A metallocene compound ligand, its preparation method and application

Abstract

This invention provides a metallocene compound ligand, its preparation method, and its applications. The metallocene compound ligand of this invention has the structure shown in formula b: wherein Ar is selected from substituted or unsubstituted C6-C30 aryl groups; and Cp′ is selected from substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl groups. The metallocene compounds synthesized using this ligand are suitable for catalyzing C6-C30 long-chain α-olefins and mixed long-branched intra-olefin feedstocks.

Description

Technical Field

[0001] This invention relates to the field of metallocene compound catalysis technology, and particularly to a metallocene compound ligand, its preparation method, and its application. Background Technology

[0002] The preparation of metallocene compounds and their application in catalyzing olefin polymerization has long been a hot topic in chemical research.

[0003] In 1990, US6548686 B2 disclosed a method for preparing and using a class of compounds with transition metal restricted geometry. The structure of the compounds is shown in Formula 1. These compounds can be used to catalyze the polymerization or copolymerization of short-chain olefins such as ethylene, propylene, butene, butadiene, and 1-hexene.

[0004] In 1997, Marks designed and synthesized two metallocene catalysts with restricted geometries containing phenoxy side chains using a one-pot method (see Formulas 2 and 3). These catalysts are mainly used for 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 appropriate alkyllithium or Grignard reagents to react and obtain a class of metallocene catalysts with restricted geometry containing propoxy side chains (see Formula 5, where R is selected from H, Ph, SiMe3 and CMe3). This type of catalyst is mainly used to catalyze propylene polymerization.

[0006] In 2008, Mu Ying's research group designed a single-carbon atom-bridged metallocene catalyst with a restricted geometry containing aryloxy groups (see Equation 6, where R1 is selected from H(1), Me(2), or...). t Bu(3,4); R2 is selected from H(2) or t Bu(1,4)) is a catalyst that can be used to catalyze the polymerization of ethylene to prepare medium molecular weight polyethylene, or to catalyze the copolymerization of ethylene and 1-hexene to prepare medium molecular weight ethylene-1-hexene copolymers.

[0007] In 2009, Hidenori Hanaoka designed and synthesized a series of novel confined geometry titanium catalysts (see Equations 7-10, where R in Equation 7 represents Me and Et respectively; in Equation 8, R represents Me and Et respectively; and in Equation 9, R...). 1 Selected from H or Me, R 2 Selected from Me and Et; in Formula 10, R represents Me and H respectively. This catalyst is mainly used for copolymerization of ethylene and 1-hexene, which can effectively improve polymerization activity, produce high molecular weight copolymers, and ensure a high insertion rate of 1-hexene.

[0008] Building on this, in 2010, Hidenori Hanaoka et al. introduced fluorene into the phenoxy-metal system to prepare a new metallocene catalyst (see Formula 11, where M is selected from Ti, Zr, or Hf; R...). 1 Selected from H or t Bu;R 2 Selected from Me or Et; X selected from NMe2 or Cl), this metallocene catalyst can greatly enhance the activity of copolymerization of ethylene and 1-hexene.

[0009]

[0010] However, metallocene compounds, including the above-mentioned structural formulas, have limitations on both raw materials and products. For example, they can only be used to catalyze the polymerization of straight-chain olefins with 6 or fewer carbon atoms, but cannot be used to catalyze the polymerization of straight-chain olefins with more than 6 carbon atoms, nor can they be used to catalyze the polymerization of branched olefins with more than 6 carbon atoms. Summary of the Invention

[0011] The present invention provides a metallocene compound ligand, and metallocene compounds including the metallocene compound ligand are suitable for catalyzing C6-C30 long straight-chain α-olefin feedstocks and mixed long branched intra-olefin feedstocks.

[0012] This invention provides a metallocene compound that is suitable for catalyzing long straight-chain α-olefin feedstocks and mixed long branched intra-olefin feedstocks.

[0013] This invention provides a method for preparing metallocene compound ligands, which can prepare the aforementioned metallocene compound ligands.

[0014] This invention provides a method for preparing metallocene compounds, wherein the ligands synthesized by the above method can be used to prepare the aforementioned metallocene compounds.

[0015] This invention provides a catalyst system that can catalyze the polymerization reaction of C6-C30 long-chain α-olefins with mixed long-branched intraolefin feedstocks.

[0016] This invention provides a metallocene compound ligand having the structure shown in formula b:

[0017]

[0018] Ar is selected from substituted or unsubstituted C6-C30 aryl groups;

[0019] Cp′ is selected from substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, or substituted or unsubstituted fluorenyl.

[0020] The metallocene compound ligands described above, wherein the substituents of the C6-C30 aryl group in Ar are selected from at least one of methyl, ethyl, methylene, isopropyl, vinyl, propenyl, and butenyl groups;

[0021] In Cp', the substituents of cyclopentadienyl, indenyl, or fluorenyl are selected from at least one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or phenyl.

[0022] The metallocene compound ligands described above, wherein the metallocene compound ligands have a structure shown in any of formulas b1-b5:

[0023]

[0024] The present invention provides a metallocene compound, wherein the metallocene compound ligand described above is included.

