Aza-cycloborane metal complexes, methods of making and using same, and copolymerization of ethylene and norbornene

Abstract

The present application relates to the technical field of metallocene compounds, in particular to a nitrogen heterocyclic boroxine metal complex, a preparation method and application thereof, and a copolymerization reaction of ethylene and norbornene, the nitrogen heterocyclic boroxine metal complex has a structure shown in formula (I), wherein, R 1 is selected from hydrogen, substituted or unsubstituted C1-C 10 alkyl, substituted or unsubstituted C6-C 12 aromatic group; Cp' is selected from substituted or unsubstituted cyclopentadienyl and derivatives thereof; M is selected from group IVB metal elements; R 2 and R 3 are each independently selected from halogen, substituted or unsubstituted C1-C 10 alkyl, substituted or unsubstituted C1-C 10 alkoxy, and substituted or unsubstituted benzyl, the nitrogen heterocyclic boroxine metal complex provided by the present application has high structural stability and catalytic activity.

Description

Technical Field

[0001] This invention relates to the field of metallocene complex technology, specifically to a nitrogen heterocyclic borooxy metal complex, its preparation method and application, and a copolymerization reaction of ethylene and norbornene. Background Technology

[0002] Polyolefin products play an increasingly important role in our daily lives, and various high-performance polymer products have been widely used in our daily lives. Among them, certain cyclic olefin copolymers (COCs) have received increasing attention due to their high transparency and excellent properties such as moisture resistance, heat resistance, and high glass transition temperature (Tg). The actual production of COCs usually involves three processes, such as: (1) ring-opening, metathesis polymerization of polycyclic olefins and subsequent hydrogenation; (2) coordination copolymerization of ethylene and cyclic olefins; and (3) homopolymerization of cyclic olefins. In particular, copolymerization, which can control the polymer ratio and microstructure, makes the polymer material properties controllable and variable. Therefore, various complexes are used to catalyze the copolymerization of ethylene and NBE, such as metallocenes, linked semi-titanium olefins (so-called restricted geometry types), unbridged semi-titanium olefins, and other so-called non-metallocenes. These COC materials are commercialized using metallocene catalysts (such as TOPASVR) as ultrapure (suitable for high-end pharmaceutical packaging and food contact films), crystal clear (glass transparent and amorphous), and high barrier (moisture, alcohol, and acid resistant) materials. However, successful examples of synthesizing random, high molecular weight copolymers with high NBE content (>50 mol%) are still limited. COC materials have been commercialized and have broad development prospects in fields such as advanced optics, medical devices, containers, and packaging, and have developed rapidly in recent years, showing strong momentum.

[0003] Monocyclic metal catalysts have been extensively studied and applied in scientific research and industrial production in recent years due to their excellent catalytic performance and diverse ligand structures. Among them, the monocyclic catalyst containing aryloxy ligands (Cp'Ti(OAr)Cl2) not only has good activity in the polymerization of ethylene, styrene and non-conjugated dienes, but also exhibits excellent copolymerization ability in the copolymerization of cyclic olefins, α-olefins and ethylene.

[0004] Nomura reported an aryl oxygen electron donor complex containing an electron-withdrawing group on its aryl group, which exhibited excellent catalytic performance in the copolymerization of ethylene and norbornene (Organometallics 2016, 35, 1895-1905). This type of aryl oxygen monoceramic titanium complex containing electron-withdrawing substituents exhibits more efficient catalytic behavior than its electron-donating substituent analogs, but it has low polymerization activity and poor thermal stability.

[0005] Kretschmer and Hessen reported an imidazolinidine-imine electron donor complex (Chemical Communications, 2002, 114(6):608-609) as a catalyst precursor for olefin polymerization. Under the condition of B(C6F5)3 as a co-catalyst, this complex exhibited high catalytic activity in the homopolymerization of ethylene, even higher than its acyl ketone imine electron donor analog and phosphorine imine electron donor analog. However, due to the isomerization of its ligands, it is unstable in the polymerization of olefins and is prone to generating multiple active centers. Summary of the Invention

[0006] The purpose of this invention is to overcome the problems of low activity, poor thermal stability, unstable polymerization, and easy generation of multiple active centers in existing metal complexes used for catalyzing the polymerization of unsaturated olefins. This invention provides a new azaheterocyclic borooxy metal complex, its preparation method and application, and a copolymerization reaction of ethylene and norbornene. By optimizing the ligand structure, this azaheterocyclic borooxy metal complex exhibits good activity, thermal stability and controllability in catalyzing the copolymerization of ethylene and norbornene.

[0007] To achieve the above objectives, a first aspect of the present invention provides a nitrogen-heterocyclic borooxy metal complex having the structure shown in formula (I):

[0008]

[0009] Among them, R 1 Selected from hydrogen, substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C6-C 12 Aromatic group; Cp' is selected from substituted or unsubstituted cyclopentadienyl groups and their derivatives; M is selected from Group IVB metal elements; R 2 and R 3 Each is independently selected from halogenated, substituted or unsubstituted C1-C. 10 Alkyl, substituted or unsubstituted C1-C 10 Alkoxy, substituted or unsubstituted benzyl.

[0010] Preferably, R 1 It is selected from hydrogen, methyl, ethyl, propyl, tert-butyl, phenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, and 2,4,6-trimethylphenyl.

[0011] Preferably, the hydrocarbon group in Cp' is selected from C1-C5 alkyl groups, and more preferably from methyl, ethyl, propyl, and tert-butyl groups.

[0012] Preferably, M is selected from Ti, Zr, and Hf.

[0013] Preferably, R 2 and R 3 Each is independently selected from fluorine, chlorine, methyl, ethyl, isopropyl, methoxy, and benzyl.

[0014] A second aspect of the present invention provides a method for preparing a nitrogen-containing heterocyclic borooxy metal complex, the method comprising the following steps:

[0015] (1) In the presence of an inert gas and a first solvent, the compound shown in formula (II) and sodium hydride are subjected to a first reaction, and then a metal ligand with the general formula Cp'MX3 is added to carry out a second reaction. The first solvent is removed by a first depressurization, and the intermediate product obtained is used as a nitrogen heterocyclic borooxy metal complex.

