Ferrocene-non-ferrocene metal complex, method for preparing the same, and use thereof in the preparation of disentangled ultra-high molecular weight polyethylene

Abstract

The complex provided by the application has the structure of formula (I), formula (II) or formula (III), which is composed of a ligand and a central metal, the ligand is a heteroatom-containing aromatic group, and the central metal is Ti, and the complex can be used for catalyzing the synthesis of ultra-high molecular weight polyethylene, the prepared ultra-high molecular weight polyethylene has a viscosity-average molecular weight of 10-80 million, a lower entanglement degree between molecular chains, a melting point of 130-145 DEG C and a polymerization activity as high as 10 6 Moreover, the complex provided by the application is simple to synthesize and has a high yield of 50-60%.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of catalysts and their applications, and particularly relates to a metallocene-non-metallocene metal complex, a preparation method thereof and application thereof in preparation of disentangled ultra-high molecular weight polyethylene. BACKGROUND

[0002] In 1975, the Netherlands invented gel spinning using decalin as a solvent, successfully prepared ultra-high molecular weight polyethylene (UHMWPE) fibers, and applied for a patent in 1979. After ten years of research and efforts, it was confirmed that the gel spinning method is an effective method for manufacturing high-strength polyethylene fibers and has industrialization prospects. Ultra-high molecular weight polyethylene has super wear resistance, self-lubricating property, relatively high strength, stable chemical properties and strong anti-aging performance, and plays an important role in modern warfare and aviation, aerospace, sea defense equipment and other fields.

[0003] Ultra-high molecular weight polyethylene has high molecular weight and poor flowability and is difficult to process. Realizing the synthesis and performance processing of ultra-high molecular weight polyethylene is of great significance to its industrial application, but there are very few catalysts that can be used at present. Moreover, almost all commercial UHMWPE is produced using Zieglar Natta catalyst (Z-N catalyst). The Z-N catalyst is a heterogeneous catalyst containing multiple active sites, and these active sites exhibit different reactivity, so the molecular weight distribution of the obtained polymer is wide. At the same time, due to the high reaction temperature, the prepared UHMWPE will have molecular chain entanglement, which will inhibit the movement ability of the polymer chain, thereby affecting the processing performance of the product. Compared with the Z-N catalyst, the metallocene catalyst and the non-metallocene catalyst are single active species catalysts, which can realize living polymerization, obtain a polymer with a narrow molecular weight distribution, and the polymerization temperature is relatively low, which can effectively avoid the occurrence of molecular chain entanglement. However, the metallocene catalyst or the non-metallocene catalyst disclosed in the prior art cannot be used to synthesize UHMWPE. SUMMARY

[0004] Therefore, the technical problem to be solved by the present application is to provide a complex, a preparation method thereof and an application thereof. The complex provided in the present application is a metallocene-non-metallocene metal complex composed of a ligand and a central metal, which can be used for catalytic synthesis of UHMWPE, has a narrow molecular weight distribution, and has a low degree of molecular chain entanglement.

[0005] The present application provides a complex represented by formula (I), formula (II) or formula (III):

[0006]

[0007] wherein Z is selected from S, O, (CH2) n; n is an integer from 1 to 5;

[0008] R1 is selected from substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted phenyl or halogen;

[0009] R2, R3 are independently selected from hydrogen, substituted or unsubstituted C1-C12 alkyl or halogen;

[0010] R4, R5, R6, R7, R8 are independently selected from hydrogen, substituted or unsubstituted C1-C12 alkyl or halogen;

[0011] R9, R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 are independently selected from hydrogen, substituted or unsubstituted silyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted aryl or halogen.

[0012] The complex provided by the application is a metallocene-non-metallocene metal complex, which is composed of a ligand and a central metal, the ligand is a heteroatom-containing aromatic group, and the central metal is Ti, and can be used for catalyzing synthesis of ultra-high molecular weight polyethylene, the prepared ultra-high molecular weight polyethylene has a viscosity average molecular weight of 10-80 million, a lower degree of entanglement between molecular chains, a melting point of 130-145 DEG C, and a polymerization activity as high as 10 6 Moreover, the complex provided by the application is simple to synthesize and has a high yield of 50-60%.

[0013] In some specific implementation manners, Z is selected from S or CH2;

[0014] R1 is selected from substituted or unsubstituted C1-C5 alkyl, halogen;

[0015] R2, R3 are independently selected from hydrogen, substituted or unsubstituted C1-C5 alkyl;

[0016] R4, R5, R6, R7, R8 are independently selected from hydrogen, substituted or unsubstituted C1-C12 alkyl or halogen;

[0017] R9, R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17each independently selected from the group consisting of hydrogen, alkyl substituted silyl, substituted or unsubstituted C1-C5 alkyl.

[0018] In some embodiments, Z is selected from S, CH2;

[0019] R1is selected from Cl, CH3;

[0020] R2, R3are independently selected from any one of t-butyl, methyl, octyl, halogen;

[0021] R4, R5, R6, R7, R8are independently selected from any one of hydrogen, methyl, t-butyl, halogen;

[0022] R9, R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 are independently selected from any one of hydrogen, methyl, ethyl, t-butyl, octyl, trimethylsilyl;

[0023] In some embodiments, the complex is selected from:

[0024] Complex 1 : Z = S, R1= Cl, R2= C(CH3)3, R3= C(CH3)3, R4= H, R5= H, R6= H, R7= H, R8= H, R9= H, R 10 = H, R 11 = H, R 12 = H, R 13 = H;

[0025] Complex 2: Z = S, R1= Cl, R2= C(CH3)3, R3= C(CH3)3, R4= F, R5= F, R6= F, R7= F, R8= F, R9= H, R 10 = H, R 11 = H, R 12 = H, R 13 = H;

[0026] Complex 3: Z = S, R1= CH3, R2= C(CH3)3, R3= C(CH3)3, R4= H, R5= H, R6= H, R7= H, R8= H, R9= H, R 10 = H, R 11 = H, R 12 = H, R 13 = H;

[0027] Complex 4: Z = CH2, R1= CI, R2= C(CH3)3, R3= C(CH3)3, R4= H, R5= H, R6= H, R7= H, R8= H, R9= H, R 10 = H, R 11 = H, R 12 = H, R 13 = H;

[0028] Complex 5: Z = CH2, R1= CI, R2= H, R3= H, R4= H, R5= H, R6= H, R7= H, R8= H, R9= H, R 10 = H, R 11 = H, R 12 = H, R 13 = H;

[0029] Complex 6: Z = CH2, R1= CH3, R2= C(CH3)3, R3= C(CH3)3, R4= F, R5= F, R6= F, R7= F, R8= F, R9= H, R 10 = H, R 11 = H, R 12 = H, R 13 = H;

[0030] Complex 7: Z = S, R1= CI, R2= C(CH3)3, R3= C(CH3)3, R4= H, R5= H, R6= H, R7= H, R8= H, R9= CH3, R 10 = CH3, R 11 = Si(CH3)3, R 12 = CH3, R 13 = CH3;

[0031] Complex 8: Z = S, R1= CI, R2= H, R3= H, R4= H, R5= H, R6= H, R7= H, R8= H, R9= CH3, R 10 = CH3, R 11 = Si(CH3)3, R 12 = CH3, R 13 = CH3;