[0025] The metallocene compounds described above, wherein the structure is shown in formula a:

[0026]

[0027] Wherein, X is a halogen, and at least one of the following: substituted or unsubstituted C1-C30 alkyl, C1-C30 alkoxy, C2-C30 dialkylamino, C2-C30 alkenyl, or C6-C30 aryl;

[0028] M is a transition metal element.

[0029] In the metallocene compounds described above, wherein in X, the substituents of C1-C30 alkyl, C1-C30 alkoxy, C2-C30 dialkylamino, C2-C30 alkenyl, or C6-C30 aryl are at least one selected from methyl, ethyl, methylene, isopropyl, vinyl, propenyl, and butenyl.

[0030] The metallocene compounds described above, wherein the metallocene compounds have a structure shown in any one of formulas a1-a6:

[0031]

[0032] This invention provides a method for preparing the metallocene compound ligand as described above, comprising the following steps:

[0033] Diarylethanol undergoes an addition reaction with dihydropyran in the presence of p-toluenesulfonic acid to generate the first compound.

[0034] The first compound was reacted with n-butyllithium, and then tetramethyldichlorodisilane was added to the system to react and give the second compound.

[0035] The second compound is reacted with the third compound to give the fourth compound, and the fourth compound is reacted with hydrochloric acid to give the ligand;

[0036] The third compound is obtained by reacting the fifth compound with n-butyllithium;

[0037] The fifth compound is selected from one of substituted or unsubstituted cyclopentadiene, indene, or fluorene.

[0038] This invention provides a method for preparing metallocene compounds, comprising the following steps:

[0039] The metallocene compound is obtained by reacting the ligand salt with MX4.

[0040] The ligand salt is obtained by reacting the ligand with a strong basic compound as described above.

[0041] The present invention provides a catalyst system comprising the aforementioned metallocene compound.

[0042] The metallocene compound ligand of the present invention has the structure shown in Formula b. This metallocene compound ligand can yield a metallocene compound with a silicon-silicon-carbon-oxygen heteroatom-restricted geometry. The metal center of this metallocene compound contains a six-membered chelate ring, and two large sterically hindered aromatic groups are attached to the two silicon atoms, making its coordination space more crowded. This greatly improves the thermal stability of the metallocene compound, exhibiting special high-activity catalytic performance under high temperature conditions, high resistance to impurities, and long catalytic lifetime. This compound is suitable for catalyzing the polymerization reaction of C6-C30 long straight-chain α-olefins and mixed long-branched intra-olefins.

[0043] The method for preparing metallocene compound ligands of the present invention can prepare metallocene compound ligands with the above-mentioned structure, and the preparation method is simple and suitable for widespread application and promotion.

[0044] The method for preparing metallocene compounds of the present invention can prepare metallocene compounds with the above-mentioned structure, and the preparation method is simple and suitable for widespread application and promotion.

[0045] The catalyst system of the present invention includes the above-mentioned metallocene compounds, and is therefore suitable for catalyzing the polymerization reactions of C6-C30 long straight-chain α-olefins and mixed long branched olefins. Attached Figure Description

[0046] To more clearly illustrate the technical solutions in the embodiments of the present invention or related technologies, the accompanying drawings used in the description of the embodiments of the present invention or related technologies are briefly introduced below. Obviously, the drawings described below are merely some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0047] Figure 1 This is a molecular weight distribution diagram of the polymer product obtained by the polymerization reaction of 1-decene catalyzed by metallocene compounds in Example 1 of the present invention. Detailed Implementation

[0048] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions in the embodiments of this invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0049] A first aspect of the present invention provides a metallocene compound ligand having the structure shown in formula b:

[0050]

[0051] Ar is selected from substituted or unsubstituted C6-C30 aryl groups;

[0052] Cp′ is selected from substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl groups.

[0053] Specifically, Ar is selected from substituted or unsubstituted C6-C30 aryl groups (e.g., it can be benzene, biphenyl, substituted benzene or substituted biphenyl);

[0054] When Cp′ is selected from substituted cyclopentadienyl, substituted indole, or substituted fluorenyl, the substituent can be one or more. For example, the substituent can be one methyl or two methyl groups, or one methyl group and one ethyl group.

[0055] The metallocene compound ligand of the present invention has the structure shown in Formula b. This metallocene compound ligand can yield a metallocene compound with a silicon-silicon-carbon-oxygen heteroatom-restricted geometry. The metal center of this metallocene compound contains a six-membered chelate ring, and two large sterically hindered aromatic groups are attached to the two silicon atoms respectively, making its coordination space more crowded. This greatly improves the thermal stability of the metallocene compound, exhibiting special high-activity catalytic performance under high temperature conditions, high resistance to impurities, and long catalytic lifetime. This compound is suitable for catalyzing the polymerization reaction of C6-C30 long straight-chain α-olefins and mixed long-branched intra-olefins.

[0056] The present invention does not impose any particular limitation on the substituents of the C6-C30 aryl group in Ar. In some embodiments, the substituents of the C6-C30 aryl group in Ar can be at least one of methyl, ethyl, methylene, isopropyl, vinyl, propenyl and butenyl.