[0016] (2) Optionally, in the presence of an inert gas and a second solvent, the intermediate product and the alkyl Grignard reagent are subjected to a third reaction to obtain a nitrogen heterocyclic borooxy metal complex;

[0017]

[0018] The nitrogen-containing heterocyclic borooxy metal complex has the structure shown in formula (I), wherein R 1 Selected from hydrogen, substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C6-C 12 Aromatic group; Cp' is selected from substituted or unsubstituted cyclopentadienyl groups and their derivatives; M is selected from Group IVB metal elements; R 2 and R 3 Each is independently selected from halogenated, substituted or unsubstituted C1-C. 10 Alkyl, substituted or unsubstituted C1-C 10 Alkoxy, substituted or unsubstituted benzyl.

[0019] The third aspect of this invention provides the application of the azaheterocyclic borooxy metal complex provided in the first aspect, or the azaheterocyclic borooxy metal complex prepared by the preparation method provided in the second aspect, in the catalytic polymerization of unsaturated olefins.

[0020] The fourth aspect of the present invention provides a copolymerization reaction of ethylene and norbornene, wherein ethylene and norbornene are contacted and copolymerized in the presence of a catalyst, a co-catalyst and a polymerization solvent to obtain an ethylene-norbornene copolymer.

[0021] The catalyst is selected from the nitrogen-heterocyclic borooxy metal complex provided in the first aspect, or the nitrogen-heterocyclic borooxy metal complex prepared by the preparation method provided in the second aspect.

[0022] Compared with the prior art, the present invention has the following advantages:

[0023] (1) This invention provides a novel aza-heterocyclic borooxy metal complex (i.e., boro-nitrophenanthrene-oxymonocyclic group IVB metal complex). By optimizing the ligand structure, an easily tunable borooxy electron donor coordinates a non-bridged monocyclic group IVB metal complex. Since the borooxy bond is an isoelectronic imine bond, the borooxy ligand has a stronger π electron-donating ability than the aryl oxygen ligand. At the same time, it has suitable steric hindrance, which makes the aza-heterocyclic borooxy metal complex have high structural stability and catalytic activity.

[0024] (2) The preparation method of the nitrogen heterocyclic borooxy metal complex provided by the present invention is simple, the raw materials are simple and readily available, the cost is low, the properties are stable, and it is easy to industrialize.

[0025] (3) The nitrogen-heterocyclic borooxy metal complex provided by the present invention broadens the COC polymer catalyst system. At the same time, it catalyzes the polymerization of unsaturated olefins, especially the copolymerization of ethylene and norbornene. Due to the boron-oxygen electron-donating structure and large substituent steric hindrance in the nitrogen-heterocyclic borooxy metal complex, the catalytic active center has good stability. In particular, the weight-average molecular weight of the copolymer and the norbornene content in the copolymer can be controlled by the type of catalyst. Attached Figure Description

[0026] Figure 1 The image shows the 1H NMR spectrum of the nitrogen-containing heterocyclic borooxy metal complex S2 prepared in Example 2.

[0027] Figure 2 This is the 1H NMR spectrum of the nitrogen-containing heterocyclic borooxy metal complex S4 prepared in Example 4. Detailed Implementation

[0028] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0029] In this invention, unless otherwise specified, the terms "first," "second," "third," and "fourth" do not indicate a sequential order, nor do they limit the specific materials or steps; they are merely used to distinguish or indicate that these are not the same material or step. For example, in "first solvent," "second solvent," "third solvent," and "fourth solvent," "first," "second," "third," and "fourth" are used only to indicate that these are not the same solvent; similarly, in "first reaction," "second reaction," and "third reaction," "first," "second," and "third" are used only to indicate that these are not the same reaction.

[0030] A first aspect of the present invention provides a nitrogen-heterocyclic borooxy metal complex having the structure shown in formula (I):

[0031]

[0032] Among them, R 1 Selected from hydrogen, substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C6-C 12 Aromatic group; Cp' is selected from substituted or unsubstituted cyclopentadienyl groups and their derivatives; M is selected from Group IVB metal elements; R 2 and R 3 Each is independently selected from halogenated, substituted or unsubstituted C1-C. 10 Alkyl, substituted or unsubstituted C1-C 10 Alkoxy, substituted or unsubstituted benzyl.

[0033] In this invention, unless otherwise specified, the substituted or unsubstituted C1-C 10 Alkyl groups are selected from substituted C1-C 10 Alkyl, unsubstituted C1-C 10 Alkyl groups, wherein the substituted C1-C 10 The substituted groups in the alkyl group include, but are not limited to, N, O, S, halogens, hydrocarbon groups, etc., preferably hydrocarbon groups, and the unsubstituted C1-C... 10 Alkyl groups contain only C and H; similarly, substituted C6-C... 12 Aromatic groups, substituted cyclopentadienyl groups and their derivatives, substituted C1-C 10 The substituent groups in the alkoxy and substituted benzyl groups each independently include, but are not limited to, N, O, S, halogens, hydrocarbon groups, etc., and are preferably hydrocarbon groups.

[0034] In some embodiments of the present invention, preferably, in formula (I), R 1 Selected from hydrogen, alkyl-substituted or unsubstituted C1-C5 alkyl groups, alkyl-substituted or unsubstituted C6-C groups. 12 Aromatic group; more preferably, R 1Selected from hydrogen, C1-C5 alkyl, phenyl, and alkyl-substituted phenyl groups.

[0035] In some preferred embodiments of the present invention, preferably, in formula (I), R 1 The compounds are selected from hydrogen, methyl, ethyl, propyl, tert-butyl, phenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, and 2,4,6-trimethylphenyl. Under preferred conditions, the nitrogen-containing heterocyclic borosilicate metal complex shown in formula (I) exhibits higher catalytic activity during catalytic polymerization.

[0036] In some embodiments of the present invention, preferably, in formula (I), Cp' is selected from cyclopentadienyl with or without alkyl substituted, pentamethylcyclopentadienyl with or without alkyl substituted, tert-butylcyclopentadienyl with or without alkyl substituted, indole with or without alkyl substituted, and fluorenyl with or without alkyl substituted.

[0037] In some embodiments of the present invention, more preferably, Cp' is selected from cyclopentadienyl (substituted or unsubstituted), pentamethylcyclopentadienyl (substituted or unsubstituted), indene (substituted or unsubstituted), and fluorenyl (substituted or unsubstituted).