[0032] Complex 9: Z = S, R1= CI, R2= H, R3= H, R4= H, R5= H, R6= H, R7= H, R8= H, R9= H, R 10 = H, R 11 = Si(CH3)3, R 12 = H, R 13 = H;

[0033] Complex 10: Z = CH2, R1 = Cl, R2 = C(CH3)3, R3 = C(CH3)3, R4 = F, R5 = F, R6 = F, R7 = F, R8 = F, R9 = H, R 10 =H,R 11 =Si(CH3)3,R 12 =H,R 13 =H;

[0034] Complex 11: Z = S, R1 = Cl, R2 = C(CH3)3, R3 = C(CH3)3, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 =H,R 11 =H,R 12 =H,R 13 =H,R 14 =H,R 15 =H;

[0035] Complex 12: Z = S, R1 = Cl, R2 = C(CH3)3, R3 = C(CH3)3, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 =H,R 11 =H,R 12 =H,R 13 =H,R 14 =H,R 15 =H,R 16 =H,R 17 =H.

[0036] In some specific implementations, the complex has the structures of formulas (1) to (4):

[0037]

[0038] The present invention also provides a method for preparing the above-mentioned complex, comprising the following steps:

[0039] The ligand shown in formula (a) is reacted with a lithium reagent and CpTiX3 to obtain the complex shown in formula (I), (II) or (III), wherein R1 is selected from X, and X is a halogen;

[0040]

[0041] In CpTiX3, Cp is selected from substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, substituted or unsubstituted fluorenyl, and X is a halogen.

[0042] Optionally, the complex of formula (I), (II) or (III) with R1 being halogen is mixed with an alkylating agent to obtain the complex of formula (I), (II) or (III) with R1 not being halogen.

[0043] The synthetic route is as follows:

[0044]

[0045] The source of the compound of formula (a) is not particularly limited in the present application, which can be purchased on the market or prepared according to the methods known to those skilled in the art. The preparation method of compound (a) is shown in the following figure.

[0046]

[0047] First, under the nitrogen atmosphere, compound b and compound c are mixed at 0-150℃ with FeCl3, MgCl2, etc. as catalysts, and the reaction is carried out for 10-72h. After the reaction is completed, the reaction solution is filtered, concentrated, and separated by column chromatography with petroleum ether: ethyl acetate at 7-10:0-3 to obtain compound a.

[0048] The compound of formula (a) is first mixed with a lithiating reagent solution under the nitrogen atmosphere at -78-0℃. In some specific embodiments, the solvent of the lithiating reagent solution is n-hexane, and the concentration of the lithiating reagent solution is 1-5M, preferably 2-4M, and more preferably 2.5-3.2M. In some specific embodiments, the molar ratio of the compound of formula (a) to the lithiating reagent is 1:1-5, preferably 1:1. In some specific embodiments, the lithiating reagent is selected from alkyl lithium, including but not limited to n-butyllithium, etc. In some specific embodiments, the reaction temperature is -78-0℃, preferably -60-0℃, and the reaction time is 10-24h, preferably 12-20h.

[0049] After the reaction is completed, the reaction mixture is filtered, concentrated, and recrystallized to obtain white solid, which is then reacted with CpTiX3 to obtain the complex of formula (I), (II) or (III) with R1 being halogen. The source of CpTiX3 is not particularly limited in the present application, which can be purchased on the market or prepared according to the methods known to those skilled in the art. In the formula, Cp is selected from substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, and substituted or unsubstituted fluorene; and X is halogen, preferably Cl.

[0050] Specifically, the obtained white solid and CpTiX3 are dissolved separately, mixed and then reacted at -78°C to 0°C under nitrogen. In some specific embodiments, the solvent for dissolving is one or more of aliphatic saturated hydrocarbons, aromatic hydrocarbons, aryl halides and cycloalkanes, preferably toluene. The concentration of the dissolved white solid is 0.05-5 mmol / mL, preferably 0.1-4 mmol / mL, and more preferably 0.15-2 mmol / mL; and the concentration of the dissolved CpTiX3 is 0.05-5 mmol / mL, preferably 0.1-4 mmol / mL, and more preferably 0.15-2 mmol / mL. In some specific embodiments, the molar ratio of CpTiX3 to the obtained white solid is 1:1-5, preferably 1:1. In some specific embodiments, the reaction temperature is -78°C to 0°C, preferably -60-0°C, and the reaction time is 10-24 h, preferably 12-20 h. After the reaction is completed, the reaction mixture is filtered, concentrated and recrystallized to obtain the complex of formula (I), (II) or (III) wherein R1 is halogen.

[0051] Alternatively, the complex of formula (I), (II) or (III) wherein R1 is halogen is mixed with an alkylating agent to obtain the complex of formula (I), (II) or (III) wherein R1 is not halogen. In some specific embodiments, the alkylating agent includes but is not limited to CH3BrMg, etc., and the molar ratio of the alkylating agent to the complex of formula (I), (II) or (III) wherein R1 is halogen is 1:2-10, preferably 1:2. In some specific embodiments, the temperature for the alkylation reaction is -78°C to 0°C, preferably -60-0°C, and the reaction time is 1-10 h, preferably 3-5 h. After the reaction is completed, the solvent is removed by filtration, extracted with hexane and concentrated to obtain the complex of formula (I), (II) or (III) wherein R1 is not halogen.

[0052] The application also provides the use of the above metallocene-nonmetallocene complex in catalyzing ethylene polymerization. The use of the above complex in catalyzing polyethylene polymerization can obtain ultra-high molecular weight polyethylene. In some specific embodiments, the ultra-high molecular weight polyethylene has a viscosity average molecular weight of 10-80 million and a low entanglement degree between molecular chains, and the molecular weight is preferably 10-60 million, and more preferably 10-50 million. The ultra-high molecular weight polyethylene has a molecular weight distribution of 1-10, preferably 1-6, and more preferably 1-4. In the application, the ultra-high molecular weight polyethylene has a crystallinity of 60-90% and a melting point of 130-150°C.

[0053] The application further provides a catalyst composition comprising the complex, the organic boron salt compound and the organic aluminum compound as described in the above technical solutions.

[0054] In the application, the organic boron salt compound can be an ionic compound composed of an organic boron anion and a cation; the organic boron anion includes but is not limited to tetraphenylborate ([BPh4] - ), tetra(monofluorophenyl)borate, tetra(difluorophenyl)borate, tetra(trifluorophenyl)borate, tetra(tetrafluorophenyl)borate, tetra(pentafluorophenyl)borate ([B(C6F5)4] - ), tetra(tetrafluoromethylphenyl)borate, tetra(tolyl)borate, tetra(xylyl)borate, (triphenyl, pentafluorophenyl)borate, [tris(pentafluorophenyl), phenyl]borate or undeca-hydrido-7,8-dicarbaundecaborate; the cation includes but is not limited to a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienyl cation or a ferrocenium cation containing a transition metal, the carbonium cation contains a tri-substituted carbonium cation such as a triphenylcarbonium cation ([Ph3C] + ) and a tri(substituted phenyl)carbonium cation, and more specific examples of the tri(substituted phenyl)carbonium cation include a tri(tolyl)carbonium cation; the ammonium cation includes a trialkylammonium cation such as a trimethylammonium cation, a triethylammonium cation ([NEt3H] + ), a tripropylammonium cation and a tributylammonium cation; a N,N-dialkylanilinium cation such as a N,N-dimethylanilinium cation ([PhNMe2H] + ), a N,N-diethylanilinium cation and a N,N-2,4,6-pentamethylanilinium cation and a dialkylammonium cation such as a diisopropylammonium cation and a dicyclohexylammonium cation; the phosphonium cation includes a triarylphosphonium cation such as a triphenylphosphonium cation, a tri(tolyl)phosphonium cation and a tri(xylyl)phosphonium cation.

