An ethylene / alpha-olefin gradient copolymer and a method for preparing the same

Abstract

The present application relates to the technical field of copolymer, in particular to a kind of ethylene / α-olefin gradient copolymer and its preparation method.The preparation method provided by the present application uses two kinds of monomers, ethylene and α-olefin, which have different polymerization activities.By adjusting the complex structure, the copolymerization ability of bisphenol oxy complex to ethylene and α-olefin is studied.The insertion rate of α-olefin and the sequence structure of the polymer are regulated by changing the polymerization reaction process (α-olefin concentration, ethylene pressure, temperature, etc.).An appropriate polymerization system is selected, so that the sequence structure of the polymer changes with the progress of the reaction, thereby forming a gradient structure in the chain, and obtaining an ethylene / ɑ-olefin gradient copolymer.The copolymer has high breakdown field strength, and is a new material that has not been reported in the prior art.

Description

Technical Field

[0001] This invention relates to the field of copolymer technology, specifically to an ethylene / α-olefin gradient copolymer and its preparation method. Background Technology

[0002] Polyolefins are among the most common polymers, with a global production capacity exceeding 200 million tons. my country's production exceeds 50 million tons, accounting for nearly 25% of global capacity, making it the largest polyolefin producer. Polyolefins are inexpensive yet possess excellent mechanical properties, corrosion resistance, and chemical stability. These advantages make them widely used in automobiles, photovoltaic materials, wires and cables, home appliances, packaging, building materials, and other fields, making them indispensable materials in people's production and daily life. However, for a long time, my country's polyolefin products have been concentrated on low-to-mid-end general-purpose materials, resulting in weak international competitiveness and low added value. Therefore, increasing the added value of polyolefins to enhance industrial competitiveness is particularly important.

[0003] Currently, ethylene is copolymerized with α-olefins such as propylene, 1-butene, 1-hexene, 1-octene, and 1-decene. With continuous improvement of catalysts, high-value-added polyolefin products such as linear low-density polyethylene (LLDPE), polyolefin plastisol (POP), polyolefin elastomer (POE), and polyolefin elastomer (OBC) can be produced by adjusting the chain microstructure, changing the type of comonomer, and the amount of comonomer insertion. Ethylene / α-olefin copolymers are mainly random copolymers and block copolymers. In the polymer chain structure, polyethylene segments provide crystalline regions, while polyα-olefin segments disrupt these crystalline regions to form an amorphous rubber phase. This results in ethylene / α-olefin copolymers possessing the high elasticity of rubber at room temperature and being able to be plasticized and molded at high temperatures. Furthermore, as the α-olefin content in the copolymer increases, the material's properties can transform from polyolefin plastics to polyolefin elastomers. Therefore, since the invention of the Ziegler-Natta catalyst, ethylene / α-olefin copolymerization has attracted considerable research interest.

[0004] Gradient copolymers possess unique phase structures, thermal properties, mechanical properties, and self-assembly behavior, making them suitable as solubilizers for blends, stabilizers for emulsions or dispersions, and shape memory materials. However, the synthesis of gradient copolymers remains challenging because it requires not only the simultaneous initiation and uniform growth of all polymer chains to ensure a continuous change in copolymer composition from one end of the chain to the other, but also significant compositional changes during polymerization. Controlled radical polymerization (CRP) can produce polymers with controllable molecular weights and narrow molecular weight distributions, making it suitable for gradient copolymer synthesis. In contrast, coordination polymerization is difficult to utilize due to side reactions such as β-H elimination and chain transfer, leading to dead polymer chains and new active species. Furthermore, the consumption of comonomers results in a heterogeneous composition between polymer chains. Therefore, the application of coordination polymerization to prepare gradient copolymers is very attractive. Currently, the preparation of ethylene / α-olefin gradient copolymers via coordination polymerization remains an unrealized goal. Summary of the Invention

[0005] In view of this, the technical problem to be solved by the present invention is to provide an ethylene / α-olefin gradient copolymer and its preparation method. The preparation method provided by the present invention successfully realizes the coordination polymerization preparation of ethylene / α-olefin gradient copolymer. The obtained ethylene / α-olefin gradient copolymer has a strong breakdown voltage and is a promising material.

[0006] This invention provides a method for preparing an ethylene / α-olefin gradient copolymer, comprising the following steps:

[0007] In a catalytic system, ethylene and α-olefins are polymerized in a reaction medium to obtain an ethylene / α-olefin gradient copolymer; the catalytic system includes an organic salt compound, an organoaluminum compound, and a bisphenol A metal complex.

[0008] The bisphenol A metal complex has the structure of Formula I;

[0009]

[0010] Wherein, M is selected from titanium, zirconium, or hafnium;

[0011] R1, R2, R3, and R4 are independently selected from hydrogen, halogens, C1 to C4. 30 Alkyl, C3-C 30 The alkyl group is selected from one of the following: cycloalkyl, aryl-substituted alkyl with a total carbon number of 7 to 30, silyl-substituted alkyl with a total carbon number of 1 to 30, or aryl with a carbon number of 6 or more; preferably, R1, R2, R3, and R4 are independently selected from hydrogen, halogen, C1 to C5 alkyl, C3 to C4 alkyl, and C5 to C6 alkyl. 10 Cycloalkyl, aryl-substituted alkyl with a total carbon number of 7–10, silyl-substituted alkyl with a total carbon number of 1–6, C6–C18 One of the aryl groups. More preferably, R1, R2, R3, and R4 are independently selected from hydrogen, halogens, C1-C5 alkyl groups, C3-C6 cycloalkyl groups, C6-C6 cycloalkyl groups, and C4-C6 cycloalkyl groups. 12 One of the aryl groups. In some embodiments of the invention, R1, R2, R3, and R4 are independently selected from one of hydrogen, Cl, Br, Ph, methyl, tert-butyl, cyclopentyl, and isopropyl.

[0012] At least two of R1, R2, R3, and R4 are different;

[0013] X is selected from hydrogen, halogens, and C1-C2. 30 Alkyl groups, aryl-substituted alkyl groups with a total carbon number of 7–30, silyl-substituted alkyl groups with a total carbon number of 1–30, C1–C2 30 The alkoxy group is selected from one of the following: hydrogen, halogen, C1-C5 alkyl, aryl-substituted alkyl with 7-10 total carbon atoms, and silyl-substituted alkyl with 1-6 total carbon atoms. More preferably, the alkoxy group is selected from one of the following: hydrogen, halogen, C1-C3 alkyl, and phenyl-substituted alkyl with 1-3 total carbon atoms. In some embodiments of the present invention, the alkoxy group is selected from one of the following: Cl, Br, methyl, and benzyl.

[0014] The Y is dimethylamino, methylthio, methoxy, tetrahydrofuranyl, or pyridyl.

[0015] The n is an integer from 0 to 4, preferably an integer from 0 to 2.

[0016] In the structural formula of the bisphenol A metal complex of the present invention, the two arrows represent coordinate bonds.

[0017] The inventors of this application have creatively discovered that by using a catalytic system composed of bisphenol A metal complexes with the structure of Formula I, organic salt compounds, and organoaluminum compounds, ethylene and α-olefins can be coordinated polymerized. For the first time, coordination polymerization has been achieved to prepare ethylene / α-olefin gradient copolymers. The compositional drift of the obtained ethylene / α-olefin gradient copolymers is sensitive to changes in the concentration of comonomers and has a strong breakdown voltage, making it a promising material.

