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 compound catalyst technology, and in particular to metallocene compounds and their preparation and use. [Background technology]

[0002] The preparation of metallocene compounds and the catalysis of olefin polymerization reactions by metallocene compounds have traditionally been one of the hot spots of chemical research.

[0003] In 1990, U.S. Pat. No. 6,548,686 described a method for preparing transition metal compounds having 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) by employing a "one-pot synthesis" method in 1997. This type of catalyst is mainly 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), and then added and reacted with an appropriate alkyllithium or Grignard reagent to obtain a type of metallocene catalyst with restricted geometry containing 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] Professor Mu Ying disclosed a kind of metallocene catalyst (see formula 6) with restricted geometric structure containing phenoxy side chain in China Patent Publication No. 101130467 in 2007. The catalyst adopts alkylaluminum and boron compound as cocatalyst, and can catalyze C6-C20 linear α-olefin to obtain colorless and transparent oil. The product has high viscosity, high viscosity index and low pour point, so it can be used as lubricant base oil. However, the coordination environment of the active center of this kind of catalyst is too open, so the produced polymer has low molecular weight.

[0007] In 2008, Mu Ying’s research team also reported the development of metallocene catalysts with restricted geometric shapes that contain a single carbon atom bridging aryloxy group (see formula 7, where R1 is H(1), Me(2) or t Bu(3,4), R2 is H(2,3) or t The catalyst can be used to catalyze the preparation of medium molecular weight polyethylene by polymerization of ethylene 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 geometrically restricted titanium metal catalysts (see formulas 8 to 11). In formula 8, R is Me and Et, respectively; in formula 9, R is Me and Et, respectively; in formula 10, R is Me and Et, respectively; 1 is selected from H or Me, 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 a high molecular weight copolymer, and ensure a high insertion rate of 1-hexene at the same time.

[0009] Based on this, Hidenori Hanaoka et al. introduced fluorenyl into the phenoxy-metal system to produce a new metallocene catalyst (see formula 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. The metallocene catalyst can maximize the activity of copolymerization of ethylene and 1-hexene.

[0010] [ka]

[0011] However, the metallocene compounds having the above structural formula have limitations in either the raw material or the product, for example, they are only applicable to catalyzing the polymerization reaction of linear olefins having 6 or less carbon atoms, and cannot be applied to catalyzing the polymerization reaction of linear olefins having more than 6 carbon atoms, or to catalyzing the polymerization reaction of branched olefins having 6 or more carbon atoms. In addition, when the 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 metallocene compounds that can catalyze long linear α-olefin feedstocks and mixed long branched internal olefin feedstocks with high efficiency, and can provide polymerization products having target molecular weights as required.

[0013] The present application provides a method for preparing a metallocene compound, which can prepare a metallocene compound that is applied to catalyze long linear α-olefin feedstock and mixed long branched internal olefin feedstock with high efficiency, and can also obtain a polymerization product of the metallocene compound having a target molecular weight as required.

[0014] The present application provides a catalyst system, which can be applied to catalyze C6-C30 long linear α-olefin feedstocks and mixed long branched internal olefin feedstocks, and can obtain 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, a substituted or unsubstituted C1-C30 alkyl, an alkoxy, a substituted or unsubstituted C2-C30 dialkylamino, an alkenyl, 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 Ar is a C6-C30 aryl group, the substituents are methyl, ethyl, methylene, isopropyl, vinyl, propenyl, and butenyl. At least one selected from .

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

[0018] For the metallocene compounds as described above, wherein 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 selected from .

[0019] Regarding 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 the diarylmethanol with 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 said ligand salt with MX4 to obtain said 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 selected from .

[0021] Regarding the above-mentioned preparation method, the strong base compound is n-butyl lithium, methyl lithium, methyl magnesium chloride, and Benzylmagnesium chloride At least one selected from .

[0022] Regarding the above-mentioned preparation method, in which during the preparation of the second compound, diarylmethanol, dihydropyran, and n- The 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 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 base compound, and MX4 are 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. Effect of the Invention

[0025] The metallocene compound according to the present invention has a structure shown in formula a, and the metallocene compound is a silicon-carbon-oxygen bridged heteroatom compound with restricted geometric structure. The metal center of the metallocene compound contains a 5-membered chelate ring, and at the same time, two aromatic groups with large steric hindrance are bonded to the bridged carbon atom. As a result, the coordination space environment is more crowded, the thermal stability of the metallocene compound is greatly improved, and the metallocene compound exhibits special high activity catalytic performance under high temperature conditions, has high tolerance to impurities, and has a long catalytic life, so that the metallocene compound can be applied to catalyze C6-C30 long linear α-olefin feedstock and mixed long branched internal olefin feedstock, and can obtain polymerization products with target molecular weight as required.