[0055] In an embodiment of the application, the organic boron salt compound is specifically selected from one or more of [Ph3C][B(C6F5)4], [PhNMe2H][BPh4], [NEt3H][BPh4], B(C6F5)3 and [PhNMe2H][B(C6F5)4].

[0056] In the catalyst composition of the application, the molar ratio of the organic boron salt to the metallocene-hetero complex is preferably (0.5-10):1, more preferably (1-5):1, and even more preferably (1-3):1.

[0057] In some embodiments, the organoaluminum compound is selected from one or more of trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisopropylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldibenzylaluminum, and ethyldi-p-tolylaluminum.

[0058] The mole ratio of the alkylaluminum to the metallocene-nonmetallocene hetero-poly-metal complex in the catalyst composition is preferably (1-200): 1, more preferably (1-100): 1, and even more preferably (1-20): 1.

[0059] The method for preparing the catalyst composition is not particularly limited, and the complex, the organoboron salt compound, and the organoaluminum compound are mixed and dissolved in a solvent. In some embodiments, the solvent can be one or more of aliphatic saturated hydrocarbons, aromatic hydrocarbons, aryl halides, and cycloalkanes, and is preferably toluene. In some embodiments, the volume ratio of the solvent to the moles of the complex in the catalyst is 100-1000 L: 1 mol, and is preferably 200-800 L: 1 mol.

[0060] The catalyst composition provided by the present application can be used to catalytically prepare ultra-high molecular weight polyethylene, including the following steps:

[0061] The ultra-high molecular weight polyethylene is obtained by polymerization of an ethylene-based monomer under the action of the catalyst composition.

[0062] Specifically, the ethylene-based monomer is first placed in a reaction kettle treated under anhydrous and anaerobic conditions, and the above-mentioned catalyst composition solution is added for reaction, i.e., the polymerization reaction is carried out under anhydrous and anaerobic conditions. In some embodiments, the ethylene-based monomer includes but is not limited to styrene, ethylene, propylene, etc. In some embodiments, the pressure of the ethylene-based monomer is 1-20 atm. In some embodiments, the reaction is carried out in a hydrocarbon solvent, which includes but is not limited to toluene, etc. In some embodiments, the mole ratio of the hydrocarbon solvent to the metallocene-nonmetallocene metal is 100-1000: 1. The temperature of the polymerization reaction is 0-60°C, and the time is 30 s-5 h. After the polymerization is completed, an acidified ethanol solution of hydrochloric acid is added to terminate the polymerization reaction, the reaction solution is poured into ethanol for sedimentation, and after drying, low entanglement ultra-high molecular weight polyethylene is obtained.

[0063] The complex provided by the application is a metallocene-non-metallocene metal complex, which is composed of a ligand and a central metal, the ligand is a heteroatom-containing aromatic group, and the central metal is Ti. The complex can be used for catalyzing synthesis of ultra-high molecular weight polyethylene. The prepared ultra-high molecular weight polyethylene has a viscosity-average molecular weight of 10-80 million, a molecular weight distribution of 1-10, a crystallinity of 60-90%, and a melting point of 130-150 DEG C. Moreover, the complex provided by the application is simple in synthesis and has a high yield of 50%-60%. BRIEF DESCRIPTION OF DRAWINGS

[0064] Figure 1 NMR hydrogen spectrum of methyl branched ultra-high molecular weight polyethylene prepared in example 14 of the application;

[0065] Figure 2 Picture of cold-pressed 3 min at room temperature of ultra-high molecular weight polyethylene prepared in example 14 of the application;

[0066] Figure 3 DSC graph of ultra-high molecular weight polyethylene prepared in example 14 of the application;

[0067] Figure 4 KPIC report of ultra-high molecular weight polyethylene prepared in example 14 of the application. DETAILED DESCRIPTION

[0068] The technical solutions of the application will be described clearly and completely in combination with the embodiments of the application. Obviously, the described embodiments are only some of the embodiments of the application, but not all the embodiments. Based on the embodiments in the application, all the other embodiments obtained by those skilled in the art without creative labor are within the protection scope of the application.

[0069] In order to further illustrate the application, the following examples are used for detailed description. The raw materials used in the following examples of the application are all commercially available.

[0070] Example 1: Preparation of complex 1

[0071]

[0072] Under the condition of nitrogen, 2,4-di-tert-butylphenol (3 mmol, 0.62 g) and m-xylene-2-sulfonyl chloride (3 mmol, 0.52 g) are used as raw materials, dissolved in dichloromethane, and reacted at room temperature for 12 h to obtain a gray-green solution with FeCl3 as a catalyst. The reaction solution is filtered and concentrated, and column chromatography separation is performed with petroleum ether: ethyl acetate being 10:1 to obtain white solid (compound 1) 0.46 g with a yield of 51%.

[0073] A 2.5 M solution of n-butyllithium in n-hexane (3 mmol, 1.2 ml) was added dropwise to a solution of the heteroatom ligand (compound 1) (3 mmol, 0.94 g) in n-hexane (20 ml) at -30 °C under nitrogen. After 10 h of reaction, the solution was filtered and concentrated. The white solid was recrystallized to obtain a white solid. The white solid (3 mmol, 0.96 g) and CpTiCl3(3 mmol, 0.63 g) were dissolved in toluene (20 ml) at -30 °C under nitrogen. The solution of the white solid was added to the solution of CpTiCl3. After 10 h of reaction, the solution was filtered and concentrated. The orange-red metallocene complex 1 was recrystallized to obtain 0.8 g in 53% yield.

[0074] NMR of hydrogen: 1 H NMR (500 MHz, CDC13) δ 1.22 (s, 9H), 1.62 (s, 9H), δ 6.41 (s, 5H), δ 6.98 (tt, 1H), δ 7.08 (tt, 2H), δ 7.34 (dt, 2H), δ 7.54 (s, 2H)

[0075] Elemental analysis of the target molecule formula is C 25 H 29 Cl2OSTi (%)

[0076] Theoretical analysis value: C, 60.50; H, 5.89. Actual value: C, 60.20; H, 6.53.

[0077] Example 2: Preparation of complex 2

[0078]

[0079] A gray-green solution was obtained by using benzyl chloride (3 mmol, 0.38 g) and 2,4-di-tert-butylphenol (3 mmol, 0.62 g) as raw materials, dissolving in dichloromethane, using FeCl3as a catalyst, and reacting at room temperature for 12 h under nitrogen. The solution was filtered and concentrated. Column chromatography was performed using petroleum ether: ethyl acetate = 10:0 to separate and obtain a white solid (compound 2) 0.40 g in 45% yield.