[0038] In some embodiments of the present invention, more preferably, Cp' is selected from cyclopentadienyl groups with or without substituted hydrocarbon groups, and pentamethylcyclopentadienyl groups with or without substituted hydrocarbon groups. Using preferred conditions is more conducive to improving the stability of the active center of the azahepto-boroxy metal complex shown in formula (I), thereby improving the catalytic activity of the azahepto-boroxy metal complex.

[0039] In some preferred embodiments of the present invention, preferably, the hydrocarbon group substitution in Cp' is selected from C1-C5 alkyl groups, and more preferably from methyl, ethyl, propyl, and tert-butyl groups.

[0040] In some embodiments of the present invention, preferably, in formula (I), M is selected from Ti, Zr, and Hf.

[0041] In some embodiments of the present invention, preferably, in formula (I), R 2 and R 3 Each is independently selected from halogenated, substituted or unsubstituted C1-C groups. 10 Alkyl, hydrocarbon-substituted or unsubstituted C1-C 10 Alkyl, hydrocarbon-substituted, or unsubstituted benzyl groups. In this invention, unless otherwise specified, halogens are abbreviated as X and are selected from fluorine, chlorine, bromine, and iodine.

[0042] In some embodiments of the present invention, R is further preferably... 2 and R 3The alkyl substituents are each independently selected from C1-C5 alkyl groups, preferably from methyl, ethyl, propyl, and tert-butyl groups; more preferably, R 2 and R 3 Each is independently selected from halogens, C1-C 10 Alkyl, C1-C 10 Alkoxy, hydrocarbon-substituted or unsubstituted benzyl groups.

[0043] In some embodiments of the present invention, more preferably, R 2 and R 3 Each is independently selected from halogens, C1-C5 alkyl groups, C1-C5 alkoxy groups, and benzyl groups; most preferably, R 2 and R 3 Each is independently selected from fluorine, chlorine, methyl, ethyl, isopropyl, methoxy, and benzyl.

[0044] In this invention, unless otherwise specified, in formula (I), R 2 and R 3 They can be the same or different; R is preferred. 2 and R 3 same.

[0045] In one specific embodiment provided by the present invention, in formula (I), R 1 Selected from 2,6-diisopropylphenyl, Cp' selected from cyclopentadienyl, M selected from Ti, R 2 and R 3 All are selected from chlorine; in formula (I), R 1 Selected from 2,4,6-trimethylphenyl, Cp' selected from pentamethylcyclopentadienyl, M selected from Ti, R 2 and R 3 All are selected from chlorine; in formula (I), R 1 Selected from 2,6-dimethylphenyl, Cp' selected from cyclopentadienyl, M selected from Ti, R 2 and R 3 All are selected from chlorine; in formula (I), R 1 Selected from phenyl, Cp' selected from cyclopentadienyl, M selected from Zr, R 2 and R 3 All are selected from chlorine; in formula (I), R 1 Selected from 2,6-diisopropylphenyl, Cp' selected from cyclopentadienyl, M selected from Ti, R 2 and R 3 All are selected from methyl groups.

[0046] A second aspect of the present invention provides a method for preparing a nitrogen-containing heterocyclic borooxy metal complex, the method comprising the following steps:

[0047] (1) In the presence of an inert gas and a first solvent, the compound shown in formula (II) and sodium hydride are subjected to a first reaction, and then a metal ligand with the general formula Cp'MX3 is added to carry out a second reaction. The first solvent is removed by a first depressurization, and the intermediate product obtained is used as a nitrogen heterocyclic borooxy metal complex.

[0048] (2) Optionally, in the presence of an inert gas and a second solvent, the intermediate product and the alkyl Grignard reagent are subjected to a third reaction to obtain a nitrogen heterocyclic borooxy metal complex;

[0049]

[0050] The nitrogen-containing heterocyclic borooxy metal complex has the structure shown in formula (I), wherein R 1 Selected from hydrogen, substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C6-C 12 Aromatic group; Cp' is selected from substituted or unsubstituted cyclopentadienyl groups and their derivatives; M is selected from Group IVB metal elements; R 2 and R 3 Each is independently selected from halogenated, substituted or unsubstituted C1-C. 10 Alkyl, substituted or unsubstituted C1-C 10 Alkoxy, substituted or unsubstituted benzyl.

[0051] In this invention, unless otherwise specified, the inert gas includes, but is not limited to, nitrogen, helium, argon and neon.

[0052] In some embodiments of the present invention, the compound represented by formula (II) is a substituted or unsubstituted boron-nitrogen-phenanthroline hydroxyl compound, wherein R 1 Selected from hydrogen, substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C6-C 12 Aromatic group; preferably selected from C1-C5 alkyl groups (hydrogen-substituted or unsubstituted) and C6-C groups (hydrocarbon-substituted or unsubstituted). 12 Aromatic group; more preferably selected from hydrogen, C1-C5 alkyl, phenyl, hydrocarbon-substituted phenyl; more preferably selected from hydrogen, methyl, ethyl, propyl, tert-butyl, phenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,4,6-trimethylphenyl.

[0053] In this invention, unless otherwise specified, in the metal ligand of the general formula Cp'MX3, Cp' and M are defined according to the Cp' and M in the above formula (I), which will not be elaborated here. X is a halogen, including but not limited to fluorine, chlorine, bromine, etc.

[0054] In some embodiments of the present invention, preferably, in step (1), the molar ratio of the compound represented by formula (II), sodium hydride and metal ligand is 1:1-3:0.8-1.5, for example, 1:1:0.8, 1:1:1, 1:1.5:1, 1:1.5:1.2, 1:1.5:1.5, 1:2:1, 1:2:1.2, 1:3:1.5, and any value within the range of any two values, preferably 1:1.5-2:1-1.2.

[0055] In some embodiments of the present invention, preferably, the addition temperature of the metal ligand is -78 to 80°C, for example, -78, -50, -25, 0, 20, 30, 40, 50, 60, 80, or any value within the range of any two of these values, preferably 20-60°C. When the addition temperature is below -78°C, the rate of the second reaction will decrease significantly; when the addition temperature is above 80°C, uncontrollable side reactions will occur during the second reaction, reducing the yield.

