyl, methylene, isopropyl, vinyl, propenyl, and butenyl. At least one of the following is selected from .

[0036] In some embodiments of the present application, the structural formula of the metallocene compound comprises: [ka]

[0037] In a second aspect, the present application provides a method for preparing the metallocene compound as described above, said method comprising: reacting a diarylmethanol with a dihydropyran in the presence of p-toluenesulfonic acid to form a first compound; reacting the first compound with n-butyllithium, and then adding dichlorodimethylsilane to the system to obtain a second compound; reacting the second compound with a third compound to obtain a fourth compound, and reacting the fourth compound with hydrochloric acid to obtain a ligand; reacting the ligand with a strong base compound to obtain a ligand salt; reacting the ligand salt with MX4 to obtain a metallocene compound; wherein the third compound is obtained by reacting the fifth compound with n-butyllithium; The fifth compound is a substituted or unsubstituted cyclopentadiene, indene, and Fluorene At least one of the following is selected from .

[0038] In the present application, the ligand is adding the diarylmethanol with dihydropyran in the presence of p-toluenesulfonic acid to form a first compound, diarylmethyl-2-tetrahydropyranyl ether; reacting the diarylmethyl-2-tetrahydropyranyl ether with n-butyllithium to obtain an intermediate product, and then reacting the intermediate product with dichlorodimethylsilane to obtain a second compound (c); The fifth compound (Cp') is reacted with n-butyllithium to obtain the third compound (Cp'HLi), which is then reacted with the second compound (c) to obtain the fourth compound (d), and finally the fourth compound (d) is reacted with hydrochloric acid to obtain the ligand. The specific reaction scheme is shown in Scheme 13.

[0039] [ka]

[0040] Here, it is understood that the first step requires the reaction to be carried out in a solvent, and the solvent can be dichloromethane; It is also understood that the next two steps also require the reaction to be carried out in a solvent, which can be an ether.

[0041] The ligand can be reacted with a strong base compound to give a ligand salt, and the ligand salt can be reacted with MX4 to give a metallocene compound.

[0042] In some embodiments of the present application, the strong base compound is n-butyllithium, methyllithium, methylmagnesium chloride, and Benzylmagnesium chloride At least one of the following is selected from The strong base compound, when selected from the aforementioned materials, can further contribute to reacting the ligand with the strong base compound to form a ligand salt.

[0043] In some embodiments of the present application, the reaction scheme of the metallocene compound is shown in Equation 14.

[0044] [ka]

[0045] In some embodiments of the present application, during the preparation of the second compound, the diarylmethanol, the dihydropyran, and n-the molar ratio of butyllithium is (29.5-30.5):(59.5-60.5):(29.7-35.1), When the molar ratio of the second compound, the fifth compound, n-butyllithium, and hydrochloric acid during the preparation of the ligand is (4.3-5.2):(4.2-4.8):(4.5-5.2):(9.8-10.4), a higher purity ligand can be produced, which contributes to obtaining the metallocene compound of the present invention. The metallocene compound can be applied to both C6-C30 long linear α-olefin feedstocks and mixed long branched internal olefin feedstocks, and further, can obtain a polymerization product with a target molecular weight as required.

[0046] Furthermore, when the molar ratio of the ligand, the strong base compound, and MX4 is (3.8-4.4):(8.0-9.2):(3.9-4.5), the ligand salt can be more effectively produced, and the metallocene compound according to the present invention can be obtained by reacting the ligand salt with MX4.

[0047] In a third aspect, the present application provides a catalyst system comprising the metallocene compound described above.

[0048] It is understood that the metallocene compounds of the present application can be used in conjunction with other compounds, including cocatalysts, to form catalyst systems for catalyzing the polymerization of compounds such as olefins.

[0049] The catalyst system of the present invention, which contains the above-mentioned metallocene compound, can be applied to catalyze C6-C30 long linear α-olefin feedstocks, and can also be applied to mixed long branched internal olefin feedstocks, and can further produce polymerization products with target molecular weights as needed.

[0050] The technical solution of the present application will be further described below with reference to specific examples.