[0080] A 2.5 M solution of n-butyllithium in hexane (3 mmol, 1.2 ml) was added dropwise to a solution of the ligand (compound 2) (3 mmol, 1.21 g) in hexane (20 ml) at -30 °C under nitrogen. After 10 h of reaction, the solution was filtered and concentrated, and the white solid was recrystallized to obtain a white solid. The white solid (3 mmol, 1.23 g) and CpTiCl3(3 mmol, 0.63 g) were separately dissolved in toluene (20 ml) at -30 °C under nitrogen, and the solution of the white solid was added to the solution of CpTiCl3. After 10 h of reaction, the solution was filtered and concentrated, and the orange-red metallocene complex 2 was recrystallized to obtain 1.21 g in a yield of 55%.

[0081] Elemental analysis of the target molecular formula C 25 H 24 Cl2F5OSTi (%)

[0082] Theoretical analysis: C, 51.22; H, 4.13. Found: C, 51.35; H, 4.52.

[0083] Example 3: Preparation of complex 3

[0084]

[0085] A 2.5 M solution of n-butyllithium in hexane (3 mmol, 1.2 ml) was added dropwise to a solution of the heteroatom-containing ligand (compound 1) (3 mmol, 0.94 g) in hexane (20 ml) at -30 °C under nitrogen. After 10 h of reaction, the solution was filtered and concentrated, and the white solid was recrystallized to obtain a white solid. The white solid (3 mmol, 0.96 g) and CpTiCl3(3 mmol, 0.63 g) were separately dissolved in toluene (20 ml) at -30 °C under nitrogen, and the solution of the white solid was added to the solution of CpTiCl3. After 10 h of reaction, the solution was filtered and concentrated, and then 3.0 M methylmagnesium bromide in ether (3 mmol, 1 ml) was added at -30 °C. After 1 h of reaction, the solution was filtered and recrystallized with celite to obtain the orange-red metallocene complex 3 in a yield of 0.67 g and a purity of 49%.

[0086] Elemental analysis of the target molecular formula C 27 H 36 OSTi (%)

[0087] Theoretical analysis: C, 71.04; H, 7.95. Found: C, 71.01; H, 8.02.

[0088] Example 4: Preparation of complex 4

[0089]

[0090] A 2.5 M solution of n-butyllithium in n-hexane (3 mmol, 1.2 ml) was added dropwise to a solution of ligand (compound 2) (3 mmol, 0.89 g) in n-hexane (20 ml) at -30 °C under nitrogen. After 10 h of reaction, the reaction solution was filtered, concentrated and recrystallized to obtain a yellow solid. The yellow solid (3 mmol, 0.94 g) and CpTiCl3(3 mmol, 0.63 g) were separately dissolved in toluene (20 ml) at -30 °C under nitrogen. The yellow solid solution was added to the CpTiCl3solution. After 10 h of reaction, the reaction solution was filtered, concentrated and recrystallized to obtain an orange-red metallocene complex 4, 0.7 g, with a yield of 50%.

[0091] NMR of hydrogen: 1 H NMR (500 MHz, CDC13) δ 1.25 (s, 9H), 1.44 (s, 9H), δ 4.18 (s, 2H), δ 6.54 (s, 5H), δ 6.95 (d, 1H), δ 7.22 (q, 4H), δ 7.34 (t, 2H)

[0092] Elemental analysis of the target molecular formula C 26 H 31 Cl2OTi (%)

[0093] Theoretical analysis: C, 65.29; H, 6.53. Found: C, 64.98; H, 6.89.

[0094] Example 5: Preparation of complex 5

[0095]

[0096] A gray-green solution was obtained by using benzyl chloride (3 mmol, 0.38 g) and phenol (3 mmol, 0.30 g) as raw materials, dissolving in dichloromethane, using FeCl3as a catalyst, and reacting at room temperature for 12 h under nitrogen. The reaction solution was filtered, concentrated, and separated by column chromatography with petroleum ether: ethyl acetate = 10: 1 to obtain a yellow solid (compound 3) 0.22 g, with a yield of 40%.

[0097] A 2.5 M solution of n-butyllithium in hexane (3 mmol, 1.2 ml) was added dropwise to a solution of the ligand (compound 3) (3 mmol, 0.55 g) in hexane (20 ml) at -30 °C under nitrogen. After 10 h of reaction, the solution was filtered and concentrated. The yellow solid was recrystallized to obtain a yellow solid. The yellow solid (3 mmol, 0.57 g) and CpTiCl3(3 mmol, 0.63 g) were separately dissolved in toluene (20 ml) at -30 °C under nitrogen. The solution of the yellow solid was added to the solution of CpTiCl3. After 10 h of reaction, the solution was filtered and concentrated. The orange-red metallocene complex 5 was recrystallized to obtain 0.52 g in 47% yield.

[0098] Elemental analysis of the target molecule with the formula C 18 H 16 Cl2OTi (%)

[0099] Theoretical analysis: C, 58.89; H, 4.39. Found: C, 58.85; H, 4.44.

[0100] Example 6: Preparation of complex 6

[0101]

[0102] A gray-green solution was obtained by using pentafluorobenzyl chloride (3 mmol, 0.65 g) and phenol (3 mmol, 0.30 g) as raw materials, dissolving in dichloromethane, using FeCl3as a catalyst, and reacting at room temperature for 12 h under nitrogen. The solution was filtered and concentrated. The yellow solid (compound 4) was separated by column chromatography using petroleum ether: ethyl acetate = 10: 1 to obtain 0.48 g in 42% yield.

[0103] A 2.5 M solution of n-butyllithium in hexane (3 mmol, 1.2 ml) was added dropwise to a solution of the ligand (compound 4) (3 mmol, 1.15 g) in hexane (20 ml) at -30 °C under nitrogen. After 10 h of reaction, the solution was filtered and concentrated. The white solid was recrystallized to obtain a white solid. The white solid (3 mmol, 1.17 g) and CpTiCl3(3 mmol, 0.63 g) were separately dissolved in toluene (20 ml) at -30 °C under nitrogen. The solution of the white solid was added to the solution of CpTiCl3. After 10 h of reaction, the solution was filtered and concentrated. Then, 3.0 M methylmagnesium bromide in ether (3 mmol, 1 ml) was added at -30 °C. After 1 h of reaction, the solution was filtered and recrystallized using diatomite to obtain the orange-red metallocene complex 6 in 51% yield.

[0104] Elemental analysis of the target molecule with the formula C 28 H 33F5OTi(%)

[0105] Theoretical analysis: C, 63.64; H, 6.29. Found: C, 63.51; H, 6.52.