[0056] In this invention, in step (1), the first reaction is intended to convert the compound shown in formula (II) (i.e., the substituted or unsubstituted boron phenanthrene hydroxyl compound) into the substituted or unsubstituted boron phenanthrene oxy group; the second reaction is intended to complex the substituted or unsubstituted boron phenanthrene oxy group with a metal ligand to obtain the complex shown in formula (I) (i.e., the substituted or unsubstituted boron phenanthrene oxy monocrole group IVB metal complex).

[0057] In some embodiments of the present invention, preferably, the conditions for the first reaction and the second reaction each independently include: a temperature of 15-40°C, preferably 20-30°C; and a time of 10-18h, preferably 12-16h.

[0058] In some embodiments of the present invention, preferably, the ratio of the compound of formula (II) in mmol to the first solvent in mL is 1:10-30, for example, 1:10, 1:15, 1:20, 1:25, 1:30, and any value within a range of any two values, preferably 1:15-25. That is, relative to 1 mmol of the compound of formula (II), the amount of the first solvent is 10-30 mL, preferably 15-25 mL.

[0059] In this invention, the type of the first solvent can be selected from a wide range, as long as the first reaction and the second reaction are carried out in the first solvent. Preferably, the first solvent is selected from organic ethers, more preferably from diethyl ether and / or tetrahydrofuran, and more preferably from diethyl ether.

[0060] In this invention, if step (2) is omitted, the intermediate product obtained in step (1) is used as a nitrogen-containing borooxy metal complex, i.e., R in the complex shown in formula (I) 2 and R 3 All are selected from halogens.

[0061] In this invention, unless otherwise specified, the first decompression is intended to remove the first solvent.

[0062] In some embodiments of the present invention, preferably, in step (2), the molar ratio of the intermediate product to the alkyl Grignard reagent is 0.8-1.2:3, for example, 0.8:3, 1:3, 1.1:3, 1.2:3, and any value within the range of any two values, preferably 1-1.2:3. Using these preferred conditions is more advantageous for reducing R in the complex shown in formula (I). 2 and R 3 (Halogen) Completely substituted to an alkyl group (i.e., substituted or unsubstituted C1-C). 10 Alkyl, substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted benzyl).

[0063] In some embodiments of the present invention, preferably, the alkyl Grignard reagent includes, but is not limited to, methyl magnesium bromide and methyl magnesium chloride.

[0064] In this invention, the third reaction aims to convert the halogen group in the intermediate product into an alkyl group. Preferably, the conditions for the third reaction include: a temperature of 15-40°C, more preferably 20-30°C; and a time of 10-18 h, more preferably 12-16 h.

[0065] In some embodiments of the present invention, preferably, the ratio of the compound of formula (II) in mmol to the second solvent in mL is 1:10-30, for example, 1:10, 1:15, 1:20, 1:25, 1:30, and any value within a range of any two values, preferably 1:15-25. That is, relative to 1 mmol of the compound of formula (II), the amount of the second solvent is 10-30 mL, preferably 15-25 mL.

[0066] In this invention, a wide range of types of the second solvent can be selected, as long as the third reaction is carried out in the second solvent. Preferably, the second solvent is selected from at least one of benzene, toluene, xylene, n-hexane, n-pentane, n-heptane, cyclohexane, and tetrahydrofuran, with toluene being the most preferred.

[0067] In some embodiments of the present invention, preferably, the preparation method further includes: performing a first extraction on the product obtained by the first depressurization and a third solvent, and then subjecting the first extract to a second depressurization to obtain the intermediate product.

[0068] In some embodiments of the present invention, preferably, the preparation method further includes: subjecting the product of the third reaction and the fourth solvent to a second extraction, and subjecting the second extract to a third depressurization to obtain the nitrogen heterocyclic borooxy metal complex.

[0069] In some embodiments of the present invention, preferably, the ratio of the compound of formula (II) in mmol to the third solvent in mL is 1:10-30, for example, 1:10, 1:15, 1:20, 1:25, 1:30, and any value within a range of any two values, preferably 1:15-25. That is, relative to 1 mmol of the compound of formula (II), the amount of the third solvent is 10-30 mL, preferably 15-25 mL.

[0070] In some embodiments of the present invention, preferably, the ratio of the compound of formula (II) in mmol to the fourth solvent in mL is 1:10-30, for example, 1:10, 1:15, 1:20, 1:25, 1:30, and any value within a range of any two values, preferably 1:15-25. That is, relative to 1 mmol of the compound of formula (II), the amount of the fourth solvent is 10-30 mL, preferably 15-25 mL.

[0071] In this invention, a wide range of types of the third and fourth solvents can be selected, as long as the first and second extractions are carried out in the third and fourth solvents respectively. Preferably, the third and fourth solvents are each independently selected from at least one of n-hexane, n-pentane, n-heptane, and cyclohexane, with n-hexane being the most preferred.

[0072] The third aspect of this invention provides the application of the azaheterocyclic borooxy metal complex provided in the first aspect, or the azaheterocyclic borooxy metal complex prepared by the preparation method provided in the second aspect, in the catalytic polymerization of unsaturated olefins.

[0073] The nitrogen-containing heterocyclic boronoxy metal complexes provided by this invention have a boron-oxygen electron-donating structure and large substituent steric hindrance, which gives the catalytic active center good stability, thereby effectively improving the catalytic activity of the nitrogen-containing heterocyclic boronoxy metal complexes.

[0074] In some embodiments of the present invention, preferably, the application of the azahexacyclic borooxy metal complex provided by the present invention in the catalytic polymerization of ethylene, propylene, 1-octene, cyclobutene, cyclopentene, norbornene, and 1,4,5,8-dimethylbridged-1,2,3,4,4a,5,8,8a-octahydronaphthalene (DMON).

[0075] In some preferred embodiments of the present invention, the application of the nitrogen heterocyclic borooxy metal complex provided by the present invention in the catalytic copolymerization of ethylene and norbornene is described.

[0076] The fourth aspect of the present invention provides a copolymerization reaction of ethylene and norbornene, wherein ethylene and norbornene are contacted and copolymerized in the presence of a catalyst, a co-catalyst and a polymerization solvent to obtain an ethylene-norbornene copolymer.