[0051] The specifications and sources of chemicals in the examples and comparative examples of this application are shown in Table 1. [Table 1] [Example]

[0052] The metallocene compound ligand according to this embodiment is Diphenylmethanol (5527 mg, 30 mmol) and 30 mL of dichloromethane were placed in a 100 mL round-bottom flask, p-toluenesulfonic acid (90 mg, 0.48 mmol) was added while stirring, and after 5 minutes of stirring, dihydropyran (5047 mg, 60 mmol) was added all at once, and after a few seconds, the reaction solution changed color from yellow to red. Potassium tert-butoxide (200 mg, 1.8 mmol) was immediately added to the reaction solution to quench the reaction, and the solvent and excess dihydropyran were evaporated under reduced pressure at 50°C. The product was extracted with 60 mL of pentane, filtered through diatomaceous earth, and the solvent was removed to obtain the product diphenylmethyl-2-tetrahydropyranyl ether (6912 mg, 27 mmol, 90.0%). Diphenylmethyl-2-tetrahydropyranyl ether (1342 mg, 5 mmol) was dissolved in 20 mL of ether, and 2 mL of n-butyllithium solution (2.5 M, 5.0 mmol) was slowly added to the solution at room temperature. After reacting for 2 hours, the reaction solution was slowly added to an ether solution (20 mL) containing 15 mmol of dichlorodimethylsilane at ice-water bath temperature. The temperature was raised to room temperature and the reaction was continued for 1 hour. The solvent and excess dichlorodimethylsilane were distilled off under reduced pressure, and the resulting solid was redissolved in 20 mL of ether and set aside for later use. Tetramethylcyclopentadiene (611 mg, 5.0 mmol) was dissolved in 20 mL of ether, and 2 mL of n-butyllithium solution (2.5 M, 5.0 mmol) was added to the solution. mL of ethyl acetate was slowly added at room temperature, and the reaction was allowed to proceed for 2 hours. Then, the reaction solution was slowly added to the ether solution at ice-water bath temperature, and the reaction was allowed to proceed overnight with stirring at room temperature. The reaction was then quenched with 50 mL of dilute hydrochloric acid (1N), and stirring was continued for 1 hour. The organic phase was separated, washed twice with 50 mL of distilled water, and dried over anhydrous magnesium sulfate. The solvent was then removed by rotary evaporation. The crude product was then purified by column chromatography (200 mesh silica gel for column chromatography, detergent (petroleum ether:dichloromethane=8:2)) to obtain tetramethylcyclopentadienyl-diphenylhydroxymethyl-dimethylsilane (1651 mg, 4.55 mmol, 91%), which is used as ligand b1. and b1 1 H NMR data (400MHz, CDCl3): δ=0.38(d,6H,Me2Si), 1.75(d,6H,Me4C5H), 1.96(s,6H,Me4C5H), 4.40(s,1H,HC5Me4), 4.69(s,1H,OH), 7.23(d,4H,Ph), 7.24(t,2H,Ph), 7.24(t,4H,Ph).

[0053] The metallocene compound according to this embodiment is b1 (1541 mg, 4.25 mmol) was dissolved in 50 mL of ether, and 3.4 mL of n-butyllithium solution (2.5 M, 8.50 mmol) was slowly added thereto at room temperature. The mixture was stirred and allowed to react overnight. The reaction mixture was then slowly added dropwise to an ether solution (20 mL) of titanium tetrachloride (806 mg, 4.25 mmol) at -20°C. The reaction mixture was then allowed to warm to room temperature and stirred overnight. The ether was evaporated under reduced pressure, and the reaction product was dissolved in 30 mL of dichloromethane. L, filtering insoluble matter, and adding about 20 mL of n-hexane to the solution until a precipitate begins to form, followed by slowly concentrating the solution to crystallize and separate out the product, filtering the product, and removing the solvent under vacuum to obtain metallocene compound a1 (dimethylsilyl-bridged-tetramethylcyclopentadienyl-[(diphenyl)-methoxy]-titanium dichloride) (896 mg, 1.87 mmol, 44%). a1 1 H NMR data (400MHz, CDCl3): δ=0.63(s,6H,Me2Si), 1.909(d,6H,Me4C5H), 1.910(s,6H,Me4C5H), 7.17(d,4H,Ph), 7.24(t,2H,Ph), 7.31(d,4H,Ph). [Example]