[0106] Example 7: Preparation of complex 7

[0107]

[0108] A 2.5M solution of n-butyllithium in n-hexane (3 mmol, 1.2 ml) was added dropwise to a solution of the heteroatomic ligand (compound 1) (3 mmol, 0.94 g) in n-hexane (20 ml) at -78°C under nitrogen. After 12 h of reaction, the reaction solution was filtered, concentrated and recrystallized to obtain a white solid. The white solid (3 mmol, 0.96 g) and C 12 H 21 SiTiCl3(3 mmol, 1.03 g) were dissolved in toluene (20 ml) respectively, and the solution of the white solid was added to the solution of SiTiCl3. After 12 h of reaction, the reaction solution was filtered, concentrated and recrystallized to obtain the orange-red metallocene-nonmetallocene complex 15, 0.9 g, with a yield of 45%. 12 H 21 SiTiCl3(3 mmol, 1.03 g) were dissolved in toluene (20 ml) respectively, and the solution of the white solid was added to the solution of SiTiCl3. After 12 h of reaction, the reaction solution was filtered, concentrated and recrystallized to obtain the orange-red metallocene-nonmetallocene complex 15, 0.9 g, with a yield of 45%.

[0109] NMR of hydrogen: 1 H NMR (500 MHz, C6D6) δ 0.48 (s, 9H), 1.12 (s, 9H), δ 1.56 (s, 9H), δ 1.87 (s, 6H), δ 2.46 (d, 6H), δ 6.88 (tt, 1H), δ 7.00 (tt, 2H), δ 7.28 (dt, 2H), δ 7.44 (q, 2H).

[0110] Elemental analysis of the target molecule formula C 33 H 48 Cl2OSSiTi(%)

[0111] Theoretical analysis: C, 65.23; H, 7.96. Found: C, 65.12; H, 8.05.

[0112] Example 8: Preparation of complex 8

[0113]

[0114] A mixture of m-xylene-2-sulfonyl chloride (3 mmol, 0.52 g) and phenol (3 mmol, 0.30 g) was dissolved in dichloromethane under nitrogen at room temperature using FeCl3as catalyst for 12 h to obtain a greenish solution. The reaction solution was filtered and concentrated, and the product was isolated by column chromatography using petroleum ether: ethyl acetate (10:1) to obtain a yellow solid (compound 5) 0.10 g with a yield of 40%.

[0115] A 2.5 M solution of n-butyllithium in n-hexane (3 mmol, 1.2 ml) was added dropwise to a solution of the ligand (compound 5) (3 mmol, 0.61 g) in n-hexane (20 ml) at -78°C under nitrogen. After 12 h, the reaction solution was filtered and concentrated, and the white solid was recrystallized. The white solid (3 mmol, 0.62 g) and C8H 12 H 21 SiTiCl3(3 mmol, 0.87 g) was dissolved in toluene (20 ml) separately, and the white solid solution was added to the C8H 12 H 21 SiTiCl3solution and reacted for 12 h. The reaction solution was filtered and concentrated, and the product was recrystallized to obtain an orange-red metallocene- nonmetallocene complex 8, 0.68 g with a yield of 50%.

[0116] Elemental analysis of the target molecule was C 24 H 29 Cl2OSSiTi (%)

[0117] Theoretical analysis: C, 56.26; H, 5.70. Found: C, 56.03; H, 5.92.

[0118] Example 9: Preparation of complex 9

[0119]

[0120] A 2.5 M solution of n-butyllithium in n-hexane (3 mmol, 1.2 ml) was added dropwise to a solution of the heteroatom-containing ligand (compound 5) (3 mmol, 0.61 g) in n-hexane (20 ml) at -78°C under nitrogen. After 12 h, the reaction solution was filtered and concentrated, and the white solid was recrystallized. The white solid (3 mmol, 0.62 g) and C8H 13 SiTiCl3(3 mmol, 0.87 g) was dissolved in toluene (20 ml) separately, and the white solid solution was added to the C8H 13 SiTiCl3solution and reacted for 12 h. The reaction solution was filtered and concentrated, and the product was recrystallized to obtain an orange-red metallocene- nonmetallocene complex 8, 0.68 g with a yield of 50%.

[0121] Elemental analysis of the target molecule formula is C 20 H 22 Cl2OSSiTi(%)

[0122] Theoretical analysis: C, 52.53; H, 4.85. Found: C, 52.39; H, 5.13.

[0123] Example 10: Preparation of complex 10

[0124]

[0125] A 2.5M solution of n-butyllithium in n-hexane (3 mmol, 1.2 ml) was added dropwise to a solution of the ligand (compound 4) (3 mmol, 1.16 g) in n-hexane (20 ml) at -78°C under nitrogen. After 12 h of reaction, the reaction solution was filtered, concentrated and recrystallized to obtain a white solid. The white solid (3 mmol, 1.17 g) and C8H 13 SiTiCl3(3 mmol, 0.87 g) were dissolved in toluene (20 ml) respectively, and the white solid solution was added to the C8H 13 SiTiCl3solution, and the reaction was carried out for 12 h. The reaction solution was filtered, concentrated and recrystallized to obtain the orange-red metallocene- nonmetallocene complex 10, 0.92 g, with a yield of 48%.

[0126] Elemental analysis of the target molecule formula is C 29 H 35 Cl2F5OSiTi(%)

[0127] Theoretical analysis: C, 54.30; H, 5.50. Found: C, 54.21; H, 5.62.

[0128] Example 11: Preparation of complex 11

[0129]

[0130] A 2.5M solution of n-butyllithium in n-hexane (3 mmol, 1.2 ml) was added dropwise to a solution of the heteroatom-containing ligand (compound 1) (3 mmol, 0.94 g) in n-hexane (20 ml) at -78°C under nitrogen. After 12 h of reaction, the reaction solution was filtered, concentrated and recrystallized to obtain a white solid. The white solid (3 mmol, 0.96 g) and C8H 10 H 10 TiCl3(3 mmol, 0.87 g) were dissolved in toluene (20 ml) respectively, and the white solid solution was added to the C8H 10 H 10The reaction solution was filtered, concentrated, and recrystallized to obtain the orange-red metallocene complex 12, 0.92 g, in a yield of 51%.

[0131] Elemental analysis of the target molecule formula C 30 H 35 Cl2OSTi (%)

[0132] Theoretical analysis: C, 64.07; H, 6.27. Actual value: C, 64.01; H, 6.53.

[0133] Example 12: Preparation of complex 12

[0134]

[0135] A 2.5 M n-butyllithium solution in n-hexane (3 mmol, 1.2 ml) was added dropwise to a solution of the heteroatomic ligand (compound 1) (3 mmol, 0.94 g) in n-hexane (20 ml) at -78°C under nitrogen. After 12 h of reaction, the solution was filtered, concentrated, and recrystallized to obtain a white solid. The white solid (3 mmol, 0.96 g) and C 10 H 10 TiCl3(3 mmol, 0.87 g) were dissolved in toluene (20 ml) respectively, and the white solid solution was added to the C 10 H 10 The reaction solution was filtered, concentrated, and recrystallized to obtain the orange-red metallocene complex 12, 0.92 g, in a yield of 51%.

[0136] Elemental analysis of the target molecule formula C 34 H 37 Cl2OSTi (%)

[0137] Theoretical analysis: C, 64.07; H, 6.27. Actual value: C, 64.01; H, 6.53.