[0077] The catalyst is selected from the nitrogen-heterocyclic borooxy metal complex provided in the first aspect, or the nitrogen-heterocyclic borooxy metal complex prepared by the preparation method provided in the second aspect.

[0078] In some embodiments of the present invention, preferably, the molar ratio of the catalyst to norbornene is 1:50-15000, for example, 1:50, 1:100, 1:500, 1:1500, 1:2000, 1:3000, 1:4000, 1:5000, 1:8000, 1:10000, 1:15000, and any value within the range of any two values, preferably 1:1500-5000.

[0079] In some embodiments of the present invention, preferably, the molar ratio of ethylene to norbornene is 1:1-10, for example, 1:1, 1:2, 1:3.5, 1:4, 1:4.5, 1:5, 1:10, and any value within the range of any two values, preferably 1:3.5-4.5, more preferably 1:4.

[0080] In some embodiments of the present invention, preferably, the molar ratio of the catalyst to the co-catalyst is 1:50-2000, for example, 1:50, 1:100, 1:200, 1:400, 1:600, 1:800, 1:1000, 1:1200, 1:1500, 1:2000, and any value within any range of any two values, preferably 1:400-1200. When the ratio of the co-catalyst to the catalyst is too low, the catalytic activity of the catalyst is significantly reduced or even no polymerization reaction occurs; when the ratio of the co-catalyst to the catalyst is too high, it will cause a decrease in polymerization activity and polymer molecular weight.

[0081] In some embodiments of the present invention, preferably, the conditions for the copolymerization reaction include: a temperature of 0-100°C, preferably 60-80°C; a pressure of 1-10 MPa, preferably 0.3-0.5 MPa; and a time of 1-20 min, preferably 1-5 min. Wherein, the pressure refers to gauge pressure.

[0082] In some embodiments of the present invention, preferably, the co-catalyst is selected from at least one of methylaluminoxane (MAO), modified methylaluminoxane, and tris(pentafluorophenylboron).

[0083] In this invention, a wide range of types of copolymerization solvents can be selected, as long as the copolymerization reaction is carried out in the copolymerization solvent. Preferably, the copolymerization solvent is selected from at least one of benzene, toluene, n-hexane, tetrahydrofuran, and dichloromethane, with toluene being the most preferred.

[0084] In some embodiments of the present invention, the ratio of the catalyst (in mmol) to the copolymerizing solvent (in mL) is 1:10-30, for example, 1:10, 1:15, 1:20, 1:25, 1:30, and any value within a range of any two values, preferably 1:15-25. That is, relative to 1 mmol of the catalyst, the amount of the copolymerizing solvent is 10-30 mL, preferably 15-25 mL.

[0085] According to a particularly preferred embodiment of the present invention, a nitrogen-heterocyclic borooxy metal complex for catalyzing the polymerization of unsaturated olefins, the nitrogen-heterocyclic borooxy metal complex having the structure shown in formula (I):

[0086]

[0087] Among them, R 1 Selected from hydrogen, methyl, ethyl, propyl, tert-butyl, phenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,4,6-trimethylphenyl; Cp' selected from alkyl-substituted or unsubstituted cyclopentadienyl, alkyl-substituted or unsubstituted pentamethylcyclopentadienyl; M selected from Ti, Zr, Hf; R 2 and R 3 Each is independently selected from fluorine, chlorine, methyl, ethyl, isopropyl, methoxy, and benzyl.

[0088] The present invention will be described in detail below through preparation examples.

[0089] The structural parameters of the nitrogen-containing heterocyclic borooxy metal complexes (S1-S7) prepared by Examples 1-7 are listed in Table 1.

[0090] Preparation Example 1

[0091] 2,6-Diisopropylphenyl-substituted boronazphenanthrene hydroxyl compound (0.335 g, 1 mmol) and sodium hydride (0.48 g, 2 mmol) were reacted at 25 °C for 18 h in the presence of argon atmosphere and 20 mL of anhydrous diethyl ether.

[0092] At a temperature of -78℃, metal ligand Cp'TiCl3 (0.218 g, 1 mmol; Cp' selected from cyclopentadienyl) was added and reacted at 25℃ for 12 h. After removing diethyl ether under reduced pressure, 15 mL of n-hexane was added for extraction. The resulting extract was then subjected to further removal of n-hexane under reduced pressure to obtain an intermediate product (yellow solid, 0.338 g, 0.63 mmol), which was identified as the nitrogen-containing borooxy metal complex S1.

[0093] The yield of the nitrogen-containing heterocyclic borooxy metal complex S1 was 63%; ¹H NMR (C6D6): δ 9.19-9.15 (m, 1H, Ar-H), 8.28-8.26 (dd, 1H, Ar-H), 8.25-8.22 (m, 1H, Ar-H), 7.49-7.47 (m, 2H, Ar-H), 7.30-7.21 (m, 3H, Ar-H), 7.06-6.97 (m, 2H, Ar-H), 6.70-6.68 (dd, 1H, Ar-H), 6.02 (s, 5H, Ti-CH), 2.71 (m, 4H, J=6.7Hz, CH3-CH), 1.10 (d, 12H, J=6.6Hz, CH-CH3), 0.87 (d, 12H, J=6.8Hz, CH-CH3).

[0094] Preparation Example 2

[0095] Following the method of Preparation Example 1, except that the substituents of the boron-nitrogen-phenanthroline hydroxy compound were replaced with 2,4,6-trimethylphenyl; and the metal ligand was replaced with the metal ligand Cp'TiCl3 (1 mmol; Cp' is selected from pentamethylcyclopentadienyl), with the other conditions remaining the same, an intermediate product (black solid, 0.277 g, 0.49 mmol) was obtained as the nitrogen-heterocyclic boronoxy metal complex S2;

[0096] The yield of the nitrogen-containing boron oxymetal complex S2 was 49%; the proton NMR spectrum of the nitrogen-containing boron oxymetal complex S2 is shown below. Figure 1 As shown, by Figure 1It can be seen that 1H NMR(C6D6): δ8.55-8.52(m,1H,Ar-H),8.32-8.28(m,2H,Ar-H),7.56-7.47(m,2H,Ar-H),7.09-7.06(m,2H,Ar-H ),6.92(s,2H,Ar-H),6.80-6.78(m,1H,Ar-H),2.24(s,3H,Ar-CH3),2.04(s,6H,Ar-CH3),1.89(s,15H,CH3-CH).