[0054] The method for preparing the metallocene compound ligand according to this embodiment is as follows: The diphenylmethanol in Example 1 was replaced with (p-methylphenyl)(phenyl)methanol to give the product (p-methylphenyl)(phenyl)methyl-2-tetrahydropyranyl ether (6793 mg, 25.16 mmol, 83.87%). The diphenylmethyl-2-tetrahydropyranyl ether in Example 1 was replaced with (p-methylphenyl)(phenyl)methyl-2-tetrahydropyranyl ether to obtain tetramethylcyclopentadienyl-[(p-methylphenyl)(phenyl)hydroxymethyl]-dimethylsilane (1680 mg, 4.45 mmol, 89%) as ligand b2; and b2 1This differs from Example 1 in that the H NMR data (400 MHz, CDCl): δ = 0.38 (s, 6H, MeSi), 1.75 (d, 6H, MeCH), 1.96 (s, 6H, MeCH), 2.35 (s, 3H, Me-Ph), 4.41 (m, 1H, HCMe), 4.69 (s, 1H, —OH), 7.13 (d, 2H, Ph-Me), 7.16 (d, 2H, Ph-Me), 7.22 (d, 2H, Ph), 7.23 (t, 1H, Ph), 7.33 (t, 2H, Ph).

[0055] The method for preparing the metallocene compound according to this embodiment includes the following steps: Ligand b1 is replaced with ligand b2 to give metallocene compound a2, dimethylsilyl-bridged tetramethylcyclopentadienyl-[(p-methylphenyl)(phenyl)methoxy]-titanium dichloride (994.16 mg, 2.003 mmol, 45%); and a2 1 This differs from Example 1 in that the H NMR data (400 MHz, CDCl): δ = 0.63 (s, 6H, MeSi), 1.91 (d, 6H, MeCH), 1.92 (s, 6H, MeCH), 2.35 (s, 3H, Me-Ph), 7.03 (s, 2H, Ph-Me), 7.13 (d, 2H, Ph-Me), 7.17 (d, 2H, Ph-Me), 7.23 (t, 1H, Ph), 7.33 (t, 2H, Ph). [Example]

[0056] The method for preparing the metallocene compound ligand according to this embodiment is as follows: The diphenylmethanol in Example 1 was replaced with (o-tolyl)(phenyl)methanol to give the product (o-tolyl)(phenyl)methyl-2-tetrahydropyranyl ether (6777 mg, 25.10 mmol, 83.67%). The diphenylmethyl-2-tetrahydropyranyl ether in Example 1 is replaced with (o-tolyl)(phenyl)methyl-2-tetrahydropyranyl ether, and the tetramethylcyclopentadiene in Example 1 is replaced with cyclopentadiene to obtain cyclopentadienyl-[(o-tolyl)(phenyl)hydroxymethyl]-dimethylsilane (1343 mg, 4.36 mmol, 87.2%) as ligand b3; and b3 1 This example differs from Example 1 in that the H NMR data (400 MHz, CDCl): δ = 0.33 (s, 6H, MeSi), 2.39 (d, 3H, Me-Ph), 3.20 (m, 2H, CH), 4.70 (s, 3H, OH), 6.32 (t, 2H, CH), 6.42 (t, 2H, CH), 7.15 (d, 1H, Ph-Me), 7.18 (d, 1H, Ph-Me), 7.20 (s, 1H, Ph-Me), 7.21 (s, 1H, Ph-Me), 7.23 (t, 1H, Ph), 7.30 (d, 2H, Ph), 7.33 (t, 2H, Ph).