[0138] Example 13

[0139] In a glove box, 40 mL of toluene was added to a 150 mL polymerization bottle, which was connected to an ethylene device for gas exchange, and ethylene = 2 atm; complex 1 (5 mg, 10 μmol), AlEt3(10 μmol), and MAO (10 mL) were added to the bottle, and the bottle was sealed and placed in an oil bath at 60°C. After 24 h of reaction, the reaction solution was filtered, concentrated, and recrystallized to obtain the orange-red metallocene complex 12, 0.92 g, in a yield of 51%. iBu3 (0.4 ml, 200 μmol, 0.5 M toluene solvent) and triphenyl carborate [Ph3C][B(C6F5)4] (9.2 mg, 10 μmol) were dissolved in toluene to prepare a catalyst composition. The catalyst composition was rapidly injected into a polymerization flask using a syringe to initiate polymerization. After 20 min, 2 ml of hydrochloric acid-ethanol solution (v / v, 1:10) was added to terminate the polymerization reaction. The polymerization reaction solution was then poured into 100 ml of ethanol to settle, filtered, and vacuum dried for 24 h to obtain ultra-high molecular weight polyethylene with a net weight of 0.43 g.

[0140] Example 14

[0141] In a glove box, 40 mL of toluene was added to a 150 mL polymerization flask, and the ethylene apparatus was placed inside for evacuation, with ethylene concentration at 4 atm. Complex 1 (5 mg, 10 μmol) and Al were then added. i Bu3 (0.4 ml, 200 μmol, 0.5 M toluene solvent) and triphenyl carborate [Ph3C][B(C6F5)4] (9.2 mg, 10 μmol) were dissolved in toluene to prepare a catalyst composition. The catalyst composition was rapidly injected into a polymerization bottle through a syringe to initiate polymerization. After 15 min, 2 ml of hydrochloric acid ethanol solution (v / v, 1:10) was added to terminate the polymerization reaction. The polymerization reaction solution was then poured into 100 ml of ethanol to settle, filtered, and vacuum dried for 24 h to obtain ultra-high molecular weight polyethylene with a net weight of 0.47 g.

[0142] The product determination in this embodiment is based on the homopolymer measured in C2D2Cl4 at 110°C. 1 The HNMR spectrum was obtained; the polymer melting point (T) was obtained. m The viscosity-average molecular weight of the polymer (M) was determined by differential scanning calorimetry (DSC). n The viscosity was determined using a viscometer at 135°C with decahydronaphthalene as the mobile phase.

[0143] The ultra-high molecular weight polyethylene obtained in Example 14 was analyzed using nuclear magnetic resonance (NMR) to obtain its... 1 H NMR spectrum

[0144] Differential scanning calorimetry was used to test and analyze it, and its DSC chart was obtained, as shown below. Figure 3 As shown. Figure 3 The DSC curves show the obtained polyethylene T g =136.9℃ and crystallinity X=74.1%. Its viscosity-average molecular weight was analyzed using a viscometer, and a KPIC chart was obtained, as shown below. Figure 4 As shown.

[0145] Example 15

[0146] In a glove box, 40 mL of toluene was added to a 150 mL polymerization bottle, which was evacuated and backfilled with ethylene = 6 atm; complex 1 (5 mg, 10 μmol), AlEt3(0.2 mL, 200 μmol, 0.5 M in toluene), and [Ph3C][B(C6F5)4] (9.2 mg, 10 μmol) were dissolved in toluene to make the catalyst composition; the polymerization was initiated by rapidly injecting the catalyst composition into the polymerization bottle via syringe; the polymerization was terminated after 2 min by adding 2 mL of an ethanolic hydrochloric acid solution (v / v, 1:10); the polymerization solution was then poured into 100 mL of ethanol to settle, filtered, and vacuum dried for 24 h to give 0.53 g of UHMWPE. i Bu3(0.4 mL, 200 μmol, 0.5 M in toluene) and [Ph3C][B(C6F5)4] (9.2 mg, 10 μmol) were dissolved in toluene to make the catalyst composition; the polymerization was initiated by rapidly injecting the catalyst composition into the polymerization bottle via syringe; the polymerization was terminated after 10 min by adding 2 mL of an ethanolic hydrochloric acid solution (v / v, 1:10); the polymerization solution was then poured into 100 mL of ethanol to settle, filtered, and vacuum dried for 24 h to give 0.18 g of UHMWPE.

[0147] Example 16

[0148] In a glove box, 40 mL of toluene was added to a 150 mL polymerization bottle, which was evacuated and backfilled with ethylene = 6 atm; complex 2 (4.5 mg, 10 μmol), AlEt3(0.2 mL, 200 μmol, 0.5 M in toluene), and [Ph3C][B(C6F5)4] (9.2 mg, 10 μmol) were dissolved in toluene to make the catalyst composition; the polymerization was initiated by rapidly injecting the catalyst composition into the polymerization bottle via syringe; the polymerization was terminated after 2 min by adding 2 mL of an ethanolic hydrochloric acid solution (v / v, 1:10); the polymerization solution was then poured into 100 mL of ethanol to settle, filtered, and vacuum dried for 24 h to give 0.53 g of UHMWPE. i Bu3(0.4 mL, 200 μmol, 0.5 M in toluene) and [Ph3C][B(C6F5)4] (9.2 mg, 10 μmol) were dissolved in toluene to make the catalyst composition; the polymerization was initiated by rapidly injecting the catalyst composition into the polymerization bottle via syringe; the polymerization was terminated after 10 min by adding 2 mL of an ethanolic hydrochloric acid solution (v / v, 1:10); the polymerization solution was then poured into 100 mL of ethanol to settle, filtered, and vacuum dried for 24 h to give 0.18 g of UHMWPE.

[0149] Example 17

[0150] In a glove box, 40 mL of toluene was added to a 150 mL polymerization bottle, which was evacuated and backfilled with ethylene = 6 atm; complex 3 (4 mg, 10 μmol), AlEt3(0.2 mL, 200 μmol, 0.5 M in toluene), and [Ph3C][B(C6F5)4] (9.2 mg, 10 μmol) were dissolved in toluene to make the catalyst composition; the polymerization was initiated by rapidly injecting the catalyst composition into the polymerization bottle via syringe; the polymerization was terminated after 2 min by adding 2 mL of an ethanolic hydrochloric acid solution (v / v, 1:10); the polymerization solution was then poured into 100 mL of ethanol to settle, filtered, and vacuum dried for 24 h to give 0.53 g of UHMWPE. i Bu3(0.4 mL, 200 μmol, 0.5 M in toluene) and [Ph3C][B(C6F5)4] (9.2 mg, 10 μmol) were dissolved in toluene to make the catalyst composition; the polymerization was initiated by rapidly injecting the catalyst composition into the polymerization bottle via syringe; the polymerization was terminated after 10 min by adding 2 mL of an ethanolic hydrochloric acid solution (v / v, 1:10); the polymerization solution was then poured into 100 mL of ethanol to settle, filtered, and vacuum dried for 24 h to give 0.18 g of UHMWPE.