[0097] Preparation Example 3

[0098] Following the method of Preparation Example 1, except that the substituents of the boron-nitrogen-phenanthroline hydroxy compound were replaced with 2,6-dimethylphenyl, and the other conditions were the same, an intermediate product (0.327 g, 0.68 mmol) was obtained as the nitrogen-heterocyclic borooxy metal complex S3;

[0099] The yield of the nitrogen-containing heterocyclic borooxy metal complex S3 was 68%; 1H NMR (C6D6): δ 8.96.8.94 (m, 1H, Ar-H), 8.29-8.23 (m, 2H, Ar-H), 7.53-7.45 (m, 2H, Ar-H), 7.07-7.03 (m, 5H, Ar-H), 6.67-6.65 (m, 1H, Ar-H), 5.93 (s, 5H, Ar-H), 1.92 (s, 6H, Ar-CH3).

[0100] Preparation Example 4

[0101] Following the method of Preparation Example 1, except that the substituents of the boron-nitrogen-phenanthroline hydroxy compound were replaced with phenyl groups, while the other conditions remained the same, an intermediate product (0.34 g, 0.75 mmol) was obtained as the nitrogen-heterocyclic boronoxy metal complex S4.

[0102] The yield of the nitrogen-containing boron oxymetal complex S4 was 75%; the proton NMR spectrum of the nitrogen-containing boron oxymetal complex S4 is shown below. Figure 2 As shown, by Figure 2 It can be seen that 1H NMR(C6D6): δ8.39-8.36(m,1H,Ar-H),8.28-8.22(m,3H,Ar-H),8.05-8.04(m,1H,Ar-H),7. 42-7.34(m,4H,Ar-H),6.93-6.90(m,2H,Ar-H),6.71-6.65(m,2H,Ar-H),3.74(s,5H,Ar-H).

[0103] Preparation Example 5

[0104] In the presence of argon atmosphere and 20 mL of toluene, the azaheptacyclic borooxy metal complex (0.537 g, 1 mmol) prepared in Example 1 and methyl magnesium bromide (1 mL, 3 mmol) were reacted at 25 °C for 18 h. After removing the toluene under reduced pressure, 15 mL of n-hexane was added for extraction. The resulting extract was then subjected to further extraction under reduced pressure to remove the n-hexane, yielding the azaheptacyclic borooxy metal complex S5 (yellow solid, 0.316 g, 0.64 mmol).

[0105] The yield of the nitrogen-containing heterocyclic borooxy metal complex S5 was 64%; 1H NMR(C6D6): δ9.22-9.18(m,1H,Ar-H),8.27-8.25(dd,1H,Ar-H),8.20-8.17(m,1H ,Ar-H),7.54-7.52(m,2H,Ar-H),7.18-7.13(m,3H,Ar-H),7.01-6.92(m,2H,Ar-H) ,6.71-6.69(dd,1H,Ar-H),5.86(s,5H,Ti-CH),2.62(m,4H,J=6.7Hz,CH3-CH),1. 29 (s, 6H, Ti-CH), 1.04 (d, 12H, J = 6.6Hz, CH-CH3), 0.77 (d, 12H, J = 6.8Hz, CH-CH3).

[0106] Preparation Example 6

[0107] Following the method of Preparation Example 1, except that the amount of sodium hydride was replaced with 1 mmol and the amount of metal ligand was replaced with 0.8 mmol, while the other conditions remained the same, the azaheptacyclic borooxy metal complex S6 was obtained; wherein, the yield of the azaheptacyclic borooxy metal complex S6 was 20%.

[0108] Preparation Example 7

[0109] Following the method of Preparation Example 5, except that methyl magnesium bromide was replaced with 1 mmol, while the other conditions remained the same, the azaheptacyclic borooxy metal complex S7 was obtained; wherein the yield of the azaheptacyclic borooxy metal complex S7 was 23%.

[0110] Table 1

[0111] Preparation Example 1 2,6-Diisopropylphenyl Cyclopentadienyl Ti chlorine chlorine 63 Preparation Example 2 2,4,6-Trimethylphenyl Pentamethylcyclopentadienyl Ti chlorine chlorine 49 Preparation Example 3 2,6-Dimethylphenyl Cyclopentadienyl Ti chlorine chlorine 68 Preparation Example 4 Phenyl Cyclopentadienyl Ti chlorine chlorine 75 Preparation Example 5 2,6-Diisopropylphenyl Cyclopentadienyl Ti methyl methyl 64 Preparation Example 6 2,6-Diisopropylphenyl Cyclopentadienyl Ti chlorine chlorine 20 Preparation Example 7 2,6-Diisopropylphenyl Cyclopentadienyl Ti methyl methyl 23

[0112] As shown in Table 1, compared with Preparation Example 6, Preparation Example 1, by adjusting the molar ratio of the compound shown in Formula (II), sodium hydride and metal ligand, is more conducive to improving the yield of the nitrogen-heterocyclic borooxy metal complex; compared with Preparation Example 7, Preparation Example 5, by adjusting the molar ratio of intermediate product and alkyl Grignard reagent, is more conducive to improving the yield of the nitrogen-heterocyclic borooxy metal complex.

[0113] Example 1

[0114] In a Schlenk flask, under anhydrous and oxygen-free conditions, norbornene (2.82 g, 30 mmol), MAO (87 mg, 0.5 mmol), and 22 mL of anhydrous toluene were added. Ethylene gas was introduced, maintaining a pressure of 0.1 MPa and a temperature of 60 °C. 0.5 μmol of the nitrogen-containing heterocyclic borosilicate metal complex S1 was dissolved in 3 mL of anhydrous toluene and added to the Schlenk flask using a syringe to catalyze polymerization. The ethylene gas pressure was adjusted to 0.4 MPa, and the ethylene concentration was 0.34 mmol / mL. The reaction was allowed to proceed for 5 min. The mixture was then poured into a mixture of ethanol and hydrochloric acid to precipitate the polymer. After filtration, the polymer was vacuum dried for 12 h to obtain the ethylene-norbornene copolymer P1. The test results are listed in Table 2.