[0018] In some embodiments of the present invention, the bisphenol A metal complex is one of the compounds with structures shown in Formulas 1 to 16:

[0019]

[0020]

[0021]

[0022] This invention first involves polymerizing ethylene and α-olefins in a reaction medium under a catalytic system, wherein the catalytic system comprises an organoboron-containing compound, an organoaluminum compound, and a bisphenol A metal complex. In some embodiments of this invention, the catalytic system is dissolved in a solvent, preferably toluene.

[0023] The organic boron-containing compound of the present invention is selected from one or more of organoboron salt compounds or organoboron compounds; the organoboron salt compound is selected from one or more of ionic compounds composed of organoboron anions and cations, wherein the organoboron anion is selected from tetraphenylborate, tetra(monofluorophenyl)borate, tetra(difluorophenyl)borate, tetra(trifluorophenyl)borate, tetra(tetrafluorophenyl)borate, tetra(pentafluorophenyl)borate, tetra(tetrafluoromethylphenyl)borate, tetra(tolyl)borate, tetra(xylyl)borate, (triphenyl,pentafluorophenyl)borate, [tri(pentafluorophenyl),phenyl]borate or undecanoyl-7,8-dicarboundecanoate; and the cation is selected from carbium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptatrienyl cation or ferrocene cation containing transition metals.

[0024] The carbium cation is preferably selected from trisubstituted carbium cations or tri(substituted phenyl) carbium cations. In some embodiments of the present invention, the carbium cation is preferably selected from triphenylcarbium cations ([Ph3C)). + Or a tri(tolyl)carbomonium cation. The ammonium cation is preferably selected from trialkylammonium cations, N,N-dialkylphenylammonium cations, or dialkylammonium cations. In some embodiments of the invention, the ammonium cation is preferably selected from trimethylammonium cations, triethylammonium cations ([NEt3H)), or trimethylammonium cations. + Tripropylammonium cation, tributylammonium cation, N,N-dimethylphenylammonium cation ([PhNMe2H]) + The phosphonium cations are N,N-diethylphenylamine cations, N,N-2,4,6-pentamethylphenylamine cations, diisopropylammonium cations, or dicyclohexylammonium cations. The phosphonium cations are preferably selected from triarylphosphonium cations. In some embodiments of the present invention, the phosphonium cations are preferably selected from triphenylphosphonium cations, tri(tolyl)phosphonium cations, or tri(xylyl)phosphonium cations. In some embodiments of the present invention, the organoboronium salt compound is selected from [Ph3C][B(C6F5)4], [PhNMe2H][BPh4], [NEt3H][BPh4], or [PhNMe2H][B(C6F5)4].

[0025] The organoboron compound described in this invention has the same function as the organoboron salt compound; the organoboron compound is selected from C6 to C6. 30 Fluorinated arylboranes or C6-C30 One or more of arylboranes. In some embodiments of the invention, the organoboron compound is one or more of B(C6F5)3, B(C6H5)3, or B(2,4-CF3-C6H3)3.

[0026] The organoaluminum compounds of this invention are selected from one or more of trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisopropylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldibenzylaluminum, or ethyldi(p-tolyl)aluminum. Preferably, the organoaluminum compounds are dissolved in a solvent selected from one or more of hexaane, cyclohexane, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, and bromobenzene, with toluene being the most preferred.

[0027] In the catalytic system of the present invention, the molar ratio of the organic boron-containing compound to the bisphenol A metal complex is (1-10):(10-1), preferably (2-8):(8-2), and more preferably (3-6):(6-3); in some embodiments of the present invention, the molar ratio of the organic boron-containing compound to the bisphenol A metal complex is (0.5-10):1. In some embodiments of the present invention, the molar ratio of the organic boron-containing compound to the bisphenol A metal complex is (1-8):1. In some embodiments of the present invention, the molar ratio of the organic boron-containing compound to the bisphenol A metal complex is (2-6):1. In one embodiment of the present invention, the molar ratio of the organic boron-containing compound to the bisphenol A metal complex is 1:1. The molar ratio of the organoaluminum compound to the bisphenol A metal complex is preferably (2-300):1, more preferably (2-250):1, more preferably (2-200):1, even more preferably (2-150):1, even more preferably (2-120):1, and most preferably (2-20):1.

[0028] This invention involves polymerizing ethylene and α-olefins in a reaction medium. The α-olefin is selected from 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, or 1-eicosene. The reaction medium is selected from one or more of aliphatic saturated hydrocarbons, aromatic hydrocarbons, aryl halides, and cycloalkanes, preferably one or more of hexane, cyclohexane, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, and bromobenzene.

[0029] The concentration of the α-olefin in this invention is not higher than 2 mol / L, preferably 0.05 mol / L to 2 mol / L, more preferably 0.05 mol / L to 1 mol / L, and most preferably 0.1 mol / L to 0.8 mol / L; the pressure of the ethylene is not higher than 30 bar, preferably 1 to 30 atmospheres, more preferably 1 to 20 atmospheres, and even more preferably 1 to 10 atmospheres. This invention does not impose any special limitations on the amount of the catalytic system used. Those skilled in the art can select an appropriate amount of catalytic system based on the catalyst dosage known in monomer polymerization and the actual situation to ensure the polymerization reaction proceeds. This invention also does not impose any special limitations on the amount of the reaction medium used. Those skilled in the art can select an appropriate amount of reaction medium based on the actual situation to ensure the polymerization reaction proceeds.

[0030] The polymerization reaction described in this invention is specifically a coordination polymerization reaction. The temperature of the polymerization reaction is -20℃ to 150℃, preferably -10℃ to 120℃, more preferably 10℃ to 90℃, even more preferably 20℃ to 80℃, even more preferably 30℃ to 60℃, and most preferably 40℃ to 50℃. The time of the polymerization reaction described in this invention is not particularly limited and is selected according to the amount of catalyst and the size of the reaction system. In some embodiments of this invention, the polymerization reaction is carried out in a batch reactor for a time of 1 minute to 10 hours; in other embodiments of this invention, the polymerization reaction is carried out in a continuous reactor for a time of 1 day to 10 days.

[0031] This invention describes a polymerization reaction of ethylene and α-olefins in a catalytic system to obtain an ethylene / α-olefin gradient copolymer. Specifically, a saturated solution of an organoaluminum compound and an organoboron-containing compound, along with a bisphenol A metal complex, are added to an α-olefin solution, and ethylene gas is introduced to initiate the polymerization reaction. The solvents used for the saturated solutions of the organoaluminum compound and the organoboron-containing compound are the same as those used in the aforementioned reaction medium, and will not be described further. Similarly, the solvent used for the α-olefin solution is the same as those used in the aforementioned reaction medium, and will not be described further.

[0032] In this invention, after the polymerization reaction is completed, it is preferable to add a methanol-hydrochloric acid solution to terminate the reaction. After the polymerization reaction is terminated, it is preferable to add the copolymer obtained by separation with ethanol and then dry it; the drying method is preferably vacuum drying; the drying temperature is 30℃~50℃, preferably 35℃~45℃, and more preferably 40℃.

[0033] This invention also provides an ethylene / α-olefin gradient copolymer obtained by the preparation method described in any of the above technical solutions. The main chain of the ethylene / α-olefin gradient copolymer of this invention comprises ethylene structural units and α-olefin structural units, wherein the content of the α-olefin structural units is not higher than 25 mol% of the ethylene / α-olefin gradient copolymer, preferably 1 mol% to 25 mol%, more preferably greater than 1 mol% and less than 25 mol%, even more preferably greater than 1 mol% and less than 20 mol%, and most preferably greater than 1 mol% and less than 15 mol%. The melting point of the crystalline sequence in the ethylene / α-olefin gradient copolymer is 80℃ to 140℃, preferably 85℃ to 140℃, and most preferably 90℃ to 140℃. The glass transition temperature of the ethylene / α-olefin gradient copolymer of this invention is -90℃ to -40℃, preferably -80℃ to -50℃. The breakdown voltage of the ethylene / α-olefin gradient copolymer described in this invention is 160 kV / mm to 250 kV / mm. This invention demonstrates that the α-olefin is gradient-distributed in the polymer chain by showcasing both a glass transition temperature (for segments with high α-olefin content) and a melting point of the crystallization sequence (for segments with low α-olefin content) in the ethylene / α-olefin gradient copolymer.