[0057] The method for preparing the metallocene compound according to this embodiment includes the following steps: Ligand b1 is replaced with ligand b3 to give metallocene compound a3, dimethylsilyl-bridged cyclopentadienyl-[(o-tolyl)(phenyl)methoxy]-titanium dichloride (967 mg, 2.27 mmol, 52%); and a3 1 This differs from Example 1 in that the H NMR data (400 MHz, CDCl): δ = 0.57 (s, 6H, MeSi), 2.31 (d, 3H, Me-Ph), 6.51 (d, 2H, CH), 6.54 (t, 2H, CH), 7.05 (d, 1H, Ph-Me), 7.16 (d, 2H, Ph), 7.18 (d, 2H, Ph-Me), 7.20 (d, 1H, Ph-Me), 7.23 (t, 1H, Ph), 7.27 (d, 1H, Ph-Me), 7.31 (t, 3H, Ph). [Example]

[0058] The method for preparing the metallocene compound ligand according to this embodiment is as follows: The diphenylmethanol in Example 1 was replaced with (p-methylphenyl)(phenyl)methanol to give the product (p-methylphenyl)(phenyl)methyl-2-tetrahydropyranyl ether (6793 mg, 25.16 mmol, 83.87%). The diphenylmethyl-2-tetrahydropyranyl ether in Example 1 is replaced with (p-methylphenyl)(phenyl)methyl-2-tetrahydropyranyl ether, and the tetramethylcyclopentadiene in Example 1 is replaced with indene to obtain indenyl-[(p-methylphenyl)(phenyl)hydroxymethyl]-dimethylsilane (1422 mg, 4.18 mmol, 83.6%) as ligand b4; and b4 1 H NMR data (400MHz, CDCl3): δ=0.34(s,6H,Me2Si), 2.35(d,3H,Me-Ph), 4.12(d,1H,C3H3-C6H4) , 4.65(s,1H,OH), 6.45(t,1H,C3H3-C6H4), 6.68(d,1H,C3H3-C6H4), 7.13(d,2H,Ph-Me), 7.16 (d, 2H, Ph-Me), 7.22 (d, 2H, Ph), 7.23 (t, 1H, Ph), 7.28 (t, 1H, C6H4-C3H3), 7.32 (t, 1H, C6H4-C3H3), 7.33 (t, 2H, Ph), 7.34 (d, 1H, C6H4-C3H3), and 7.41 (t, 2H, C6H4-C3H3).

[0059] The method for preparing the metallocene compound according to this embodiment includes the following steps: Ligand b1 is replaced with ligand b4, and titanium tetrachloride is replaced with zirconium tetrachloride to give metallocene compound a4, dimethylsilyl-bridged-indenyl-(p-methylphenyl)(phenyl)methoxy-zirconium dichloride (1130 mg, 2.34 mmol, 56.0%); and A4 1H NMR data (400MHz, CDCl3): δ=0.63(s,6H,Me2Si), 2.35(s,3H,Me-Ph), 6.69(d,1H,C3H3-C6H4), 6.94(d,1H,C3H3-C6H4), 7.05(d,2H,Ph-Me), 7.14(d,2H,Ph-Me), 7.15(d,2H,Ph-Me), 7.23(t,1H,Ph), 7.27(t,1H,C6H4-C3H3), 7.31(t,2H,Ph), This example differs from Example 1 in that the values ​​are 7.36 (d, 1H, C6H4-C3H3), 7.3 (d, 1H, C6H4-C3H3), and 7.39 (t, 1H, C6H4-C3H3). [Example]

[0060] The method for preparing the metallocene compound ligand according to this embodiment is as follows: The diphenylmethanol in Example 1 was replaced with (p-methylphenyl)(phenyl)methanol to give the product (p-methylphenyl)(phenyl)methyl-2-tetrahydropyranyl ether (6793 mg, 25.16 mmol, 83.87%). The diphenylmethyl-2-tetrahydropyranyl ether in Example 1 is replaced with (p-methylphenyl)(phenyl)methyl-2-tetrahydropyranyl ether, and the tetramethylcyclopentadiene in Example 1 is replaced with fluorene to obtain fluorenyl-[(p-methylphenyl)(phenyl)hydroxymethyl]-dimethylsilane (1769 mg, 4.24 mmol, 84.8%) as ligand b5; and b5 1 H NMR data (400MHz, CDCl3): δ=0.45(s,6H,Me2Si), 2.35(s,3H,Me-Ph), 4.57(d,1H,OH), 5.31(s,1H,C 13 H9), 7.13(d,2H,Ph-Me), 7.15(d,2H,Ph-Me), 7.24(t,1H,Ph), 7.33(t,2H,Ph), 7.35(t,2H,C 13 H9), 7.40(t,2H,C 13 H9), 7.55(d,2H,C 13H9), 7.73(d,2H,C 13 H9) is different from Example 1.