[0115] The ethylene-norbornene copolymer P1 has a weight-average molecular weight of 27,300 g / mol and a molecular weight distribution of 3.42; based on the total weight of the ethylene-norbornene copolymer P1, the norbornene content is 36 wt%.

[0116] Examples 2-7

[0117] Following the method of Example 1, except that 0.5 μmol of nitrogen-heterocyclic borooxy metal complex S1 was replaced with 0.5 μmol of nitrogen-heterocyclic borooxy metal complexes S2-S7, while the other conditions remained the same, ethylene-norbornene copolymers P2-P7 were obtained respectively, and the test results are listed in Table 2.

[0118] The ethylene-norbornene copolymer P3 has a weight-average molecular weight of 43,000 g / mol and a molecular weight distribution of 3.0.

[0119] Example 8

[0120] Following the method of Example 3, except that the amount of nitrogen heterocyclic borooxy metal complex S3 was replaced with 0.1 μmol, while the other conditions remained the same, ethylene-norbornene copolymer P8 was obtained, and the test results are listed in Table 2.

[0121] Example 9

[0122] Following the method of Example 3, except that the copolymerization time was replaced with 10 min while the other conditions remained the same, ethylene-norbornene copolymer P9 was obtained, and the test results are listed in Table 2.

[0123] Example 10

[0124] Following the method of Example 3, except that the temperature of the copolymerization reaction was replaced with 50°C, while the other conditions remained the same, ethylene-norbornene copolymer P9 was obtained, and the test results are listed in Table 2.

[0125] Comparative Example 1

[0126] CpTi(O-Dipp)Cl2 and MAO catalyze ethylene-norbornene copolymerization (Chemical Communications, 2006(25):2659-2661)

[0127] In a Schlenk flask, under anhydrous and oxygen-free conditions, 2.82 g of norbornene, 232 mg of MAO, and 22 mL of anhydrous toluene were added. Ethylene gas was introduced, and the pressure was maintained at 0.1 MPa. The temperature was controlled at 60 °C. 0.1 μmol of the complex Flu-CGC (0.047 mg) was dissolved in 3 mL of anhydrous toluene and added to the Schlenk flask using a syringe to catalyze polymerization. After reacting for 10 min, the polymer was poured into a mixture of ethanol and hydrochloric acid to precipitate it. After filtration, the polymer was vacuum dried for 12 h to obtain the ethylene-norbornene copolymer DP1. The test results are listed in Table 2.

[0128] Table 2

[0129]

[0130]

[0131] As shown in Table 2, compared with Comparative Example 1, the nitrogen-containing heterocyclic borooxy metal complex provided by the present invention has higher catalytic activity in the copolymerization of ethylene and norbornene.

[0132] Meanwhile, compared to Example 8, Example 3, by adjusting the amount of catalyst used to make the molar ratio of catalyst and co-catalyst within the preferred protection range, is more conducive to improving catalyst activity; compared to Example 9, Example 3, by adjusting the copolymerization reaction time within the preferred protection range, is more conducive to improving catalyst activity; compared to Example 10, Example 3, by adjusting the copolymerization reaction temperature within the preferred protection range, is more conducive to improving catalytic activity.

[0133] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A nitrogen-containing heterocyclic boronoxy metal complex, characterized in that, The nitrogen-containing heterocyclic borooxy metal complex has the structure shown in formula (I): （I） Among them, R 1 Selected from phenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,4,6-trimethylphenyl; Cp' selected from C1-C5 alkyl-substituted or unsubstituted cyclopentadienyl; M selected from Ti, Zr, Hf; R 2 and R 3 Each is independently selected from halogens, C1-C 10 alkyl.

2. The nitrogen-containing heterocyclic borooxy metal complex according to claim 1, wherein, In formula (I), Cp' is selected from cyclopentadienyl or pentamethylcyclopentadienyl.

3. The nitrogen-containing heterocyclic borooxy metal complex according to claim 1 or 2, wherein, In equation (I), R 2 and R 3 Each is independently selected from halogens and C1-C5 alkyl groups.

4. The nitrogen-containing heterocyclic borooxy metal complex according to claim 3, wherein, In equation (I), R 2 and R 3 Each is independently selected from fluorine, chlorine, methyl, ethyl, and isopropyl.

5. A method for preparing a nitrogen-containing heterocyclic borooxy metal complex, characterized in that, The preparation method includes the following steps: (1) In the presence of an inert gas and a first solvent, the compound shown in formula (II) and sodium hydride are subjected to a first reaction, and then a metal ligand with the general formula Cp'MX3 is added to carry out a second reaction. The first solvent is removed by a first depressurization, and the intermediate product obtained is used as a nitrogen heterocyclic borooxy metal complex. (2) Optionally, in the presence of an inert gas and a second solvent, the intermediate product and the alkyl Grignard reagent are subjected to a third reaction to obtain a nitrogen-heterocyclic borooxy metal complex; (AND); (II); The nitrogen-containing heterocyclic borooxy metal complex has the structure shown in formula (I), wherein R 1 Selected from phenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,4,6-trimethylphenyl; Cp' selected from C1-C5 alkyl-substituted or unsubstituted cyclopentadienyl; M selected from Ti, Zr, Hf; R 2 and R 3 Each is independently selected from halogens, C1-C 10 Alkyl group; X is a halogen.

6. The preparation method according to claim 5, wherein, In step (1), the molar ratio of the compound represented by formula (II), sodium hydride and metal ligand is 1:1-3:0.8-1.

5.

7. The preparation method according to claim 6, wherein, In step (1), the molar ratio of the compound represented by formula (II), sodium hydride and metal ligand is 1:1.5-2:1-1.

2.

8. The preparation method according to claim 5, wherein, In step (1), the temperature at which the metal ligand is added is between -78°C and 80°C.

9. The preparation method according to claim 8, wherein, In step (1), the temperature at which the metal ligand is added is 20-60℃.

10. The preparation method according to claim 5, wherein, In step (1), the conditions for the first reaction and the second reaction are each independent of each other: the temperature is 15-40℃ and the time is 10-18h.

11. The preparation method according to claim 10, wherein, In step (1), the conditions for the first reaction and the second reaction are each independent of each other: the temperature is 20-30℃ and the time is 12-16h.