[0057] This invention does not specifically limit the substituents of cyclopentadienyl, indenyl, or fluorenyl in Cp'. In some embodiments, the substituents of cyclopentadienyl, indenyl, or fluorenyl in Cp' are selected from at least one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or phenyl. Preferably, the substituents of Cp' are selected from at least one of methyl, ethyl, n-propyl, isopropyl, or butyl.

[0058] In some embodiments of the present invention, the metallocene compound ligand has a structure shown in any of formulas b1-b5:

[0059]

[0060] A second aspect of the present invention provides a metallocene compound comprising the metallocene compound ligand described above.

[0061] The metallocene compound of the present invention includes the aforementioned metallocene compound ligand. This metallocene compound is a compound with a restricted geometry of silicon-silicon-carbon-oxygen heteroatoms. The metal center of this metallocene compound contains a six-membered chelate ring, and two large sterically hindered aromatic groups are attached to the two silicon atoms, making its coordination space more crowded. This greatly improves the thermal stability of the metallocene compound, exhibiting special high-activity catalytic performance under high-temperature conditions, high resistance to impurities, and long catalytic lifetime. Therefore, this metallocene compound is suitable for catalyzing the polymerization reaction of C6-C30 long-chain α-olefins and long-branched mixed olefin feedstocks.

[0062] In some embodiments of the present invention, the metallocene compound has the structure shown in formula a:

[0063]

[0064] Wherein, X is a halogen, and at least one of the following: substituted or unsubstituted C1-C30 alkyl, C1-C30 alkoxy, C2-C30 dialkylamino, C2-C30 alkenyl or C6-C30 aryl;

[0065] M is a transition metal element.

[0066] Specifically, X can be a halogen (e.g., -F, -Cl, -Br, -I), a substituted or unsubstituted C1-C30 alkyl (e.g., C1-C30 straight-chain alkyl, C1-C30 branched alkyl), a C1-C30 alkoxy (e.g., C1-C30 branched alkoxy, C1-C30 straight-chain alkoxy), a C2-C30 dialkylamino (e.g., an amino group substituted with two C1-C15 straight-chain alkyl), a C2-C30 alkenyl (e.g., C2-C30 straight-chain alkenyl), or a C6-C30 aryl (e.g., can be benzene, biphenyl, substituted benzene, or substituted biphenyl);

[0067] M is a transition metal element (e.g., Ti, Ni, Zr, Hf).

[0068] The metallocene compounds of the present invention, comprising the structure shown in formula a, have superior thermal stability, catalytic activity, and catalytic lifetime, and are more suitable for catalyzing the polymerization reaction of C6-C30 long-chain α-olefins and long-branched mixed olefin feedstocks, and can obtain polymer products with target molecular weights as required.

[0069] In some embodiments of the present invention, in X, the substituents of C1-C30 alkyl, C1-C30 alkoxy, C2-C30 dialkylamino, C2-C30 alkenyl or C6-C30 aryl are at least one selected from methyl, ethyl, methylene, isopropyl, vinyl, propenyl and butenyl.

[0070] In some embodiments of the present invention, the metallocene compounds have a structure represented by any of formulas a1-a6:

[0071]

[0072]

[0073] A third aspect of the present invention provides a method for preparing metallocene compound ligands, comprising the following steps:

[0074] Diarylethanol undergoes an addition reaction with dihydropyran in the presence of p-toluenesulfonic acid to generate the first compound.

[0075] The first compound was reacted with n-butyllithium, and then a second compound was obtained by reacting it with tetramethyldichlorodisilane.

[0076] The second compound is reacted with the third compound to give the fourth compound, and the fourth compound is reacted with hydrochloric acid to give the ligand;

[0077] The third compound was obtained by reacting the fifth compound with n-butyllithium;

[0078] The fifth compound is selected from one of substituted or unsubstituted cyclopentadiene, indene, or fluorene.

[0079] In this invention, the ligand can be prepared by a method including the following steps, the specific reaction formula of which is shown in Formula 13:

[0080] Diarylethanol is reacted with dihydropyran in the presence of p-toluenesulfonic acid to produce the first compound, diarylmethyl-2-tetrahydropyranyl ether.

[0081] Diarylmethyl-2-tetrahydropyranyl ether was reacted with n-butyllithium to give an intermediate product, which was then reacted with tetramethyldichlorodisilane to give a second compound (c).

[0082] The fifth compound (Cp') was reacted with n-butyllithium to give the third compound (Cp'HLi), then the third compound (Cp'HLi) was reacted with the second compound (c) to give the fourth compound (d), and finally the fourth compound (d) was reacted with hydrochloric acid to give the ligand.

[0083] It is understood that all of the above reactions require a solvent. In some embodiments, the first compound can be prepared in dichloromethane solvent; the second compound and ligands can be prepared in diethyl ether solvent.

[0084]

[0085] The method for preparing metallocene compound ligands of the present invention can prepare the above-mentioned metallocene compound ligands, and the preparation method is simple and suitable for wide application and promotion.