[0034] The number average molecular weight of the ethylene / α-olefin gradient copolymer of the present invention is 50,000 to 400,000, preferably 70,000 to 400,000, more preferably 100,000 to 300,000; the molecular weight distribution of the ethylene / α-olefin gradient copolymer is not higher than 4, preferably 1 to 4, more preferably 1 to 3.5, and most preferably 1 to 3.

[0035] This invention provides an ethylene / α-olefin gradient copolymer and its preparation method. The preparation method uses two monomers with different polymerization activities, ethylene and α-olefin. The copolymerization ability of bisphenol A complex catalyzing ethylene and α-olefin was studied by adjusting the complex structure. The insertion rate of α-olefin and the sequence structure of the polymer were controlled by changing the polymerization process (α-olefin concentration, ethylene pressure, temperature, etc.). A suitable polymerization system was screened so that the polymer sequence structure changes with the reaction, thereby forming a gradient structure within the chain, resulting in an ethylene / α-olefin gradient copolymer. Gradient polymers are very difficult to prepare, requiring not only a catalytic system with the characteristics of active polymerization but also a high degree of sensitivity to comonomer growth and changes in comonomer concentration. For coordination copolymerization, due to chain transfer, even if the copolymer composition changes in concentration, the composition between molecular chains in the resulting polymer is not uniform, and therefore cannot be called a gradient copolymer. This invention achieves the preparation of an ethylene / α-olefin gradient copolymer for the first time. This copolymer has a high breakdown field strength and is a novel material not previously reported in the art. Attached Figure Description

[0036] Figure 1 The copolymer sample prepared in Example 1 of this invention 1 H NMR spectrum;

[0037] Figure 2 The copolymer sample prepared in Example 17 of this invention 1 H NMR spectrum;

[0038] Figure 3 The copolymer sample prepared in Example 17 of this invention 13 C NMR spectrum;

[0039] Figure 4 The following are DSC curves of the copolymer samples from Examples 20, 21, 24 and 25 of this invention;

[0040] Figure 5 This is a graph showing the mechanical properties of the copolymer sample prepared in Example 24 of the present invention.

[0041] Figure 6 This is a breakdown voltage test diagram of the copolymer prepared in Example 24 of the present invention. Detailed Implementation

[0042] This invention discloses an ethylene / α-olefin gradient copolymer and its preparation method. Those skilled in the art can refer to the content of this document and appropriately modify the process parameters to achieve the desired result. It should be particularly noted that all similar substitutions and modifications are obvious to those skilled in the art and are considered to be included in this invention. The methods and applications of this invention have been described through preferred embodiments, and those skilled in the art will clearly be able to modify or appropriately change and combine the methods and applications described herein without departing from the content, spirit, and scope of this invention to realize and apply the technology of this invention.

[0043] The complexes with structures of formulas 1 to 16 used in the specific embodiments of this invention are the same as the compounds with structures shown in formulas 1 to 16 above, and will not be described again. The complexes with structures of formulas 1 to 16 used in the specific embodiments of this invention are all prepared according to the method disclosed in Organometallics 2002, 21, 662-670.

[0044] The present invention will be further described below with reference to the embodiments:

[0045] Example 1

[0046] In a glove box, add 30 mL of a 0.2 mol / L toluene solution of 1-hexene to a 150 mL glass pressure-resistant bottle, and then add Al. i Bu3 (40 μL, 20 μmol). Then, tighten the pressure bottle cap, remove the glove box, and introduce 1.0 atm ethylene while stirring to saturate the toluene, forming a polymerization reaction system.

[0047] In a glove box, a catalyst solution was prepared by dissolving the complex of formula 1 (8.3 mg, 10 μmol) and tris(pentafluorophenyl)borane B(C6F5)3 (5.2 mg, 10 μmol) in 1 mL of toluene. The catalyst solution was then removed from the glove box and rapidly added to the polymerization reaction system at 40 °C to initiate polymerization. The ethylene pressure was then quickly adjusted to 4.0 atm. After 5 min of reaction, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction. A large amount of ethanol was then added to separate the copolymer, which was then vacuum dried at 40 °C until the polymer weight showed no change. Figure 1 As shown, Figure 1 The copolymer sample prepared in Example 1 of this invention 1 H NMR spectrum. (From) Figure 1 As can be seen, the hydrogen NMR spectrum of the obtained polymer has no absorption peak in the range of 4.5 to 5.5 ppm, indicating that no chain transfer caused by β-H elimination occurred, and that the molecular chains in the obtained polymer are of uniform composition.

[0048] Example 2

[0049] In a glove box, add 30 mL of a 0.2 mol / L toluene solution of 1-hexene to a 150 mL glass pressure-resistant bottle, and then add Al. i Bu3 (40 μL, 20 μmol). Then, tighten the pressure bottle cap, remove the glove box, and introduce 1.0 atm ethylene while stirring to saturate the toluene, forming a polymerization reaction system.

[0050] In a glove box, a catalyst solution was prepared by dissolving the complex of formula 2 (9.0 mg, 10 μmol) and tris(pentafluorophenyl)borane B(C6F5)3 (5.2 mg, 10 μmol) in 1 mL of toluene. The catalyst solution was then removed from the glove box and rapidly added to the polymerization reaction system at 40 °C to initiate polymerization. The ethylene pressure was then quickly adjusted to 4.0 atm. After 5 min of reaction, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction. A large amount of ethanol was then added to separate the copolymer, which was then vacuum dried at 40 °C until the polymer weight showed no change.

[0051] Example 3

[0052] In a glove box, add 30 mL of a 0.2 mol / L toluene solution of 1-hexene to a 150 mL glass pressure-resistant bottle, and then add Al. i Bu3 (40 μL, 20 μmol). Then, tighten the pressure bottle cap, remove the glove box, and introduce 1.0 atm ethylene while stirring to saturate the toluene, forming a polymerization reaction system.

[0053] In a glove box, a catalyst solution was prepared by dissolving the complex of formula 3 (8.0 mg, 10 μmol) and tris(pentafluorophenyl)borane B(C6F5)3 (5.2 mg, 10 μmol) in 1 mL of toluene. The catalyst solution was then removed from the glove box and rapidly added to the polymerization reaction system at 40 °C to initiate polymerization. The ethylene pressure was then quickly adjusted to 4.0 atm. After 5 min of reaction, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction. A large amount of ethanol was then added to separate the copolymer, which was then vacuum dried at 40 °C until the polymer weight showed no change.

[0054] Example 4

[0055] In a glove box, add 30 mL of a 0.2 mol / L toluene solution of 1-hexene to a 150 mL glass pressure-resistant bottle, and then add Al. i Bu3 (40 μL, 20 μmol). Then, tighten the pressure bottle cap, remove the glove box, and introduce 1.0 atm ethylene while stirring to saturate the toluene, forming a polymerization reaction system.

[0056] In a glove box, a catalyst solution was prepared by dissolving the complex of formula 4 (6.9 mg, 10 μmol) and tris(pentafluorophenyl)borane B(C6F5)3 (5.2 mg, 10 μmol) in 1 mL of toluene. The catalyst solution was then removed from the glove box and rapidly added to the polymerization reaction system at 40 °C to initiate polymerization. The ethylene pressure was then quickly adjusted to 4.0 atm. After 5 min of reaction, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction. A large amount of ethanol was then added to separate the copolymer, which was then vacuum dried at 40 °C until the polymer weight showed no change.