[0151] Example 18

[0152] In a glove box, 40 mL of toluene was added to a 150 mL polymerization bottle, which was evacuated and backfilled with ethylene = 6 atm; complex 4 (4 mg, 10 μmol), Al i Bu3(0.4 ml, 200 μmol, 0.5 M in toluene) and [Ph3C][B(C6F5)4] (9.2 mg, 10 μmol) were dissolved in toluene to make the catalyst composition; the polymerization was initiated by injecting the catalyst composition into the polymerization bottle via syringe, and the polymerization was terminated after 10 min by adding 2 mL of an ethanolic hydrochloric acid solution (v / v, 1:10), and the polymerization solution was poured into 100 mL of ethanol to precipitate the polymer, which was filtered and vacuum dried for 24 h to give 0.07 g of UHMWPE.

[0153] Example 19

[0154] In a glove box, 40 mL of toluene was added to a 150 mL polymerization bottle, which was evacuated and backfilled with ethylene = 6 atm; complex 5 (3.6 mg, 10 μmol), Al i Bu3(0.4 ml, 200 μmol, 0.5 M in toluene) and [Ph3C][B(C6F5)4] (9.2 mg, 10 μmol) were dissolved in toluene to make the catalyst composition; the polymerization was initiated by injecting the catalyst composition into the polymerization bottle via syringe, and the polymerization was terminated after 10 min by adding 2 mL of an ethanolic hydrochloric acid solution (v / v, 1:10), and the polymerization solution was poured into 100 mL of ethanol to precipitate the polymer, which was filtered and vacuum dried for 24 h to give 0.13 g of UHMWPE.

[0155] Example 20

[0156] In a glove box, 40 mL of toluene was added to a 150 mL polymerization bottle, which was evacuated and backfilled with ethylene = 6 atm; complex 6 (5 mg, 10 μmol), Al i Bu3(0.4 ml, 200 μmol, 0.5 M in toluene) and [Ph3C][B(C6F5)4] (9.2 mg, 10 μmol) were dissolved in toluene to make the catalyst composition; the polymerization was initiated by injecting the catalyst composition into the polymerization bottle via syringe, and the polymerization was terminated after 10 min by adding 2 mL of an ethanolic hydrochloric acid solution (v / v, 1:10), and the polymerization solution was poured into 100 mL of ethanol to precipitate the polymer, which was filtered and vacuum dried for 24 h to give 0.24 g of UHMWPE.

[0157] Example 21

[0158] In a glove box, 40 mL of toluene was added to a 150 mL polymerization bottle, which was evacuated and backfilled with ethylene = 6 atm; complex 7 (5 mg, 10 μmol), AlEt3(0.2 mL, 200 μmol, 0.5 M in toluene), and [Ph3C][B(C6F5)4] (9.2 mg, 10 μmol) were dissolved in toluene to make the catalyst composition; the catalyst composition was quickly injected into the polymerization bottle via syringe to initiate polymerization; the polymerization was terminated after 10 min by adding 2 mL of an ethanolic HCl solution (v / v, 1:10); the polymerization solution was then poured into 100 mL of ethanol to precipitate the polymer; the polymer was filtered and vacuum dried for 24 h to give 0.11 g of UHMWPE. i Bu3(0.4 mL, 200 μmol, 0.5 M in toluene) and [Ph3C][B(C6F5)4] (9.2 mg, 10 μmol) were dissolved in toluene to make the catalyst composition; the catalyst composition was quickly injected into the polymerization bottle via syringe to initiate polymerization; the polymerization was terminated after 10 min by adding 2 mL of an ethanolic HCl solution (v / v, 1:10); the polymerization solution was then poured into 100 mL of ethanol to precipitate the polymer; the polymer was filtered and vacuum dried for 24 h to give 0.05 g of UHMWPE.

[0159] Example 22

[0160] In a glove box, 40 mL of toluene was added to a 150 mL polymerization bottle, which was evacuated and backfilled with ethylene = 6 atm; complex 8 (5 mg, 10 μmol), AlEt3(0.2 mL, 200 μmol, 0.5 M in toluene), and [Ph3C][B(C6F5)4] (9.2 mg, 10 μmol) were dissolved in toluene to make the catalyst composition; the catalyst composition was quickly injected into the polymerization bottle via syringe to initiate polymerization; the polymerization was terminated after 10 min by adding 2 mL of an ethanolic HCl solution (v / v, 1:10); the polymerization solution was then poured into 100 mL of ethanol to precipitate the polymer; the polymer was filtered and vacuum dried for 24 h to give 0.05 g of UHMWPE. i Bu3(0.4 mL, 200 μmol, 0.5 M in toluene) and [Ph3C][B(C6F5)4] (9.2 mg, 10 μmol) were dissolved in toluene to make the catalyst composition; the catalyst composition was quickly injected into the polymerization bottle via syringe to initiate polymerization; the polymerization was terminated after 10 min by adding 2 mL of an ethanolic HCl solution (v / v, 1:10); the polymerization solution was then poured into 100 mL of ethanol to precipitate the polymer; the polymer was filtered and vacuum dried for 24 h to give 0.05 g of UHMWPE.

[0161] Example 23

[0162] In a glove box, 40 mL of toluene was added to a 150 mL polymerization bottle, which was evacuated and backfilled with ethylene = 6 atm; complex 9 (4.5 mg, 10 μmol), AlEt3(0.2 mL, 200 μmol, 0.5 M in toluene), and [Ph3C][B(C6F5)4] (9.2 mg, 10 μmol) were dissolved in toluene to make the catalyst composition; the catalyst composition was quickly injected into the polymerization bottle via syringe to initiate polymerization; the polymerization was terminated after 10 min by adding 2 mL of an ethanolic HCl solution (v / v, 1:10); the polymerization solution was then poured into 100 mL of ethanol to precipitate the polymer; the polymer was filtered and vacuum dried for 24 h to give 0.05 g of UHMWPE. i Bu3(0.4 mL, 200 μmol, 0.5 M in toluene) and [Ph3C][B(C6F5)4] (9.2 mg, 10 μmol) were dissolved in toluene to make the catalyst composition; the catalyst composition was quickly injected into the polymerization bottle via syringe to initiate polymerization; the polymerization was terminated after 10 min by adding 2 mL of an ethanolic HCl solution (v / v, 1:10); the polymerization solution was then poured into 100 mL of ethanol to precipitate the polymer; the polymer was filtered and vacuum dried for 24 h to give 0.05 g of UHMWPE.

[0163] Example 24

[0164] In a glove box, 40 mL of toluene was added to a 150 mL polymerization bottle, which was evacuated and backfilled with ethylene = 6 atm; complex 10 (6.4 mg, 10 μmol), AlEt3(0.2 mL, 200 μmol, 0.5 M in toluene), and Bu3(0.4 mL, 200 μmol, 0.5 M in toluene) were added to the bottle. The polymerization was initiated by rapidly injecting the catalyst composition into the bottle via syringe. The polymerization was terminated after 10 min by adding 2 mL of an ethanolic HCl solution (v / v, 1:10). The polymerization solution was then poured into 100 mL of ethanol to precipitate the polymer. The polymer was filtered and vacuum dried for 24 h to give 0.21 g of UHMWPE. i Bu3(0.4 mL, 200 μmol, 0.5 M in toluene) and [Ph3C][B(C6F5)4] (9.2 mg, 10 μmol) were dissolved in toluene to make the catalyst composition; the polymerization was initiated by rapidly injecting the catalyst composition into the polymerization bottle via syringe. The polymerization was terminated after 10 min by adding 2 mL of an ethanolic HCl solution (v / v, 1:10). The polymerization solution was then poured into 100 mL of ethanol to precipitate the polymer. The polymer was filtered and vacuum dried for 24 h to give 0.75 g of UHMWPE.