[0086] In some embodiments of the present invention, during the preparation of the second compound, the molar ratio of diarylethanol, dihydropyran, and n-butyllithium is (29.5-30.5):(59.5-60.5):(29.7-35.1);

[0087] During the preparation of the ligand, when the molar ratio of the second compound, the fifth compound, n-butyllithium, and hydrochloric acid is (4.3-5.2):(4.2-4.8):(4.5-5.2):(9.8-10.4), a ligand with higher purity can be generated, which is beneficial to obtaining the metallocene compound of the present invention. This metallocene compound is suitable for catalyzing the polymerization reaction of C6-C30 long-chain α-olefins with mixed long-branched intra-olefin feedstocks.

[0088] A fourth aspect of the present invention provides a method for preparing the above-mentioned metallocene compound, comprising the following steps:

[0089] The metallocene compound is obtained by reacting the ligand salt with MX4.

[0090] Among them, ligand salts are obtained by reacting ligands with strong basic compounds.

[0091] It is understood that the above metallocene compounds are obtained by reacting ligand salts with MX4, and the ligand salts are obtained by reacting the ligands shown in formula b with strong basic compounds.

[0092] The preparation method of the present invention can prepare metallocene compounds with the above-mentioned structure, and the preparation process is simple and convenient for widespread application and promotion.

[0093] In some embodiments of the present invention, the strong base compound is selected from at least one of n-butyllithium, methyllithium, methylmagnesium chloride, or benzylmagnesium chloride. When the strong base compound is selected from the above-mentioned substances, it is more conducive to the reaction of the ligand with the strong base compound to form a ligand salt.

[0094] The reaction formulas for the metallocene compounds in some embodiments of the present invention are shown in Formula 14:

[0095]

[0096] Furthermore, when the molar ratio of ligand, strong basic compound, and MX4 is (3.8-4.4):(8.0-9.2):(3.9-4.5), the ligand salt can be generated more effectively, and the reaction of the ligand salt with MX4 can yield the metallocene compound of the present invention.

[0097] A fifth aspect of the present invention provides a catalyst system comprising the metallocene compound described above.

[0098] It is understood that the metallocene compounds of the present invention can be used in combination with other compounds, including co-catalysts, to form a catalyst system for catalyzing the polymerization reactions of compounds such as olefins. The co-catalyst includes at least one of alkylating agents and borides.

[0099] The catalyst system of the present invention, since it includes the above-mentioned metallocene compounds, is suitable for catalyzing the polymerization reaction of C6 to C30 long-chain α-olefins with mixed long-branched intraolefin feedstocks.

[0100] The technical solution of the present invention will be further described below with reference to specific embodiments. The specifications and sources of the chemical reagents used in the embodiments and comparative examples of the present invention are shown in Table 1.

[0101] Table 1

[0102]

[0103]

[0104] Example 1

[0105] The metallocene compound ligand in this embodiment was prepared by a method including the following steps:

[0106] Diphenylmethanol (5520 mg, 30 mmol) and 30 mL of dichloromethane were placed in a 100 mL round-bottom flask. P-Toluenesulfonic acid (90 mg, 0.5 mmol) was added with stirring. After stirring for 5 minutes, dihydropyran (5047 mg, 60 mmol) was added rapidly in one go. The reaction solution changed from yellow to red within seconds. Potassium tert-butoxide (200 mg, 1.8 mmol) was immediately added to quench the reaction. The solvent and excess dihydropyran were distilled off under reduced pressure at 50 °C. The product was extracted with 60 mL of pentane and filtered through diatomaceous earth to remove the solvent, yielding diphenylmethyl-2-tetrahydropyranyl ether (7245 mg, 27.3 mmol, 90.0%).

[0107] Diphenylmethyl-2-tetrahydropyranyl ether (1342 mg, 5 mmol) was dissolved in 20 mL of diethyl ether. At room temperature, 2 mL of n-butyllithium solution (2.5 M, 5.0 mmol) was slowly added. After reacting for 2 hours, the reaction solution was slowly added to 20 mL of diethyl ether solution containing 15 mmol of tetramethyldichlorodisilane under an ice-water bath. The reaction was continued at room temperature for 1 hour. The solvent and excess tetramethyldichlorodisilane were removed by distillation under reduced pressure. The resulting solid was redissolved in 20 mL of diethyl ether for later use. Tetramethylcyclopentadiene (611 mg, 5.0 mmol) was dissolved in 20 mL of diethyl ether. At room temperature, 2 mL of n-butyllithium solution was slowly added. After reacting with butyllithium solution (2.5M, 5.0mmol) for 2 hours, the reaction solution was slowly added to the above diethyl ether solution at an ice-water bath temperature, and the reaction was stirred overnight at room temperature. The reaction was quenched with 50mL of dilute hydrochloric acid (1N) and stirred for another hour. The organic phase was separated and washed twice with 50mL of distilled water. The organic phase was dried with anhydrous magnesium sulfate and the solvent was removed by rotary evaporation. The crude product was purified by column chromatography (200-mesh silica gel column, eluent (petroleum ether: dichloromethane = 8:2)) to obtain ligand b1 tetramethylcyclopentadienyl-(diphenyl)hydroxymethyl-tetramethyldisilane (1956mg, 4.66mmol, 93%).