[0061] The method for preparing the metallocene compound according to this embodiment includes the following steps: Ligand b1 is replaced with ligand b5, and titanium tetrachloride is replaced with zirconium tetrachloride to give metallocene compound a5, dimethylsilyl-bridged fluorenyl-[(p-methylphenyl)(phenyl)methoxy]-zirconium dichloride (1250 mg, 2.15 mmol, 50.7%); and A5 1 H NMR data (400MHz, CDCl3): δ=0.57(s,6H,Me2Si), 2.35(s,3H,Me-Ph), 7.06(d,2H,Me-Ph), 7.13(d,2H,C 13 H9), 7.15(d,2H,Ph-Me), 7.16(d,2H,Ph), 7.24(t,1H,Ph), 7.30(t,2H,C 13 H9), 7.31(t,2H,Ph), 7.36(t,2H,C 13 H9), 7.51(t,2H,C 13 H9) is different from Example 1. [Example]

[0062] The preparation method of the metallocene compound ligand of this example is the same as that of Example 2.

[0063] The method for preparing the metallocene compound according to this embodiment includes the following steps: Ligand b1 is replaced with ligand b2 and titanium tetrachloride is replaced with zirconium tetrachloride to give metallocene compound a6, dimethylsilyl-bridged tetramethylcyclopentadienyl-[(p-methylphenyl)(phenyl)methoxy]-zirconium dichloride (1090 mg, 2.08 mmol, 44.8%); and Dimethylsilyl-bridged tetramethylcyclopentadienyl-[(p-methylphenyl)(phenyl)methoxy]-zirconium dichloride 1The H NMR data (400 MHz, CDCl): δ = 0.67 (s, 6H, MeSi), 1.84 (d, 6H, MeC), 1.92 (s, 6H, MeC), 2.35 (s, 3H, Me-Ph), 7.05 (d, 2H, Ph-Me), 7.14 (d, 2H, Ph-Me), 7.16 (d, 2H, Ph), 7.24 (t, 1H, Ph), 7.33 (t, 2H, Ph). [Example]

[0064] The preparation method of the metallocene compound ligand of this example is the same as that of Example 5.

[0065] The method for preparing the metallocene compound according to this embodiment includes the following steps: Ligand b1 is replaced by ligand b5 and titanium tetrachloride is replaced by HfCl4 to give metallocene compound a7, dimethylsilyl-bridged fluorenyl-[(p-methylphenyl)(phenyl)methoxy]-zirconium dichloride (1090 mg, 2.08 mmol, 44.8%); and a7 1 H NMR data (400MHz, CDCl3): δ=0.69(s,6H,Me2Si), 2.35(s,3H,Me-Ph), 7.04(d,2H,Ph-Me), 7.14(d,2H,Ph-Me), 7.15(d,2H,C 13 H8), 7.18(d,2H,Ph), 7.21(t,1H,Ph), 7.31(t,2H,Ph), 7.33(t,2H,C 13 H8), 7.36(d,2H,C 13 H8), 7.51(t,2H,C 13 H8) is different from Example 1.

[0066] [ka]

[0067] Test Example Test Example 1 The polymerization reaction of 1-decene was catalyzed using the metallocene compounds according to Examples 1 to 7, 2,4-di-tert-butyl-6-(2,3,4,5-tetramethylcyclopentadienyl)phenoxytitanium dichloride (Comparative Example 1), (4,6-di-tert-butyl-9-fluorenyl)phenoxytitanium dichloride (Comparative Example 2), (3,4-diphenyl-6-cyclopentadienyl)phenoxy]titanium dichloride (Comparative Example 3), and rac-vinylbis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride (Comparative Example 4), respectively. A 300 mL stainless steel polymerization reactor equipped with a magnetic stirrer was heated to 90°C and evacuated for 1 hour. 150 mL of 1-decene liquid containing 0.4 mL of triisobutylaluminum was then added. 10 mL of a toluene solution containing 5 mg of Ph3CB(CF5)4 and 2 mg of catalyst was then added to the reactor, and the reaction temperature was controlled at 90°C. The reaction was continued for 1.5 hours with stirring. 2 mL of absolute ethanol was then added to the reactor to terminate the reaction. The product was then separated from the crude product under normal pressure and reduced pressure to separate the toluene, monomer, and dimer to obtain the final polymerization product. The process includes testing the catalytic activity of the catalyst, the yield of the polymerization product, the conversion of 1-decene, the weight-average molecular weight of the obtained polymerization product, the kinematic viscosity at 100°C, the viscosity index, and the pour point. The test results are shown in Table 2.