[0026] 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 mixed long branched internal olefin feedstocks, and can obtain 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 some embodiments of the present application, and those skilled in the art can think of other drawings based on these drawings without creative efforts. [Brief description 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 the metallocene compound according to Example 1 of the present application. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[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 based on the embodiments of the present application without creative work, all belong to the protection scope 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, a substituted or unsubstituted C1-C30 alkyl, an alkoxy, a substituted or unsubstituted C2-C30 dialkylamino, an alkenyl, 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., A phenyl group, a biphenyl group, a substituted phenyl group, or a substituted biphenyl group (can be When Cp' is selected from substituted cyclopentadienyl, substituted indenyl, or substituted fluorenyl, the substituent may be one or more, for example, the substituent may be one methyl or two methyl, 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 compound with restricted geometric structure of heteroatoms bridged by silicon-carbon-oxygen, the metal center of the metallocene compound contains a 5-membered chelate ring, and at the same time, two aromatic groups with large steric hindrance are bonded to the bridge carbon atom, so that the coordination space environment is more crowded, the thermal stability of the metallocene compound is greatly improved, it shows special high activity catalytic performance under high temperature conditions, has high resistance to impurities, and has a long catalyst life, so that the metallocene compound can be applied to both long linear α-olefin raw materials and long branched internal olefin raw materials, and can obtain polymerization products with target molecular weights as required. For example, it can be applied to the polymerization reaction of linear olefins with more than 6 carbon atoms, and the polymerization reaction of branched olefins with 6 or more carbon atoms, and can obtain 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 are methyl, ethyl, methylene, isopropyl, vinyl, propenyl, and butenyl. At least one selected from .

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

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

[0037] In a second aspect, the present application provides a method for preparing a metallocene compound as described above, the method comprising the steps of: reacting the diarylmethanol with 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 selected from .

[0038] In the present application, the ligand is reacting 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-butyl lithium to obtain a third compound (Cp'HLi), which is then reacted with a second compound (c) to obtain a fourth compound (d), and finally the fourth compound (d) is reacted with hydrochloric acid to obtain the ligand. The specific reaction formula is shown in Formula 13.

[0039] [ka]

[0040] Here, it is understood that the first step requires the reaction to be carried out in a solvent, which 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-butyl lithium, methyl lithium, methyl magnesium chloride, and Benzylmagnesium chloride At least one selected from The strong base compound, when selected from those previously mentioned, 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, the diarylmethanol, dihydropyran, and n-The molar ratio of butyllithium is (29.5-30.5):(59.5-60.5):(29.7-35.1), During the preparation of the ligand, when the molar ratio of the second compound, the fifth compound, n-butyl lithium and hydrochloric acid 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, which can be applied to both C6-C30 long linear α-olefin feedstock and mixed long branched internal olefin feedstock, and 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 produced more effectively, and the metallocene compound according to the present application 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 will be 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 obtain polymerization products with target molecular weights as required.

[0050] The technical solutions of the present application are 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] EXAMPLES

[0052] The metallocene compound ligand according to this embodiment is Diphenylmethanol (5527 mg, 30 mmol) and 30 mL of dichloromethane are placed in a 100 mL round-bottom flask, p-toluenesulfonic acid (90 mg, 0.48 mmol) is added while stirring, and after 5 minutes of stirring, dihydropyran (5047 mg, 60 mmol) is quickly added all at once, after a few seconds the reaction solution changes from yellow to red, potassium tert-butoxide (200 mg, 1.8 mmol) is immediately added to the reaction solution to quench the reaction, the solvent and excess dihydropyran are evaporated under reduced pressure at 50° C., the product is extracted with 60 mL of pentane, filtered through diatomaceous earth, and the product diphenylmethyl-2-tetrahydropyranyl ether (6912 mg, 27 mmol, 90.0%) is obtained by removing the solvent; 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 thereto 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, and the reaction was continued for 1 hour after warming to room temperature. The solvent and excess dichlorodimethylsilane were distilled off under reduced pressure, and the obtained solid was redissolved in 20 mL of ether and set aside for later use. Then, 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 thereto. 50 mL of distilled water was added slowly at room temperature and reacted for 2 hours, then the reaction solution was added slowly to the above 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 then separated and washed twice with 50 mL of distilled water. The organic phase was then dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation. The crude product was then separated and 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%) as ligand b1; The method includes the steps of: 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 reacted overnight, and then the reaction mixture was 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 naturally 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 insolubles, and adding about 20 mL of n-hexane to the solution until precipitation begins, followed by slow concentration to crystallize and precipitate the product, filtering the product, and vacuuming the solvent 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). EXAMPLES

[0054] The method for preparing the metallocene compound ligand according to this embodiment includes the following steps: 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 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, CDCl3): δ = 0.38 (s, 6H, Me2Si), 1.75 (d, 6H, Me4C5H), 1.96 (s, 6H, Me4C5H), 2.35 (s, 3H, Me-Ph), 4.41 (m, 1H, HC5Me4), 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 steps of: Ligand b1 is replaced by 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, CDCl3): δ = 0.63 (s, 6H, Me2Si), 1.91 (d, 6H, Me4C5H), 1.92 (s, 6H, Me4C5H), 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). EXAMPLES