[0057] Example 5

[0058] In a glove box, add 30 mL of a 0.2 mol / L toluene solution of 1-hexene to a 150 mL glass pressure-resistant bottle, and then add Al. i Bu3 (40 μL, 20 μmol). Then, tighten the pressure bottle cap, remove the glove box, and introduce 1.0 atm ethylene while stirring to saturate the toluene, forming a polymerization reaction system.

[0059] In a glove box, a catalyst solution was prepared by dissolving the complex of formula 5 (7.1 mg, 10 μmol) and tris(pentafluorophenyl)borane B(C6F5)3 (5.2 mg, 10 μmol) in 1 mL of toluene. The catalyst solution was then removed from the glove box and rapidly added to the polymerization reaction system at 40 °C to initiate polymerization. The ethylene pressure was then quickly adjusted to 4.0 atm. After 5 min of reaction, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction. A large amount of ethanol was then added to separate the copolymer, which was then vacuum dried at 40 °C until the polymer weight showed no change.

[0060] Example 6

[0061] In a glove box, add 30 mL of a 0.2 mol / L toluene solution of 1-hexene to a 150 mL glass pressure-resistant bottle, and then add Al. i Bu3 (40 μL, 20 μmol). Then, tighten the pressure bottle cap, remove the glove box, and introduce 1.0 atm ethylene while stirring to saturate the toluene, forming a polymerization reaction system.

[0062] In a glove box, a catalyst solution was prepared by dissolving the complex of formula 6 (5.8 mg, 10 μmol) and tris(pentafluorophenyl)borane B(C6F5)3 (5.2 mg, 10 μmol) in 1 mL of toluene. The catalyst solution was then removed from the glove box and rapidly added to the polymerization reaction system at 40 °C to initiate polymerization. The ethylene pressure was then quickly adjusted to 4.0 atm. After 5 min of reaction, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction. A large amount of ethanol was then added to separate the copolymer, which was then vacuum dried at 40 °C until the polymer weight showed no change.

[0063] Example 7

[0064] In a glove box, add 30 mL of a 0.2 mol / L toluene solution of 1-hexene to a 150 mL glass pressure-resistant bottle, and then add Al. i Bu3 (40 μL, 20 μmol). Then, tighten the pressure bottle cap, remove the glove box, and introduce 1.0 atm ethylene while stirring to saturate the toluene, forming a polymerization reaction system.

[0065] In a glove box, a catalyst solution was prepared by dissolving the complex of formula 7 (6.8 mg, 10 μmol) and tris(pentafluorophenyl)borane B(C6F5)3 (5.2 mg, 10 μmol) in 1 mL of toluene. The catalyst solution was then removed from the glove box and rapidly added to the polymerization reaction system at 40 °C to initiate polymerization. The ethylene pressure was then quickly adjusted to 4.0 atm. After 5 min of reaction, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction. A large amount of ethanol was then added to separate the copolymer, which was then vacuum dried at 40 °C until the polymer weight showed no change.

[0066] Example 8

[0067] In a glove box, add 30 mL of a 0.2 mol / L toluene solution of 1-hexene to a 150 mL glass pressure-resistant bottle, and then add Al. i Bu3 (40 μL, 20 μmol). Then, tighten the pressure bottle cap, remove the glove box, and introduce 1.0 atm ethylene while stirring to saturate the toluene, forming a polymerization reaction system.

[0068] In a glove box, a catalyst solution was prepared by dissolving the complex of formula 8 (7.5 mg, 10 μmol) and tris(pentafluorophenyl)borane B(C6F5)3 (5.2 mg, 10 μmol) in 1 mL of toluene. The catalyst solution was then removed from the glove box and rapidly added to the polymerization reaction system at 40 °C to initiate polymerization. The ethylene pressure was then quickly adjusted to 4.0 atm. After 5 min of reaction, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction. A large amount of ethanol was then added to separate the copolymer, which was then vacuum dried at 40 °C until the polymer weight showed no change.

[0069] Example 9

[0070] In a glove box, add 30 mL of a 0.2 mol / L toluene solution of 1-hexene to a 150 mL glass pressure-resistant bottle, and then add Al. i Bu3 (40 μL, 20 μmol). Then, tighten the pressure bottle cap, remove the glove box, and introduce 1.0 atm ethylene while stirring to saturate the toluene, forming a polymerization reaction system.

[0071] In a glove box, a catalyst solution was prepared by dissolving the complex of formula 9 (8.1 mg, 10 μmol) and tris(pentafluorophenyl)borane B(C6F5)3 (5.2 mg, 10 μmol) in 1 mL of toluene. The catalyst solution was then removed from the glove box and rapidly added to the polymerization reaction system at 40 °C to initiate polymerization. The ethylene pressure was then quickly adjusted to 4.0 atm. After 5 min of reaction, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction. A large amount of ethanol was then added to separate the copolymer, which was then vacuum dried at 40 °C until the polymer weight showed no change.

[0072] Example 10

[0073] In a glove box, add 30 mL of a 0.2 mol / L toluene solution of 1-hexene to a 150 mL glass pressure-resistant bottle, and then add Al. i Bu3 (40 μL, 20 μmol). Then, tighten the pressure bottle cap, remove the glove box, and introduce 1.0 atm ethylene while stirring to saturate the toluene, forming a polymerization reaction system.

[0074] In a glove box, a catalyst solution was prepared by dissolving the complex of formula 10 (6.7 mg, 10 μmol) and tris(pentafluorophenyl)borane B(C6F5)3 (5.2 mg, 10 μmol) in 1 mL of toluene. The catalyst solution was then removed from the glove box and rapidly added to the polymerization reaction system at 40 °C to initiate polymerization. The ethylene pressure was then quickly adjusted to 4.0 atm. After 5 min of reaction, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction. A large amount of ethanol was then added to separate the copolymer, which was then vacuum dried at 40 °C until the polymer weight showed no change.

[0075] Example 11

[0076] In a glove box, add 30 mL of a 0.2 mol / L toluene solution of 1-hexene to a 150 mL glass pressure-resistant bottle, and then add Al. i Bu3 (40 μL, 20 μmol). Then, tighten the pressure bottle cap, remove the glove box, and introduce 1.0 atm ethylene while stirring to saturate the toluene, forming a polymerization reaction system.

[0077] In a glove box, a catalyst solution was prepared by dissolving the complex of formula 11 (6.3 mg, 10 μmol) and tris(pentafluorophenyl)borane B(C6F5)3 (5.2 mg, 10 μmol) in 1 mL of toluene. The catalyst solution was then removed from the glove box and rapidly added to the polymerization reaction system at 40 °C to initiate polymerization. The ethylene pressure was then quickly adjusted to 4.0 atm. After 5 min of reaction, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction. A large amount of ethanol was then added to separate the copolymer, which was then vacuum dried at 40 °C until the polymer weight showed no change.

[0078] Example 12

[0079] In a glove box, add 30 mL of a 0.2 mol / L toluene solution of 1-hexene to a 150 mL glass pressure-resistant bottle, and then add Al. i Bu3 (40 μL, 20 μmol). Then, tighten the pressure bottle cap, remove the glove box, and introduce 1.0 atm ethylene while stirring to saturate the toluene, forming a polymerization reaction system.