[0108] b1 1 HNMR data (400MHz, CDCl3): δ = 0.22 (s, 6H, Me2Si), 0.38 (s, 6H, Me2Si), 1.69 (d, 6H, Me4C5H), 1.96 (s, 6H , Me4C5H), 4.10 (m, 1H, H-C5Me4), 4.39 (s, 1H, OH), 7.24 (t, 2H, Ph), 7.27 (d, 4H, Ph), 7.33 (d, 4H, Ph).

[0109] The metallocene compound of this embodiment was prepared by a method including the following steps:

[0110] Dissolve b1 (1788 mg, 4.26 mmol) in 50 mL of diethyl ether. Slowly add 3.4 mL of n-butyllithium solution (2.5 M, 8.50 mmol) to the solution at room temperature and stir overnight. Then, slowly add the reaction mixture dropwise to a 20 mL solution of titanium tetrachloride (806 mg, 4.25 mmol) in diethyl ether at -20 °C. Allow the reaction mixture to rise to room temperature naturally and stir overnight. Diethyl ether is evaporated under reduced pressure, and the reaction product is dissolved in 30 mL of dichloromethane. Filter out the insoluble matter. Add approximately 20 mL of n-hexane to the solution until a precipitate begins to form. Then, slowly concentrate the solution to allow the product to crystallize. Filter out the product, and remove the solvent under vacuum to obtain the metallocene compound a1 tetramethyldisil-bridged-tetramethylcyclopentadienyl-[(diphenyl)-methoxy]-titanium dichloride (961 mg, 1.79 mmol, 42%).

[0111] a1 1 HNMR data (400MHz, CDCl3): δ=0.38 (s, 6H, Me2Si), 0.64 (s, 6H, Me2Si), 1.89 (d, 6H, Me4C5), 1.96 (s, 6H, Me4C5), 7.13 (d, 4H, Ph), 7.24 (t, 4H, Ph), 7.31 (t, 2H, Ph).

[0112] Example 2

[0113] The difference between the preparation method of the metallocene compound ligand in this embodiment and that in Example 1 is as follows:

[0114] Replacing diphenylmethanol in Example 1 with (p-tolyl)(phenyl)methanol yielded the product (p-tolyl)(phenyl)methyl-2-tetrahydropyranyl ether (7725 mg, 27.65 mmol, 92%).

[0115] By replacing the diphenylmethyl-2-tetrahydropyranyl ether in Example 1 with (p-tolyl)(phenyl)methyl-2-tetrahydropyranyl ether, and by replacing the tetramethylcyclopentadiene in Example 1 with indene, ligand b2 indene-[(p-tolyl)(phenyl)hydroxymethyl]-tetramethyldisilane (1777 mg, 4.15 mmol, 83%) was obtained;

[0116] b2 1HNMR data (400MHz, CDCl3): δ = 0.22 (s, 6H, Me2Si), 0.31 (s, 6H, Me2Si), 2.35 (s, 3H, Me-P h), 3.95 (d, 1H, C3H3-C6H4), 4.40 (t, 1H, OH), 6.59 (t, 1H, C3H3-C6H4), 6.64 (d, 1H, C3H 3-C6H4), 7.13(d, 4H, Ph-Me), 7.24(t, 1H, Ph), 7.27(d, 2H, Ph), 7.28(t, 1H, C6H4-C3H3 ), 7.31 (d, 1H, C6H4-C3H3), 7.33 (t, 2H, Ph), 7.35 (t, 1H, C6H4-C3H3), 7.41 (t, 1H, Ph).

[0117] The preparation method of the metallocene compound in this embodiment differs from that in Example 1 in that:

[0118] Replacing ligand b1 with ligand b2 (1691 mg, 3.95 mmol) yielded the metallocene compound a2 tetramethyldisil-bridged-indenyl-[(p-tolyl)(phenyl)methoxy]-titanium dichloride (844 mg, 1.55 mmol, 39.2%).

[0119] a2 1 HNMR data (400MHz, CDCl3): δ = 0.35 (s, 6H, Me2Si), 0.56 (s, 6H, Me2Si), 2.35 (s, 3H, Me-Ph), 6. 67 (d, 1H, C3H3-C6H4), 6.90 (d, 1H, C3H3-C6H4), 6.64 (t, 1H, C6H4-C3H3), 7.13 (d, 4H, Ph-Me) ,7.24(t,1H,Ph),7.00(d,2H,Me-Ph),7.14(t,3H,(Me-Ph)C(Ph)),7.31(t,2H,Ph),7.32(t, 2H, C6H4-C3H3), 7.34 (d, 2H, C6H4-C3H3), 7.39 (d, 1H, C6H4-C3H3), 7.41 (t, 1H, C6H4-C3H3).

[0120] Example 3

[0121] The difference between the preparation method of the metallocene compound ligand in this embodiment and that in Example 1 is as follows:

[0122] Replacing diphenylmethanol in Example 1 with (o-tolyl)(phenyl)methanol yielded the product (o-tolyl)(phenyl)methyl-2-tetrahydropyranyl ether (7867 mg, 28.15 mmol, 94%).