[0165] Example 25

[0166] In a glove box, 40 mL of toluene was added to a 150 mL polymerization bottle, which was evacuated and backfilled with ethylene = 6 atm; complex 10 (6.4 mg, 10 μmol), AlEt3(0.2 mL, 200 μmol, 0.5 M in toluene), and Bu3(0.4 mL, 200 μmol, 0.5 M in toluene) were added to the bottle. The polymerization was initiated by rapidly injecting the catalyst composition into the bottle via syringe. The polymerization was terminated after 10 min by adding 2 mL of an ethanolic HCl solution (v / v, 1:10). The polymerization solution was then poured into 100 mL of ethanol to precipitate the polymer. The polymer was filtered and vacuum dried for 24 h to give 0.21 g of UHMWPE. i Bu3(0.4 mL, 200 μmol, 0.5 M in toluene) and [Ph3C][B(C6F5)4] (9.2 mg, 10 μmol) were dissolved in toluene to make the catalyst composition; the polymerization was initiated by rapidly injecting the catalyst composition into the polymerization bottle via syringe. The polymerization was terminated after 10 min by adding 2 mL of an ethanolic HCl solution (v / v, 1:10). The polymerization solution was then poured into 100 mL of ethanol to precipitate the polymer. The polymer was filtered and vacuum dried for 24 h to give 0.75 g of UHMWPE.

[0167] Example 25

[0168] In a glove box, 40 mL of toluene was added to a 150 mL polymerization bottle, which was evacuated and backfilled with ethylene = 6 atm; complex 10 (6.4 mg, 10 μmol), AlEt3(0.2 mL, 200 μmol, 0.5 M in toluene), and Bu3(0.4 mL, 200 μmol, 0.5 M in toluene) were added to the bottle. The polymerization was initiated by rapidly injecting the catalyst composition into the bottle via syringe. The polymerization was terminated after 10 min by adding 2 mL of an ethanolic HCl solution (v / v, 1:10). The polymerization solution was then poured into 100 mL of ethanol to precipitate the polymer. The polymer was filtered and vacuum dried for 24 h to give 0.21 g of UHMWPE. i Bu3(0.4 mL, 200 μmol, 0.5 M in toluene) and [Ph3C][B(C6F5)4] (9.2 mg, 10 μmol) were dissolved in toluene to make the catalyst composition; the polymerization was initiated by rapidly injecting the catalyst composition into the polymerization bottle via syringe. The polymerization was terminated after 10 min by adding 2 mL of an ethanolic HCl solution (v / v, 1:10). The polymerization solution was then poured into 100 mL of ethanol to precipitate the polymer. The polymer was filtered and vacuum dried for 24 h to give 0.75 g of UHMWPE.

[0169] Referring to Table 1, Table 1 is the condition and result data of preparing the ultra-high molecular weight polyethylene in Examples 13-26 of the present application.

[0170] Table 1 Condition and result data table of ethylene homopolymerization

[0171]

[0172] The results show that the metallocene-non-metallocene metal complex in the embodiments of the present disclosure can catalyze ethylene to polymerize after being activated by the boron-containing cocatalyst, and the polymerization activity can be as high as 1.59 x 10 6 g / mol h, the melting point can be as high as 136.9℃, the crystallinity can be as high as 74.1%, and the viscosity-average molecular weight of the ultra-high molecular weight polyethylene is in the range of 100w-500w.

[0173] The above description is merely preferred specific embodiments of the present application, but the protection scope of the present application is not limited thereto, and any person skilled in the art can make equivalent replacements or changes to the technical solutions and the inventive concept of the present application within the technical scope disclosed by the present application, which should be covered within the protection scope of the present application.

Claims

1. A complex represented by formula (I), formula (II) or formula (III): Formula (I); Formula (II); Formula (III); wherein, Z is selected from S, O, (CH2) n ; n is 1 ; R1 is selected from unsubstituted C1-C12 alkyl or halogen; R2, R3 are independently selected from tert-butyl; R4, R5, R6, R7, R8 are independently selected from hydrogen or halogen; R9, R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 are each independently selected from hydrogen or unsubstituted C1-C12 alkyl.

2. The complex of claim 1, wherein Z is selected from S or CH2; R1 is selected from unsubstituted C1-C5 alkyl or halogen.

3. The complex of claim 2, wherein The R1 is selected from Cl, CH3; R9, R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 are each independently selected from the group consisting of hydrogen, methyl, ethyl, t-butyl, octyl.

4. A complex represented by formula (I), formula (II) or formula (III): Formula (I); Formula (II); Formula (III); wherein Z is selected from S, O, (CH2) n ; n is 1 ; R1 is selected from unsubstituted C1-C12 alkyl or halogen; R2, R3 are independently selected from hydrogen or unsubstituted C1-C12 alkyl; R4, R5, R6, R7, R8 are independently selected from hydrogen or halogen; R9 is selected from trimethylsilyl; R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 are each independently selected from hydrogen or an unsubstituted C1-C12 alkyl group.

5. The complex of claim 4, wherein Z is selected from S or CH2; R1 is selected from unsubstituted C1-C5 alkyl or halogen; R2, R3 are independently selected from hydrogen or unsubstituted C1-C5 alkyl.

6. The complex of claim 5, wherein, The R1 is selected from Cl, CH3; The R2, R3 are any one of tert-butyl, methyl, octyl; R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 are each independently selected from the group consisting of hydrogen, methyl, ethyl, t-butyl, octyl.

7. The complex according to any one of claims 1 to 6, characterized in that, The complex is selected from: Complex 1: ； Complex 2: ； Complex 3: ； Complex 4: ； Complex 6: ； Complex 7: ； Complex 8: ； Complex 9: ； Complex 10: ； Complex 11: ； Complex 12: 。 8. The complex according to claim 7, having a structure of formula (1) to formula (4): Formula (1); Formula (2); Formula (3); Formula (4).

9. A catalyst composition comprising the complex according to any one of claims 1 to 8, an organic boron salt compound and an organic aluminum compound.

10. The composition of claim 9, wherein, The molar ratio of the complex, the organic boron salt compound and the organic aluminum compound is 1:0.5-5:1-100; The organic boron salt compound is selected from one or more of [Ph3C][B(C6F5)4], [PhNMe2H][BPh4], [NEt3H][BPh4], B(C6F5)3 and [PhNMe2H][B(C6F5)4]; The organic aluminum compound is selected from one or more of trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisopropylaluminum, triisobutylaluminum, tri-n-pentylaluminum, tri-n-hexylaluminum, tricyclohexylaluminum, tri-n-octylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldibenzylaluminum and ethyldi(p-tolyl)aluminum.

11. A method for preparing ultra-high molecular weight polyethylene, comprising the following steps: Polymerizing an ethylene-based monomer under the action of the catalyst composition according to claim 9 or 10 to obtain ultra-high molecular weight polyethylene.

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