[0068] Here, the conversion rate of 1-decene=(mass of 1-decene before the reaction−mass of 1-decene after the reaction) / mass of 1-decene before the reaction×100%. Yield of polymerization product = (mass of 1-decene before reaction - mass of 1-decene after reaction - mass of dimer after reaction) / mass of 1-decene before reaction × 100%, Catalytic activity of catalyst = (total mass of reaction products) / number of moles of catalyst / catalytic time / number of active sites. Here, the number of active sites of a metallocene compound is 1, The kinematic viscosity of the polymerization product is measured according to the GB / T256-1988 method: the kinematic viscosity of the obtained polymerization product sample at 40°C and 100°C is measured using a SYP1003V1 kinematic viscometer, and its viscosity index is calculated according to the conversion relationship between viscosity and viscosity index (using the ASTM D2270 method); The pour point of the polymerization product is tested according to the method of GB / T3535-83(91). The weight average molecular weight of the polymerization product is measured according to GB / T 27843-2011.

[0069] [Table 2]

[0070] As can be seen from Table 2, when the metallocene compounds prepared in the examples of the present application were used to catalyze the polymerization reaction of 1-decene, the conversion rate of 1-decene was high, the activity of the metallocene compounds was high, the yield of the obtained product was high, and the molecular weight of the obtained product was high.

[0071] The polymerization reaction of 1-decene was catalyzed by the metallocene compound of Example 1. Polymer NMR FIG. 1 shows the nuclear magnetic resonance hydrogen spectrum (H spectrum) of the polymerization product obtained by catalyzing the polymerization reaction of 1-decene using the metallocene compound according to Example 1 of the present application. 1 1H NMR), and as can be seen from Figure 1, From polymerization products Toluene, 1-decene, and dimer After separation The polymerization product obtained in 1 In the H NMR spectrum, the chemical shift value of the olefin double bond was δ = 4.6 to 4.8 ppm, which indicated that the olefin terminal was vinylidene, proving that the insertion method of 1-decene during the polymerization reaction was 1,2-insertion.

[0072] Test Example 2 The polymerization reaction of the mixed decene liquid was catalyzed using the metallocene compound of Example 1, 2,4-di-tert-butyl-6-(2,3,4,5-tetramethylcyclopentadienyl)phenoxytitanium dichloride (Comparative Example 1), (4,6-di-tert-butyl-9-fluorenyl)phenoxytitanium dichloride (Comparative Example 2), (3,4-diphenyl-6-cyclopentadienyl)phenoxy]titanium dichloride (Comparative Example 3), and rac-vinylbis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride (Comparative Example 4) as catalysts, respectively. A 300 mL stainless steel polymerization reactor equipped with a magnetic stirrer was heated to 70 °C, evacuated for 1 h, and purged with N2 2 to 3 times. Then, a mixed decene liquid containing 0.4 mL of triisobutylaluminum was obtained (the composition of the mixed decene was 30.99% 1-decene, 2.35% cis-4-decene, 8.60% trans-4-decene, 19.43% 4-ethyl-1-octene, 22.83% 3-propyl-1-heptene, 12.26% 2-butyl-1-hexene, and 5-methyl-1-nonene). 100 mL of toluene solution containing 45 mg of Ph3CB(CF6F5) and 2.2 mg of catalyst was added to the reactor, and the reaction temperature was controlled at 60°C. After stirring for 1.5 hours, 5 mL of absolute ethanol was added to the reactor to terminate the reaction and obtain the product. The crude product was separated under normal pressure and reduced pressure to obtain the final polymerization product, which contained ethanol, toluene, monomers (mixed decene), and dimers. The process includes testing the catalytic activity of the catalyst, the yield of the polymerization product, the conversion rate of mixed decene, the weight-average molecular weight of the obtained polymerization product, the kinematic viscosity at 100°C, the viscosity index, and the pour point. The test results are shown in Table 3. For the test methods, see the test methods in Test Example 1.