[0123] By replacing the diphenylmethyl-2-tetrahydropyranyl ether in Example 1 with (o-tolyl)(phenyl)methyl-2-tetrahydropyranyl ether, and by replacing the tetramethylcyclopentadiene in Example 1 with an indenyl group, ligand b3 indenyl-[(o-tolyl)(phenyl)hydroxymethyl]-tetramethyldisilane (1832 mg, 4.28 mmol, 85.6%) was obtained.

[0124] b3 1 HNMR data (400 MHz, CDCl3): δ = 0.21 (s, 6H, Me2Si), 0.37 (s, 6H, Me2Si), 2.39 (s, 3H, Me-Ph), 3.95 (d, 1H, C3H3-C6H4), 4.69 (d, 1H, OH), 6.59 (t, 1H, C6H4). 4- C3H3), 6.64 (d, 2H, C3H3-C6H4), 7.14 (d, 1H, Me-Ph), 7.00 (d, 2H, Me-Ph), 7.13 (d, 4H, Me-Ph), 7.20 (t, 2H, Me-Ph), 7.18 (d, 1H, Me-Ph), 7.24 (d, 1 H, Me-Ph), 7.28 (d, 1H, C6H4-C3H3), 7.29 (d, 2H, Ph), 7.32 (d, 1H, C6H4-C 3H3), 7.33 (t, 2H, Ph), 7.37 (d, 1H, C6H4-C3H3), 7.41 (d, 1H, C6H4-C3H3).

[0125] The preparation method of the metallocene compound in this embodiment differs from that in Example 1 in that:

[0126] Ligand b1 was replaced with ligand b3 (1746 mg, 4.08 mmol), and titanium tetrachloride was replaced with zirconium tetrachloride to obtain metallocene compound a3 tetramethyldisil-bridged-indenyl-[(o-tolyl)(phenyl)methoxy]-zirconium dichloride (970 mg, 1.65 mmol, 40.4%).

[0127] a3 1HNMR data (400MHz, CDCl3): δ = 0.39 (s, 6H, Me2Si), 0.56 (s, 6H, Me2Si), 2.33 (s, 3H, Me-Ph ), 6.83 (d, 1H, C3H3-C6H4), 6.9 (d, 1H, C3H3-C6H4), 7.02 (d, 1H, Me-Ph), 7.18 (d, 1H, Me -Ph), 7.20(d, 2H, Ph), 7.22(t, 1H, Me-Ph), 7.24(t, 1H, Ph), 7.27(t, 2H, Me-Ph), 7.31( t, 2H, Ph), 7.34 (t, 1H, C6H4-C3H3), 7.37 (t, 1H, C6H4-C3H3), 7.40 (t, 1H, C6H4-C3H3).

[0128] Example 4

[0129] The difference between the preparation method of the metallocene compound ligand in this embodiment and that in Example 1 is as follows:

[0130] Replacing diphenylmethanol in Example 1 with (o-tolyl)(phenyl)methanol yielded the product (o-tolyl)(phenyl)methyl-2-tetrahydropyranyl ether (7867 mg, 28.15 mmol, 94%).

[0131] By replacing the diphenylmethyl-2-tetrahydropyranyl ether in Example 1 with ((o-tolyl)(phenyl)methyl-2-tetrahydropyranyl ether) and by replacing the tetramethylcyclopentadiene in Example 1 with fluorene, ligand b4fluorenyl-[(o-tolyl)(phenyl)hydroxymethyl]-tetramethyldisilane (2080 mg, 4.35 mmol, 87%) was obtained;

[0132] b4 1 HNMR data (400MHz, CDCl3): δ = 0.26 (s, 6H, Me2Si), 0.41 (s, 6H, Me2Si), 2.39 (s, 3H, Me-Ph), 4.69 (s, 1H, OH), 7.14 (s, 1 H, Me-Ph), 7.18 (d, 1H, Me-Ph), 7.20 (t, 2H, Me-Ph), 7.24 (t, 1H, Ph), 7.29 (d, 2H, Ph), 7.33 (t, 2H, Ph), 7.35 (t, 2H, C 13 H9), 7.41(t, 2H, C) 13 H9), 7.49 (t, 2H, C) 13 H9).

[0133] The preparation method of the metallocene compound in this embodiment differs from that in Example 1 in that:

[0134] Ligand b1 was replaced with ligand b4 (1884 mg, 3.94 mmol), and titanium tetrachloride was replaced with zirconium tetrachloride to obtain metallocene compound a4 tetramethyldisil-bridged-fluorenyl-(o-tolyl)(phenyl)methoxy-zirconium dichloride (1128 mg, 1.75 mmol, 44.4%).

[0135] a4 1 HNMR data (400 MHz, CDCl3): δ = 0.42 (s, 6H, Me2Si), 0.64 (s, 6H, Me2Si), 2.31 (s, 3H, Me-Ph), 7.01 (dd, 1H, Me-Ph), 7.15 (dd, 2H, C 13 H9), 7.19(d, 1H, (t, 3H, (Me-Ph)C(Ph)), 7.28(dt, 1H, Ph), 7.30(t, 2H, C 13 H9), 7.31(t, 2H, Ph), 7.35(dt, 2H, C 13 H9), 7.51 (d, 2H, C) 13 H9).