12. The preparation method according to claim 5, wherein, In step (1), the ratio of the compound represented by formula (II) in mmol to the first solvent in mL is 1:10-30.

13. The preparation method according to claim 12, wherein, In step (1), the ratio of the compound represented by formula (II) in mmol to the first solvent in mL is 1:15-25.

14. The preparation method according to claim 5, wherein, In step (1), the first solvent is selected from organic ethers.

15. The preparation method according to claim 14, wherein, In step (1), the first solvent is selected from diethyl ether and / or tetrahydrofuran.

16. The preparation method according to any one of claims 5-15, wherein, In step (2), the molar ratio of the intermediate product to the alkyl Grignard reagent is 0.8-1.2:

3.

17. The preparation method according to claim 16, wherein, In step (2), the molar ratio of the intermediate product to the alkyl Grignard reagent is 1-1.2:

3.

18. The preparation method according to any one of claims 5-15, wherein, In step (2), the alkyl Grignard reagent is selected from methyl magnesium bromide and / or methyl magnesium chloride.

19. The preparation method according to any one of claims 5-15, wherein, In step (2), the conditions for the third reaction include: a temperature of 15-40℃ and a time of 10-18h.

20. The preparation method according to claim 19, wherein, In step (2), the conditions for the third reaction include: a temperature of 20-30℃ and a time of 12-16h.

21. The preparation method according to any one of claims 5-15, wherein, The ratio of the compound represented by formula (II) in mmol to the second solvent in mL is 1:10-30.

22. The preparation method according to claim 21, wherein, The ratio of the compound represented by formula (II) in mmol to the second solvent in mL is 1:15-25.

23. The preparation method according to any one of claims 5-15, wherein, In step (2), the second solvent is selected from at least one of benzene, toluene, xylene, n-hexane, n-pentane, n-heptane, cyclohexane and tetrahydrofuran.

24. The preparation method according to claim 23, wherein, In step (2), the second solvent is toluene.

25. The preparation method according to any one of claims 5-15, wherein, The preparation method further includes: performing a first extraction on the product obtained by the first depressurization and a third solvent, and then subjecting the first extract to a second depressurization to obtain the intermediate product.

26. The preparation method according to any one of claims 5-15, wherein, The preparation method further includes: subjecting the product of the third reaction and the fourth solvent to a second extraction, and subjecting the second extract to a third depressurization to obtain the nitrogen-heterocyclic borooxy metal complex.

27. The preparation method according to claim 25, wherein, The ratio of the compound represented by formula (II) in mmol to the third solvent in mL is 1:10-30.

28. The preparation method according to claim 27, wherein, The ratio of the compound represented by formula (II) in mmol to the third solvent in mL is 1:15-25.

29. The preparation method according to claim 26, wherein, The ratio of the compound represented by formula (II) in mmol to the fourth solvent in mL is 1:10-30.

30. The preparation method according to claim 29, wherein, The ratio of the compound represented by formula (II) in mmol to the fourth solvent in mL is 1:15-25.

31. The preparation method according to claim 25, wherein, The third solvent is selected from at least one of n-hexane, n-pentane, n-heptane, and cyclohexane.

32. The preparation method according to claim 31, wherein, The third solvent is n-hexane.

33. The preparation method according to claim 26, wherein, The fourth solvent is selected from at least one of n-hexane, n-pentane, n-heptane, and cyclohexane.

34. The preparation method according to claim 33, wherein, The fourth solvent is n-hexane.

35. The use of the azaheptacyclic borooxy metal complex according to any one of claims 1-4, or the azaheptacyclic borooxy metal complex prepared by the preparation method according to any one of claims 5-34, in the catalytic polymerization of unsaturated olefins.

36. The application according to claim 35, characterized in that, The application refers to the use of the azaheptacyclic borooxy metal complex in the catalytic polymerization of ethylene, propylene, 1-octene, cyclobutene, cyclopentene, norbornene, and 1,4,5,8-dimethylbridged-1,2,3,4,4a,5,8,8a-octahydronaphthalene.

37. The application according to claim 35 or 36, characterized in that, The application is the use of the nitrogen-containing heterocyclic borooxy metal complex in the catalytic copolymerization of ethylene and norbornene.

38. A copolymerization reaction of ethylene and norbornene, characterized in that, In the presence of a catalyst, a co-catalyst, and a polymerization solvent, ethylene and norbornene are contacted and copolymerized to obtain an ethylene-norbornene copolymer. The catalyst is selected from the nitrogen-heterocyclic borooxy metal complexes according to any one of claims 1-4, or the nitrogen-heterocyclic borooxy metal complexes prepared by the preparation method according to any one of claims 5-34.

39. The copolymerization reaction according to claim 38, wherein, The molar ratio of the catalyst to norbornene is 1:50-15000.

40. The copolymerization reaction according to claim 39, wherein, The molar ratio of the catalyst to norbornene is 1:1500-5000.

41. The copolymerization reaction according to claim 38, wherein, The molar ratio of ethylene to norbornene is 1:1-10.

42. The copolymerization reaction according to claim 41, wherein, The molar ratio of ethylene to norbornene is 1:3.5-4.

5.

43. The copolymerization reaction according to claim 38, wherein, The molar ratio of the catalyst to the co-catalyst is 1:50-2000.

44. The copolymerization reaction according to claim 43, wherein, The molar ratio of the catalyst to the co-catalyst is 1:400-1200.

45. The copolymerization reaction according to claim 38, wherein, The conditions for the copolymerization reaction include: temperature of 0-100℃, pressure of 0-10MPa, and time of 1-20min.

46. ​​The copolymerization reaction according to claim 45, wherein, The conditions for the copolymerization reaction include: a temperature of 60-80℃, a pressure of 0.3-0.5MPa, and a time of 1-5min.

47. The copolymerization reaction according to claim 38, wherein, The cocatalyst is selected from at least one of methylaluminoxane, modified methylaluminoxane, and tris(pentafluorophenylboron).

48. The copolymerization reaction according to claim 38, wherein the copolymerization solvent is selected from at least one of benzene, toluene, n-hexane, tetrahydrofuran, and dichloromethane.

49. The copolymerization reaction according to claim 48, wherein the copolymerization solvent is toluene.

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