[0080] In a glove box, a catalyst solution was prepared by dissolving the complex of formula 12 (8.0 mg, 10 μmol) and tris(pentafluorophenyl)borane B(C6F5)3 (5.2 mg, 10 μmol) in 1 mL of toluene. The catalyst solution was then removed from the glove box and rapidly added to the polymerization reaction system at 40 °C to initiate polymerization. The ethylene pressure was then quickly adjusted to 4.0 atm. After 5 min of reaction, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction. A large amount of ethanol was then added to separate the copolymer, which was then vacuum dried at 40 °C until the polymer weight showed no change.

[0081] Example 13

[0082] In a glove box, add 30 mL of a 0.2 mol / L toluene solution of 1-hexene to a 150 mL glass pressure-resistant bottle, and then add Al. i Bu3 (40 μL, 20 μmol). Then, tighten the pressure bottle cap, remove the glove box, and introduce 1.0 atm ethylene while stirring to saturate the toluene, forming a polymerization reaction system.

[0083] In a glove box, a catalyst solution was prepared by dissolving the complex of formula 13 (6.7 mg, 10 μmol) and tris(pentafluorophenyl)borane B(C6F5)3 (5.2 mg, 10 μmol) in 1 mL of toluene. The catalyst solution was then removed from the glove box and rapidly added to the polymerization reaction system at 40 °C to initiate polymerization. The ethylene pressure was then quickly adjusted to 4.0 atm. After 5 min of reaction, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction. A large amount of ethanol was then added to separate the copolymer, which was then vacuum dried at 40 °C until the polymer weight showed no change.

[0084] Example 14

[0085] In a glove box, add 30 mL of a 0.2 mol / L toluene solution of 1-hexene to a 150 mL glass pressure-resistant bottle, and then add Al. i Bu3 (40 μL, 20 μmol). Then, tighten the pressure bottle cap, remove the glove box, and introduce 1.0 atm ethylene while stirring to saturate the toluene, forming a polymerization reaction system.

[0086] In a glove box, a catalyst solution was prepared by dissolving the complex of formula 14 (6.0 mg, 10 μmol) and tris(pentafluorophenyl)borane B(C6F5)3 (5.2 mg, 10 μmol) in 1 mL of toluene. The catalyst solution was then removed from the glove box and rapidly added to the polymerization reaction system at 40 °C to initiate polymerization. The ethylene pressure was then quickly adjusted to 4.0 atm. After 5 min of reaction, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction. A large amount of ethanol was then added to separate the copolymer, which was then vacuum dried at 40 °C until the polymer weight showed no change.

[0087] Example 15

[0088] In a glove box, add 30 mL of a 0.2 mol / L toluene solution of 1-hexene to a 150 mL glass pressure-resistant bottle, and then add Al. i Bu3 (40 μL, 20 μmol). Then, tighten the pressure bottle cap, remove the glove box, and introduce 1.0 atm ethylene while stirring to saturate the toluene, forming a polymerization reaction system.

[0089] In a glove box, a catalyst solution was prepared by dissolving the complex of formula 15 (5.6 mg, 10 μmol) and tris(pentafluorophenyl)borane B(C6F5)3 (5.2 mg, 10 μmol) in 1 mL of toluene. The catalyst solution was then removed from the glove box and rapidly added to the polymerization reaction system at 40 °C to initiate polymerization. The ethylene pressure was then quickly adjusted to 4.0 atm. After 5 min of reaction, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction. A large amount of ethanol was then added to separate the copolymer, which was then vacuum dried at 40 °C until the polymer weight showed no change.

[0090] Example 16

[0091] In a glove box, add 30 mL of a 0.2 mol / L toluene solution of 1-hexene to a 150 mL glass pressure-resistant bottle, and then add Al. i Bu3 (40 μL, 20 μmol). Then, tighten the pressure bottle cap, remove the glove box, and introduce 1.0 atm ethylene while stirring to saturate the toluene, forming a polymerization reaction system.

[0092] In a glove box, a catalyst solution was prepared by dissolving the complex of formula 16 (8.5 mg, 10 μmol) and tris(pentafluorophenyl)borane B(C6F5)3 (5.2 mg, 10 μmol) in 1 mL of toluene. The catalyst solution was then removed from the glove box and rapidly added to the polymerization reaction system at 40 °C to initiate polymerization. The ethylene pressure was then quickly adjusted to 4.0 atm. After 5 min of reaction, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction. A large amount of ethanol was then added to separate the copolymer, which was then vacuum dried at 40 °C until the polymer weight showed no change.

[0093] Example 17

[0094] In a glove box, add 30 mL of a 0.5 mol / L toluene solution of 1-hexene to a 150 mL glass pressure-resistant bottle, and then add Al. i Bu3 (40 μL, 20 μmol). Then, tighten the pressure bottle cap, remove the glove box, and introduce 1.0 atm ethylene while stirring to saturate the toluene, forming a polymerization reaction system.

[0095] In a glove box, a catalyst solution was prepared by dissolving the complex of formula 3 (8.0 mg, 10 μmol) and tris(pentafluorophenyl)borane B(C6F5)3 (5.2 mg, 10 μmol) in 1 mL of toluene. The catalyst solution was then removed from the glove box and rapidly added to the polymerization reaction system at 80 °C to initiate polymerization. The ethylene pressure was then quickly adjusted to 4.0 atm. After 5 min of reaction, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction. A large amount of ethanol was then added to separate the copolymer, which was then vacuum-dried at 40 °C until the polymer weight remained unchanged. The copolymer sample prepared in Example 17 of this invention was subjected to... 1 H NMR spectrum and 13 C NMR spectral detection, such as Figures 2-3 As shown, Figure 2 The copolymer sample prepared in Example 17 of this invention 1 H NMR spectrum Figure 3 The copolymer sample prepared in Example 17 of this invention 13 C10 NMR spectrum.

[0096] Example 18

[0097] In a glove box, add 30 mL of a 0.5 mol / L toluene solution of 1-hexene to a 150 mL glass pressure-resistant bottle, and then add Al. iBu3 (40 μL, 20 μmol). Then, tighten the pressure bottle cap, remove the glove box, and introduce 1.0 atm ethylene while stirring to saturate the toluene, forming a polymerization reaction system.

[0098] In a glove box, a catalyst solution was prepared by dissolving the complex of formula 3 (8.0 mg, 10 μmol) and tris(pentafluorophenyl)borane B(C6F5)3 (5.2 mg, 10 μmol) in 1 mL of toluene. The catalyst solution was then removed from the glove box and rapidly added to the polymerization reaction system at 60 °C to initiate polymerization. The ethylene pressure was then quickly adjusted to 4.0 atm. After 5 min of reaction, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction. A large amount of ethanol was then added to separate the copolymer, which was then vacuum dried at 40 °C until the polymer weight showed no change.

[0099] Example 19

[0100] In a glove box, add 30 mL of a 0.5 mol / L toluene solution of 1-hexene to a 150 mL glass pressure-resistant bottle, and then add Al. i Bu3 (40 μL, 20 μmol). Then, tighten the pressure bottle cap, remove the glove box, and introduce 1.0 atm ethylene while stirring to saturate the toluene, forming a polymerization reaction system.

[0101] In a glove box, a catalyst solution was prepared by dissolving the complex of formula 3 (8.0 mg, 10 μmol) and tris(pentafluorophenyl)borane B(C6F5)3 (5.2 mg, 10 μmol) in 1 mL of toluene. The catalyst solution was then removed from the glove box and rapidly added to the polymerization reaction system at 40 °C to initiate polymerization. The ethylene pressure was then quickly adjusted to 4.0 atm. After 5 min of reaction, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction. A large amount of ethanol was then added to separate the copolymer, which was then vacuum dried at 40 °C until the polymer weight showed no change.