[0136] Example 5

[0137] The difference between the preparation method of the metallocene compound ligand in this embodiment and that in Example 1 is as follows:

[0138] Replacing diphenylmethanol in Example 1 with (p-tolyl)(phenyl)methanol yielded the product (p-tolyl)(phenyl)methyl-2-tetrahydropyranyl ether (7725 mg, 27.65 mmol, 92%).

[0139] By replacing the diphenylmethyl-2-tetrahydropyranyl ether in Example 1 with (p-tolyl)(phenyl)methyl-2-tetrahydropyranyl ether, and by replacing the tetramethylcyclopentadiene in Example 1 with fluorene, ligand b5 fluorenyl-[(p-tolyl)(phenyl)hydroxymethyl]-tetramethyldisilane (1889 mg, 3.95 mmol, 79%) was obtained;

[0140] b5 1 HNMR data (400 MHz, CDCl3): δ = 0.26 (s, 6H, Me2Si), 0.38 (s, 6H, Me2Si), 2.35 (s, 3H, Me-Ph), 4.40 (s, 1H, OH), 5.52 (s, 1H, C 13 H9), 7.13 (d, 4H, Me-Ph), 7.24 (t, 1H, Ph), 7.26 (d, 2H, Ph), 7.33 (t, 2H, Ph), 7.41 (dt, 2H, C 13H9), 7.49 (d, 2H, C) 13 H9), 7.72 (d, 2H, C) 13 H9).

[0141] The preparation method of the metallocene compound in this embodiment differs from that in Example 1 in that:

[0142] Replacing ligand b1 with ligand b5 (1442 mg, 3.0 mmol) and titanium tetrachloride with HfCl4 yielded the metallocene compound a5 tetramethyldisil-bridged-fluorenyl-[(p-tolyl)(phenyl)methoxy]-hafnium dichloride (944 mg, 1.44 mmol, 48%).

[0143] a5 1 HNMR data (400 MHz, CDCl3): δ = 0.39 (s, 6H, Me2Si), 0.65 (s, 6H, Me2Si), 2.35 (s, 3H, Me-Ph), 7.01 (d, 2H, Me-Ph), 7.14 (d, 2H, C 13 H9), 7.16(d, 2H, Ph-Me), 7.18(d, 2H, Ph), 7.22(t, H, C 13 H9), 7.31 (d, 2H, C) 13 H9), 7.32(t, 2H, C) 13 H9), 7.36(dt, 2H, C) 13 H9), 7.51 (dd, 2H, C) 13 H9).

[0144] Test case

[0145] Experimental Example 1

[0146] The metallocene compounds of Examples 1-5, 2,4-di-tert-butyl-6-(2,3,4,5-tetramethylcyclopentadienyl)phenoxy titanium dichloride (Comparative Example 1), (4,6-di-tert-butyl-9-fluorenyl)phenoxy titanium 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)zirconia dichloride (Comparative Example 4) were used as catalysts to catalyze the polymerization reaction of 1-decene, specifically including:

[0147] A 300mL stainless steel polymerization reactor equipped with a magnetic stirrer was heated to 120℃ and evacuated for 1 hour. After N2 replacement 2-3 times, 100mL of 1-decene (98% purity) containing 0.2mL of triisobutylaluminum was introduced. Then, 10mL of toluene solution containing 5mg of Ph3CB(C6F5)4 and 2mg of catalyst was added to the reactor. The reaction temperature was controlled at 70℃ and the reaction was stirred for 1.5 hours. Then, 2mL of anhydrous ethanol was added to the reactor to terminate the reaction and obtain the product. The crude product was then separated from ethanol, toluene, monomer and dimer under reduced pressure to obtain the final polymer product.

[0148] The catalytic activity of the catalyst, the yield of the polymerization product, the conversion of 1-decene, the weight-average molecular weight, kinematic viscosity at 100℃, viscosity index and pour point of the obtained polymerization product were tested respectively. The test results are shown in Table 2.

[0149] Wherein, 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%;

[0150] The yield of the 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%;

[0151] Catalytic activity of a catalyst = (total mass of reaction products) / number of moles of catalyst / catalytic time / number of active sites on the catalyst. Typically, the number of active sites for metallocene compounds is 1.

[0152] The kinematic viscosity of the polymer product was determined according to GB / T256-1988. The kinematic viscosity of the polymer product sample at 40℃ and 100℃ was tested using a SYP1003V1 kinematic viscosity meter. The viscosity index was then calculated according to the conversion relationship between viscosity and viscosity index (using ASTM D2270 method).

[0153] The pour point of the polymer product was tested using the method of GB / T3535--83(91).

[0154] The weight-average molecular weight, number-average molecular weight, and polydispersity index of the polymer products were measured using the GB / T 27843-2011 method. Table 2

[0155]

[0156] As can be seen from Table 2, the metallocene compounds prepared in the embodiments of the present invention catalyze the polymerization reaction of 1-decene, resulting in a high conversion rate of 1-decene and high activity of the metallocene compounds, leading to a high yield of the obtained product.