[0056] The method for preparing the metallocene compound ligand according to this embodiment includes the following steps: 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 H NMR data (400 MHz, CDCl3): δ = 0.33 (s, 6H, Me2Si), 2.39 (d, 3H, Me-Ph), 3.20 (m, 2H, C5H4), 4.70 (s, 3H, OH), 6.32 (t, 2H, C5H5), 6.42 (t, 2H, C5H5), 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 steps of: Ligand b1 is replaced by 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, CDCl3): δ = 0.57 (s, 6H, Me2Si), 2.31 (d, 3H, Me-Ph), 6.51 (d, 2H, C5H4), 6.54 (t, 2H, C5H4), 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). EXAMPLES

[0058] The method for preparing the metallocene compound ligand according to this embodiment includes the following steps: 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 by (p-methylphenyl)(phenyl)methyl-2-tetrahydropyranyl ether, and the tetramethylcyclopentadiene in Example 1 is replaced by 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 steps of: Ligand b1 is replaced by ligand b4 and titanium tetrachloride is replaced by 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 differs from Example 1 in that the eqs are 7.36 (d, 1H, C6H4-C3H3), 7.3 (d, 1H, C6H4-C3H3), and 7.39 (t, 1H, C6H4-C3H3). EXAMPLES

[0060] The method for preparing the metallocene compound ligand according to this embodiment includes the following steps: 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 by (p-methylphenyl)(phenyl)methyl-2-tetrahydropyranyl ether, and the tetramethylcyclopentadiene in Example 1 is replaced by 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 steps of: Ligand b1 is replaced by ligand b5 and titanium tetrachloride is replaced by 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. EXAMPLES

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

[0063] The method for preparing the metallocene compound according to this embodiment includes the steps of: Ligand b1 is replaced by ligand b2 and titanium tetrachloride is replaced by 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, CDCl3): δ = 0.67 (s, 6H, Me2Si), 1.84 (d, 6H, Me4C5), 1.92 (s, 6H, Me4C5), 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). EXAMPLES

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

[0065] The method for preparing the metallocene compound according to this embodiment includes the steps of: 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). A 300mL stainless steel polymerization reactor equipped with a magnetic stirrer is heated to 90°C, evacuated for 1 hour, and 150mL of 1-decene liquid containing 0.4mL of triisobutylaluminum is added, and 10mL of toluene solution containing 5mg of Ph3CB(C6F5)4 and 2mg of catalyst is added to the reactor, and the reaction temperature is controlled at 90°C and stirred for 1.5 hours. Then, 2mL of anhydrous ethanol is added to the reactor to terminate the reaction and obtain the product. The above crude product is separated into toluene, monomer, and dimer under normal pressure and reduced pressure 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 reaction−mass of 1-decene after reaction) / mass of 1-decene before 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 the 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 are used to catalyze the polymerization reaction of 1-decene, the conversion rate of 1-decene is high, the activity of the metallocene compound is high, the yield of the obtained product is high, and the molecular weight of the obtained product is 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 ( 1 1 H NMR), as can be seen in Figure 1. From the polymerization product 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=4.6-4.8 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 according to 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. 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 (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 19.43% 5-methyl-1-nonene) was obtained. 100mL of toluene solution containing 45mg of Ph3CB(C6F5) and 2.2mg of catalyst was added to the reactor, the reaction temperature was controlled at 60℃, and the reaction was carried out with stirring for 1.5 hours. Then, 5mL of anhydrous ethanol was added to the reactor to terminate the reaction and obtain the product. The above crude product was subjected to normal and reduced pressure to separate ethanol, toluene, monomer (mixed decene), 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 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 method, see the test method 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 compound is high, and the yield of the obtained product is high.

[0075] Each embodiment in this specification is described in relation to each other, and the same or similar parts between each embodiment may be referred to each other, and each embodiment is described by focusing on the differences from other embodiments. 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. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present application shall be included in the scope of protection of the present application.

[0076] This application claims priority to a Chinese patent application entitled "Metallocene Compounds, Preparation Methods and Use", filed with the China Patent Office on September 26, 2022, bearing application number 202211178402.1, 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, or substituted or unsubstituted C6-C30 aryl; M is a transition metal element; Metallocene compounds.

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

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

4. The metallocene compound according to any one of claims 1 to 3, wherein in X, the substituent of C1-C30 alkyl, C1-C30 alkoxy, C2-C30 dialkylamino, C2-C30 alkenyl, or C6-C30 aryl is selected from at least one of methyl, ethyl, methylene, isopropyl, vinyl, propenyl, and butenyl.

5. The metallocene compound according to any one of claims 1 to 4, wherein the structural formula of the metallocene compound comprises: 【Chemistry 2】

6. A process for preparing the metallocene compound according to any one of claims 1 to 5, comprising the steps of: 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; 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 method of preparing the fifth compound is selected from one of substituted or unsubstituted cyclopentadiene, indene, or fluorene.

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

8. During the preparation of the second compound, the diarylmethanol, the dihydropyran, and the first n-butyllithium are in 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 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 any one of claims 6 to 8, 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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