[0102] Example 20

[0103] In a glove box, add 30 mL of a 0.5 mol / L toluene solution of 1-hexene to a 150 mL glass pressure-resistant bottle, and then add Al. i Bu3 (40 μL, 20 μmol). Then, tighten the pressure bottle cap, remove the glove box, and introduce 1.0 atm ethylene while stirring to saturate the toluene, forming a polymerization reaction system.

[0104] In a glove box, a catalyst solution was prepared by dissolving the complex of formula 3 (8.0 mg, 10 μmol) and tris(pentafluorophenyl)borane B(C6F5)3 (5.2 mg, 10 μmol) in 1 mL of toluene. The catalyst solution was then removed from the glove box and rapidly added to the polymerization reaction system at 40 °C to initiate polymerization. The ethylene pressure was then quickly adjusted to 4.0 atm. After 10 min of reaction, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction. A large amount of ethanol was then added to separate the copolymer, which was then vacuum dried at 40 °C until the polymer weight showed no change.

[0105] Example 21

[0106] In a glove box, add 30 mL of a 0.3 mol / L toluene solution of 1-hexene to a 150 mL glass pressure-resistant bottle, and then add Al. i Bu3 (40 μL, 20 μmol). Then, tighten the pressure bottle cap, remove the glove box, and introduce 1.0 atm ethylene while stirring to saturate the toluene, forming a polymerization reaction system.

[0107] In a glove box, a catalyst solution was prepared by dissolving the complex of formula 3 (8.0 mg, 10 μmol) and tris(pentafluorophenyl)borane B(C6F5)3 (5.2 mg, 10 μmol) in 1 mL of toluene. The catalyst solution was then removed from the glove box and rapidly added to the polymerization reaction system at 40 °C to initiate polymerization. The ethylene pressure was then quickly adjusted to 4.0 atm. After 10 min of reaction, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction. A large amount of ethanol was then added to separate the copolymer, which was then vacuum dried at 40 °C until the polymer weight showed no change.

[0108] Example 22

[0109] In a glove box, add 30 mL of a 0.2 mol / L toluene solution of 1-hexene to a 150 mL glass pressure-resistant bottle, and then add Al. i Bu3 (40 μL, 20 μmol). Then, tighten the pressure bottle cap, remove the glove box, and introduce 1.0 atm ethylene while stirring to saturate the toluene, forming a polymerization reaction system.

[0110] In a glove box, a catalyst solution was prepared by dissolving the complex of formula 3 (8.0 mg, 10 μmol) and tris(pentafluorophenyl)borane B(C6F5)3 (5.2 mg, 10 μmol) in 1 mL of toluene. The catalyst solution was then removed from the glove box and rapidly added to the polymerization reaction system at 40 °C to initiate polymerization. The ethylene pressure was then quickly adjusted to 4.0 atm. After 1 min of reaction, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction. A large amount of ethanol was then added to separate the copolymer, which was then vacuum dried at 40 °C until the polymer weight showed no change.

[0111] Example 23

[0112] In a glove box, add 30 mL of a 0.2 mol / L toluene solution of 1-hexene to a 150 mL glass pressure-resistant bottle, and then add Al. i Bu3 (40 μL, 20 μmol). Then, tighten the pressure bottle cap, remove the glove box, and introduce 1.0 atm ethylene while stirring to saturate the toluene, forming a polymerization reaction system.

[0113] In a glove box, a catalyst solution was prepared by dissolving the complex of formula 3 (8.0 mg, 10 μmol) and tris(pentafluorophenyl)borane B(C6F5)3 (5.2 mg, 10 μmol) in 1 mL of toluene. The catalyst solution was then removed from the glove box and rapidly added to the polymerization reaction system at 40 °C to initiate polymerization. The ethylene pressure was then quickly adjusted to 4.0 atm. After 7 min of reaction, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction. A large amount of ethanol was then added to separate the copolymer, which was then vacuum dried at 40 °C until the polymer weight showed no change.

[0114] Example 24

[0115] In a glove box, add 30 mL of a 0.2 mol / L toluene solution of 1-hexene to a 150 mL glass pressure-resistant bottle, and then add Al. i Bu3 (40 μL, 20 μmol). Then, tighten the pressure bottle cap, remove the glove box, and introduce 1.0 atm ethylene while stirring to saturate the toluene, forming a polymerization reaction system.

[0116] In a glove box, a catalyst solution was prepared by dissolving the complex of formula 3 (8.0 mg, 10 μmol) and tris(pentafluorophenyl)borane B(C6F5)3 (5.2 mg, 10 μmol) in 1 mL of toluene. The catalyst solution was then removed from the glove box and rapidly added to the polymerization reaction system at 40 °C to initiate polymerization. The ethylene pressure was then quickly adjusted to 4.0 atm. After 10 min of reaction, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction. A large amount of ethanol was then added to separate the copolymer, which was then vacuum dried at 40 °C until the polymer weight showed no change.

[0117] Example 25

[0118] In a glove box, add 30 mL of a 0.1 mol / L toluene solution of 1-hexene to a 150 mL glass pressure-resistant bottle, and then add Al. i Bu3 (40 μL, 20 μmol). Then, tighten the pressure bottle cap, remove the glove box, and introduce 1.0 atm ethylene while stirring to saturate the toluene, forming a polymerization reaction system.

[0119] In a glove box, a catalyst solution was prepared by dissolving the complex of formula 3 (8.0 mg, 10 μmol) and tris(pentafluorophenyl)borane B(C6F5)3 (5.2 mg, 10 μmol) in 1 mL of toluene. The catalyst solution was then removed from the glove box and rapidly added to the polymerization reaction system at 40 °C to initiate polymerization. The ethylene pressure was then quickly adjusted to 4.0 atm. After 10 min of reaction, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction. A large amount of ethanol was then added to separate the copolymer, which was then vacuum dried at 40 °C until the polymer weight showed no change.

[0120] Example 26

[0121] In a glove box, add 30 mL of a 0.1 mol / L toluene solution of 1-hexene to a 150 mL glass pressure-resistant bottle, and then add Al. i Bu3 (40 μL, 20 μmol). Then, tighten the pressure bottle cap, remove the glove box, and introduce 1.0 atm ethylene while stirring to saturate the toluene, forming a polymerization reaction system.

[0122] In a glove box, a catalyst solution was prepared by dissolving the complex of formula 3 (8.0 mg, 10 μmol) and tris(pentafluorophenyl)borane B(C6F5)3 (5.2 mg, 10 μmol) in 1 mL of toluene. The catalyst solution was then removed from the glove box and rapidly added to the polymerization reaction system at 40 °C to initiate polymerization. The ethylene pressure was then quickly adjusted to 3.0 atm. After 10 min of reaction, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction. A large amount of ethanol was then added to separate the copolymer, which was then vacuum dried at 40 °C until the polymer weight showed no change.

[0123] Example 27

[0124] In a glove box, add 30 mL of a 0.1 mol / L toluene solution of 1-hexene to a 150 mL glass pressure-resistant bottle, and then add Al. i Bu3 (40 μL, 20 μmol). Then, tighten the pressure bottle cap, remove the glove box, and introduce 10 atm ethylene while stirring to saturate the toluene, forming a polymerization reaction system.

[0125] In a glove box, a catalyst solution was prepared by dissolving the complex of formula 3 (8.0 mg, 10 μmol) and tris(pentafluorophenyl)borane B(C6F5)3 (5.2 mg, 10 μmol) in 1 mL of toluene. The catalyst solution was then removed from the glove box and rapidly added to the polymerization reaction system at 40 °C to initiate polymerization. The ethylene pressure was then quickly adjusted to 1.0 atm. After 10 min of reaction, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction. A large amount of ethanol was then added to separate the copolymer, which was then vacuum dried at 40 °C until the polymer weight showed no change.