[0157] Figure 1This is a molecular weight distribution diagram of the polymerization product obtained by the polymerization reaction of 1-decene catalyzed by a metallocene compound in Example 1 of the present invention. Figure 1 As shown, the polymer obtained by using the metallocene compound of Example 1 of the present invention to catalyze the polymerization reaction of 1-decene has a weight-average molecular weight MW = 3873, a number-average molecular weight Mn = 1359, and a polydispersity index PD = 2.85. The polydispersity index is between 1.5 and 20, indicating that the compound can catalyze the chain polymerization of 1-decene.

[0158] Experimental Example 2

[0159] The metallocene compound of Example 1, 2,4-di-tert-butyl-6-(2,3,4,5-tetramethylcyclopentadienyl)phenoxy titanium dichloride (Comparative Example 1), (4,6-di-tert-butyl-9-fluorenyl)phenoxy titanium 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) were used as catalysts to catalyze the polymerization reaction of mixed decene liquid, specifically including:

[0160] A 300mL stainless steel polymerization reactor equipped with a magnetic stirrer was heated to 80℃ and evacuated for 1 hour. After N2 replacement 2-3 times, 150mL of a mixed decene liquid containing 0.4mL of triisobutylaluminum (mixed decene composition: 1-decene 30.99%, cis-4-decene 2.35%, trans-4-decene 8.60%, 4-ethyl-1-octene 19.43%, 3-propyl-1-heptene 22.83%, 2-butyl-1-hexene 12.26%, and 5-methyl-1-nonene 3.54%) was introduced. Then, 10mL of a toluene solution containing 5mg of Ph3CB(C6F5)4 and 2.2mg of catalyst was added to the reactor. The reaction temperature was controlled at 60℃, and the reaction was stirred for 1.5 hours. Finally, 5mL of anhydrous ethanol was added to the reactor to terminate the reaction and obtain the product. The crude product was then subjected to constant vacuum separation of ethanol, toluene, monomer, and dimer to obtain the final polymer product.

[0161] The catalytic activity of the catalyst, the yield of the polymerization product, the conversion rate of the mixed decene, the weight-average molecular weight, kinematic viscosity at 100℃, viscosity index and pour point of the obtained polymerization product were tested respectively. The test results are shown in Table 3. The test methods are the same as those in Experiment 1.

[0162] Table 3

[0163]

[0164] As can be seen from Table 3, the metallocene compounds prepared in the embodiments of the present invention catalyze the polymerization reaction of decene mixtures, resulting in a high conversion rate of decene and high activity of the metallocene compounds, leading to a high yield of the obtained products.

[0165] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A metallocene compound ligand characterized in that, It has the structure shown in equation b: Formula b, Ar is selected from substituted or unsubstituted C6-C30 aryl groups; Cp' is selected from substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl groups; In Ar, the substituents of the C6-C30 aryl group are selected from at least one of methyl, ethyl and isopropyl; In Cp', the substituents of cyclopentadienyl, indenyl, or fluorenyl are selected from at least one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or phenyl.

2. The metallocene compound ligand according to claim 1, characterized in that, The metallocene compound ligands have structures shown in any of formulas b1-b5: b1 b2 b3 b4 b5.

3. A metallocene compound, characterized in that, It has the structure shown in equation a: Formula a; Ar is selected from substituted or unsubstituted C6-C30 aryl groups; Cp' is selected from substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl groups; In Ar, the substituents of the C6-C30 aryl group are selected from at least one of methyl, ethyl and isopropyl; In Cp', the substituents of cyclopentadienyl, indenyl, or fluorenyl are selected from at least one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or phenyl; X is a halogen; M is Ti, Zr, or Hf.

4. The metallocene compound according to claim 3, characterized in that, The metallocene compound has a structure shown in any of formulas a1-a6: a1 a2 a3 a4 a5 a6.

5. A method for preparing the metallocene compound ligand according to any one of claims 1-2, characterized in that, Includes the following steps: Diarylethanol undergoes an addition reaction with dihydropyran in the presence of p-toluenesulfonic acid to generate the first compound. The first compound was reacted with n-butyllithium, and then tetramethyldichlorodisilane was added to the system to obtain the second compound; The second compound is reacted with the third compound to give the fourth compound, and the fourth compound is reacted with hydrochloric acid to give the ligand; The third compound is obtained by reacting the fifth compound with n-butyllithium; The fifth compound is selected from one of substituted or unsubstituted cyclopentadiene, indene, or fluorene.

6. A method for preparing the metallocene compound according to any one of claims 3-4, characterized in that, Includes the following steps: The metallocene compound is obtained by reacting the ligand salt with MX4. The ligand salt is obtained by reacting the metallocene compound ligand according to any one of claims 1-2 with a strong basic compound; The strongly basic compound is at least one of n-butyllithium, methyllithium, methylmagnesium chloride, and benzylmagnesium chloride.

7. A catalyst system, characterized in that, Including the metallocene compounds according to any one of claims 3-4.

Images