[0073] [Table 3]

[0074] As can be seen from Table 3, when the metallocene compounds prepared in the examples of the present application are used to catalyze the polymerization reaction of a decene mixture, the conversion of decene is high, the activity of the metallocene compounds is high, and the yield of the resulting product is high.

[0075] Each embodiment in this specification is described in relation to one another, and the same or similar parts between the embodiments may be referred to, and each embodiment is described by focusing on the differences from other embodiments. The above are only preferred embodiments of the present application and are not intended to limit the scope of protection of the present application. All modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present application shall be included in the scope of protection of the present application.

[0076] This application claims priority from a Chinese patent application bearing application number 202211178402.1 and entitled "Metallocene Compounds, Preparation Methods and Uses," filed with the China Patent Office on September 26, 2022, the entire contents of which are incorporated herein by reference.

Claims

1. A metallocene compound having a structure shown in formula a: 【Chemistry 1】 During the ceremony, Ar is selected from substituted or unsubstituted C6-C30 aryl; Cp' is selected from substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl; X is selected from at least one of halogen, substituted or unsubstituted C1-C30 alkyl, alkoxy, substituted or unsubstituted C2-C30 dialkylamino, alkenyl, and substituted or unsubstituted C6-C30 aryl; M is selected from Ti, Zr or Hf; Metallocene compounds.

2. 2. The metallocene compound according to claim 1, wherein the substituent of the C6-C30 aryl in Ar is at least one selected from the group consisting of methyl, ethyl, methylene, isopropyl, vinyl, propenyl, and butenyl.

3. 2. The metallocene compound according to claim 1, wherein in Cp', a substituent of cyclopentadienyl, indenyl, or fluorenyl is at least one selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and phenyl.

4. 2. The metallocene compound according to claim 1, wherein the substituent of the C1-C30 alkyl, C1-C30 alkoxy, C2-C30 dialkylamino, C2-C30 alkenyl, or C6-C30 aryl in X is at least one selected from methyl, ethyl, methylene, isopropyl, vinyl, propenyl, and butenyl.

5. The metallocene compound according to claim 1, wherein the metallocene compound is a compound represented by any one of the following structural formulas: 【Chemistry 2】

6. A method for preparing the metallocene compound according to any one of claims 1 to 5, comprising the steps of: adding a diarylmethanol with a dihydropyran in the presence of p-toluenesulfonic acid to form a first compound; reacting the first compound with n-butyllithium, and then adding dichlorodimethylsilane to the system to obtain a second compound; reacting the second compound with a third compound to obtain a fourth compound, and reacting the fourth compound with hydrochloric acid to obtain a ligand; reacting the ligand with a strong base compound to obtain a ligand salt; The ligand salt is MX ４ to obtain the metallocene compound, wherein the third compound is obtained by reacting the fifth compound with n-butyllithium; The fifth compound is at least one selected from the group consisting of substituted or unsubstituted cyclopentadiene, indene, and fluorene.

7. 7. The method according to claim 6, wherein the strong base compound is at least one selected from the group consisting of n-butyllithium, methyllithium, methylmagnesium chloride, and benzylmagnesium chloride.

8. During the preparation of the second compound, the diarylmethanol, dihydropyran, and n-butyllithium were in a molar ratio of (29.5-30.5):(59.5-60.5):(29.7-35.1); and / or the preparation method according to claim 6, wherein during the preparation of the ligand, the second compound, the fifth compound, n-butyllithium, and hydrochloric acid are present in a molar ratio of (4.3-5.2):(4.2-4.8):(4.5-5.2):(9.8-10.4).

9. Ligand, Strong Base Compound, and MX ４ The method according to claim 6, wherein the molar ratio of is (3.8-4.4):(8.0-9.2):(3.9-4.5).

10. A catalyst system comprising the metallocene compound according to any one of claims 1 to 5.

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