[0126] Example 28

[0127] In a glove box, add 30 mL of a 0.2 mol / L toluene solution of 1-hexene to a 150 mL glass pressure-resistant bottle, and then add Al. i Bu3 (40 μL, 20 μmol). Then, tighten the pressure bottle cap, remove the glove box, and introduce 1.0 atm ethylene while stirring to saturate the toluene, forming a polymerization reaction system.

[0128] In a glove box, a catalyst solution was prepared by dissolving the complex of formula 3 (8.0 mg, 10 μmol) and tris(pentafluorophenyl)borane B(C6F5)3 (5.2 mg, 10 μmol) in 1 mL of toluene. The catalyst solution was then removed from the glove box and rapidly added to the polymerization reaction system at 40 °C to initiate polymerization. The ethylene pressure was then quickly adjusted to 4.0 atm. After 10 min of reaction, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction. A large amount of ethanol was then added to separate the copolymer, which was then vacuum dried at 40 °C until the polymer weight showed no change.

[0129] Example 29

[0130] In a glove box, add 30 mL of a 0.2 mol / L toluene solution of 1-octene to a 150 mL glass pressure-resistant bottle, and then add Al. i Bu3 (40 μL, 20 μmol). Then, tighten the pressure bottle cap, remove the glove box, and introduce 1.0 atm ethylene while stirring to saturate the toluene, forming a polymerization reaction system.

[0131] In a glove box, a catalyst solution was prepared by dissolving the complex of formula 3 (8.0 mg, 10 μmol) and tris(pentafluorophenyl)borane B(C6F5)3 (5.2 mg, 10 μmol) in 1 mL of toluene. The catalyst solution was then removed from the glove box and rapidly added to the polymerization reaction system at 40 °C to initiate polymerization. The ethylene pressure was then quickly adjusted to 4.0 atm. After 10 min of reaction, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction. A large amount of ethanol was then added to separate the copolymer, which was then vacuum dried at 40 °C until the polymer weight showed no change.

[0132] Example 30

[0133] In a glove box, add 30 mL of a 0.2 mol / L toluene solution of 1-decene to a 150 mL glass pressure-resistant bottle, and then add Al. i Bu3 (40 μL, 20 μmol). Then, tighten the pressure bottle cap, remove the glove box, and introduce 1.0 atm ethylene while stirring to saturate the toluene, forming a polymerization reaction system.

[0134] In a glove box, a catalyst solution was prepared by dissolving the complex of formula 3 (8.0 mg, 10 μmol) and tris(pentafluorophenyl)borane B(C6F5)3 (5.2 mg, 10 μmol) in 1 mL of toluene. The catalyst solution was then removed from the glove box and rapidly added to the polymerization reaction system at 40 °C to initiate polymerization. The ethylene pressure was then quickly adjusted to 4.0 atm. After 10 min of reaction, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction. A large amount of ethanol was then added to separate the copolymer, which was then vacuum dried at 40 °C until the polymer weight showed no change.

[0135] Example 31

[0136] In a glove box, add 30 mL of a 0.2 mol / L toluene solution of 1-dodecene to a 150 mL glass pressure-resistant bottle, and then add Al. i Bu3 (40 μL, 20 μmol). Then, tighten the pressure bottle cap, remove the glove box, and introduce 1.0 atm ethylene while stirring to saturate the toluene, forming a polymerization reaction system.

[0137] In a glove box, a catalyst solution was prepared by dissolving the complex of formula 3 (8.0 mg, 10 μmol) and tris(pentafluorophenyl)borane B(C6F5)3 (5.2 mg, 10 μmol) in 1 mL of toluene. The catalyst solution was then removed from the glove box and rapidly added to the polymerization reaction system at 40 °C to initiate polymerization. The ethylene pressure was then quickly adjusted to 4.0 atm. After 10 min of reaction, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction. A large amount of ethanol was then added to separate the copolymer, which was then vacuum dried at 40 °C until the polymer weight showed no change.

[0138] Example 32

[0139] In a glove box, add 30 mL of a 0.2 mol / L toluene solution of 1-tetradecene to a 150 mL glass pressure-resistant bottle, and then add Al. i Bu3 (40 μL, 20 μmol). Then, tighten the pressure bottle cap, remove the glove box, and introduce 1.0 atm ethylene while stirring to saturate the toluene, forming a polymerization reaction system.

[0140] In a glove box, a catalyst solution was prepared by dissolving the complex of formula 3 (8.0 mg, 10 μmol) and tris(pentafluorophenyl)borane B(C6F5)3 (5.2 mg, 10 μmol) in 1 mL of toluene. The catalyst solution was then removed from the glove box and rapidly added to the polymerization reaction system at 40 °C to initiate polymerization. The ethylene pressure was then quickly adjusted to 4.0 atm. After 10 min of reaction, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction. A large amount of ethanol was then added to separate the copolymer, which was then vacuum dried at 40 °C until the polymer weight showed no change.

[0141] Example 33

[0142] In a glove box, add 30 mL of a 0.2 mol / L toluene solution of 1-hexadecene to a 150 mL glass pressure-resistant bottle, and then add Al. i Bu3 (40 μL, 20 μmol). Then, tighten the pressure bottle cap, remove the glove box, and introduce 1.0 atm ethylene while stirring to saturate the toluene, forming a polymerization reaction system.

[0143] In a glove box, a catalyst solution was prepared by dissolving the complex of formula 3 (8.0 mg, 10 μmol) and tris(pentafluorophenyl)borane B(C6F5)3 (5.2 mg, 10 μmol) in 1 mL of toluene. The catalyst solution was then removed from the glove box and rapidly added to the polymerization reaction system at 40 °C to initiate polymerization. The ethylene pressure was then quickly adjusted to 4.0 atm. After 10 min of reaction, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction. A large amount of ethanol was then added to separate the copolymer, which was then vacuum dried at 40 °C until the polymer weight showed no change.

[0144] Determination of the composition of ethylene / α-olefin copolymers:

[0145] The content of ethylene (E) and α-olefin in the copolymer is based on the copolymer content measured at 110°C in C6D2Cl4. 1 The HNMR spectra were obtained and calculated using the following formulas:

[0146] f 1-己烯 =4×I (0.93-1.00) / (3×I (1.20-1.43) -5×I (0.93-1.00) )*100%

[0147] f 1-辛烯 =4×I (0.93-1.00) / (3×I (1.20-1.43) -9×I (0.93-1.00) )*100%

[0148] f1-癸烯 =4×I (0.93-1.00) / (3×I (1.20-1.43) -13×I (0.93-1.00) )*100%

[0149] f 1-十二烯 =4×I (0.93-1.00) / (3×I (1.20-1.43) -17×I (0.93-1.00) )*100%

[0150] f 1-十四烯 =4×I (0.93-1.00) / (3×I (1.20-1.43) -21×I (0.93-1.00) )*100%

[0151] f 1-十六烯 =4×I (0.93-1.00) / (3×I (1.20-1.43) -25×I (0.93-1.00) )*100%

[0152] Thermal property determination of ethylene / α-olefin copolymer:

[0153] Copolymer glass transition temperature (T) g ) and melting point (T m Determination of the glass transition temperature and melting point of the copolymer: The glass transition temperature and melting point of the copolymer were determined by differential scanning calorimetry (DSC) using a Mettler TOPEM™ instrument. Figure 4 As shown, Figure 4 The above are DSC curves of the copolymer samples of Examples 20, 21, 24 and 25 of this invention.

[0154] Determination of molecular weight and molecular weight distribution of ethylene / α-olefin copolymers:

[0155] Number-average molecular weight of copolymers (M) n Determination of number-average molecular weight distribution (PDI) of copolymers: n The molecular weight distribution (PDI) was determined by gel permeation chromatography (GPC) using polystyrene as a standard at 150 °C with C6H6Cl3 as the mobile phase.

[0156] Mechanical testing of ethylene / α-olefin copolymers:

[0157] 1) Cut three 150μm thick polyimide films with an aspect ratio of 20×20cm. Wipe them sequentially with deionized water, ethanol, and then deionized water to ensure the film surface is clean. Select one of the polyimide films and make a circular hole with a radius of 2cm.

[0158] 2) Weigh 1.7g of ethylene / α-olefin copolymer and place it in the pores of the open-cell polyimide film, and place it on a 150μm thick polyimide film. Heat them together in a flat vulcanizing machine at 150℃ for 10 minutes.

[0159] 3) After confirming that the copolymer has melted, cover it with a complete 20×20cm polyimide film, and vent the copolymer film at 10MPa pressure and 150℃, with an venting interval of 3s, and venting 10 times.

[0160] 4) The ethylene / α-olefin copolymer powder was hot-pressed at 20 MPa and 140 °C for 10 min. After completion, the prepared film sample was rapidly cooled by circulating water cooling to bring the sample to room temperature.

[0161] 5) Remove the hot-pressed ethylene / α-olefin copolymer film and anneal it for 30 minutes.

[0162] Mechanical tests and breakdown voltage tests were performed on the copolymer sample prepared in Example 24 of this invention, and the results are as follows: Figures 5-6 As shown, Figure 5 This is a graph showing the mechanical properties of the copolymer sample prepared in Example 24 of the present invention. Figure 6 This is a breakdown voltage test diagram of the copolymer prepared in Example 24 of the present invention.

[0163] The copolymers prepared by different catalysts in Examples 1-16 are shown in Table 1:

[0164] Table 1

[0165] 1 2.21 2.65 9.5 8.6 2.52 2 1.92 2.30 11.6 9.6 2.23 3 1.63 2.0 10.7 11.8 1.23 4 0.02 0.02 - - - 5 2.50 3.00 7.5 8.2 2.72 6 2.06 2.47 8.7 7.2 2.50 7 2.43 2.92 7.7 8.7 2.68 8 2.13 2.56 10.2 8.3 2.23 9 0.01 0.01 - - - 10 1.85 2.22 11.8 13.4 1.42 11 0.01 0.01 - - - 12 1.65 1.98 11.3 10.8 1.38 13 0.32 0.38 5.6 4.8 1.21 14 0.04 0.05 - - - 15 0.02 0.02 - - - 16 1.60 1.92 11.0 10.5 1.32 The polymerization conditions in Table 1 are as follows: 40℃, catalyst = 10 μmol, polymerization time 5 minutes, ethylene pressure = 4 bar, [1-hexene] = 0.2 mol / L, Al i Bu3 = 20 μmol.

[0166] The copolymers prepared under different monomer concentrations, polymerization temperatures, ethylene pressures, and polymerization times in Examples 17–27 are shown in Table 2.

[0167] Table 2

[0168]

[0169] Unless otherwise specified, the polymerization conditions in Table 2 are: 40℃, 10μmol catalyst, 4bar ethylene pressure, and Al... i Bu3 = 20 μmol;

[0170] Special notes in Table 2: b 80℃; c 60℃;d Ethylene pressure 3 bar; e Ethylene pressure 1 bar.

[0171] The copolymers prepared using different α-olefins in Examples 28–33 are shown in Table 3:

[0172] Table 3

[0173]

[0174] The polymerization conditions in Table 3 are as follows: 40℃, catalyst = 10 μmol, polymerization time 10 minutes, ethylene pressure = 4 bar, [α-olefin] = 0.2 mol / L, Al i Bu3 = 20 μmol.

[0175] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A method for preparing an ethylene / α-olefin gradient copolymer, characterized in that, Includes the following steps: In a catalytic system, ethylene and α-olefins are polymerized in a reaction medium to obtain an ethylene / α-olefin gradient copolymer; the catalytic system includes an organoboron-containing compound, an organoaluminum compound, and a bisphenol A metal complex; the melting point of the crystalline sequence in the ethylene / α-olefin gradient copolymer is 80 °C to 140 °C. The bisphenol A metal complex is one of the compounds with the structure shown in Formula 1 to 3, Formula 5 to 8, Formula 10, Formula 12, Formula 13 or Formula 16: Formula 1; Formula 2; Formula 3; Formula 5; Formula 6; Formula 7; Formula 8; Formula 10; Equation 12; Equation 13; Formula 16.

2. The method for preparing the ethylene / α-olefin gradient copolymer according to claim 1, characterized in that, The molar ratio of the organic boron-containing compound to the bisphenol A metal complex is (1~10):(10~1); The molar ratio of the organoaluminum compound to the bisphenol A metal complex is (2~20):

1.

3. The method for preparing the ethylene / α-olefin gradient copolymer according to claim 1, characterized in that, The organic boron-containing compound is selected from one or more organic boron salt compounds or organic boron compounds; The organoboron salt compound is selected from one or more ionic compounds composed of organoboron anions and cations. The organoboron anion is selected from tetraphenylborate, tetra(monofluorophenyl)borate, tetra(difluorophenyl)borate, tetra(trifluorophenyl)borate, tetra(tetrafluorophenyl)borate, tetra(pentafluorophenyl)borate, tetra(tetrafluoromethylphenyl)borate, tetra(tolyl)borate, tetra(xyl)borate, (triphenyl,pentafluorophenyl)borate, [tri(pentafluorophenyl),phenyl]borate, or undecanoyl-7,8-dicarboundecanoate. The cation is selected from carbium cations, oxonium cations, ammonium cations, phosphonium cations, cycloheptatrienyl cations, or ferrocene cations containing transition metals. The organoboron compound is selected from C6~C6. 30 Fluorinated arylboranes or C6~C 30 One or more of arylboranes; 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, ethyl dibenzylaluminum, or ethyl di(p-tolyl)aluminum.

4. The method for preparing the ethylene / α-olefin gradient copolymer according to claim 1, characterized in that, The α-olefin is selected from 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, or 1-eicosene. The reaction medium is selected from one or more of aliphatic saturated hydrocarbons, aromatic hydrocarbons, aryl halides, and cycloalkanes.

5. The method for preparing the ethylene / α-olefin gradient copolymer according to claim 1, characterized in that, The concentration of the α-olefin is not higher than 2 mol / L, and the pressure of the ethylene is not higher than 30 bar.

6. The method for preparing the ethylene / α-olefin gradient copolymer according to claim 1, characterized in that, The polymerization reaction occurs at temperatures ranging from -20 ℃ to 150 ℃.

7. The ethylene / α-olefin gradient copolymer obtained by any of the preparation methods according to claims 1 to 6; The content of the α-olefin structural unit is not higher than 25 mol% of the ethylene / α-olefin gradient copolymer. The glass transition temperature of the ethylene / α-olefin gradient copolymer is -90 ℃ to -40 ℃; The breakdown voltage of the ethylene / α-olefin gradient copolymer is between 160 kV / mm and 250 kV / mm.

8. The ethylene / α-olefin gradient copolymer according to claim 7, characterized in that, The number average molecular weight of the ethylene / α-olefin gradient copolymer is 50,000 to 400,000. The molecular weight distribution of the ethylene / α-olefin gradient copolymer is not higher than 4.

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