A method for preparing high-purity cyclic polyolefins

Abstract

This invention relates to the field of organic synthesis technology, specifically to a method for preparing high-purity cyclic polyolefins. The preparation of this high-purity cyclic polyolefin includes at least the steps of catalyzing the polymerization of cyclic olefin monomers using a metathesis catalyst containing polar groups at a temperature not exceeding 60°C and a polymerization time not exceeding 30 min, quenching the reaction using a quencher containing polar groups, and separating the cyclic polyolefins from the product. This method functionalizes the end groups of the linear polyolefins in the metathesis reaction product, thereby utilizing the polarity difference between linear and cyclic polyolefins to separate the cyclic polyolefins and obtain high-purity polyolefins. This method is of great significance for obtaining high-molecular-weight, high-topological-purity cyclic polyolefin products.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis technology, and specifically to a method for preparing high-purity cyclic polyolefins. Background Technology

[0002] Cyclic polyolefins are a class of polyolefins without end groups. Their cyclic topology gives them different physical properties from linear polyolefins. Currently, methods for large-scale preparation of high-purity cyclic polyolefins are still very limited, mainly involving two approaches: one is the ring-closing method, which involves first synthesizing a linear polyolefin with reactive end groups, and then reacting the two end groups at low concentrations to transform the linear structure into a cyclic structure. The other is the ring-expansion method, which directly synthesizes cyclic polyolefins from cyclic monomers. One type of ring-expansion method uses ring-opening metathesis polymerization to polymerize cyclic polyolefin monomers to obtain cyclic polyolefins. Numerous reports have been published on the preparation of cyclic polyolefins using ring expansion methods (J.Am.Chem.Soc.2013,135(15),5717–5725; Org.Lett.2010,12(17),3729–3731; J.Am.Chem.Soc.2007,129(5),1105–1112; Chem.Sci.2011,2(3),429–438).

[0003] In existing ring-expansion methods, fully cyclic polyolefins can be easily obtained at low monomer concentrations, but the molecular weight of the cyclic polyolefins is also relatively low. Increasing the monomer concentration can effectively increase the molecular weight of the product, but the problem that arises is that linear polyolefins begin to be generated as the monomer concentration increases, and this increase is further compounded by the presence of cyclic polyolefins. Currently, there is no effective method to separate linear and cyclic polyolefins.

[0004] Therefore, providing a method for preparing cyclic polyolefins that are easy to separate linear and cyclic polyolefins is of great significance for obtaining cyclic polyolefins with high topological purity and achieving molecular weight adjustment. Summary of the Invention

[0005] Based on this, the present invention provides a method for preparing high-purity cyclic polyolefins. This method functionalizes the end groups of linear polyolefins in metathesis reaction products, thereby utilizing the polarity difference between linear and cyclic polyolefins to separate cyclic polyolefins and obtain high-purity polyolefins.

[0006] The present invention achieves the above-mentioned technical objectives through the following technical solutions:

[0007] A method for preparing high-purity cyclic polyolefins includes at least the steps of catalyzing the polymerization of cyclic olefin monomers using a metathesis catalyst containing polar groups at a temperature not exceeding 60°C and a polymerization time not exceeding 30 min, quenching the reaction using a quencher containing polar groups, and separating the cyclic polyolefins in the product.

[0008] Based on the preparation method described above, the cyclic polyolefins in the product are separated by column chromatography or sedimentation.

[0009] According to the preparation method described above, during column chromatography separation, the stationary phase is silica gel or alumina, and the mobile phase is one or more combinations of straight-chain aliphatic hydrocarbons, cyclic aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, and tetrahydrofuran.

[0010] According to the preparation method described above, during sedimentation separation, both the good solvent and the bad solvent are one or more combinations of straight-chain aliphatic hydrocarbons, cyclic aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, and tetrahydrofuran.

[0011] Based on the preparation method described above, the structure of the metathesis catalyst is shown in Formula 7:

[0012]

[0013] Wherein, M is ruthenium or osmium; m is 0, 1 or 2; X1 and X2 are anionic ligands; L1 and L2 are neutral electron-donating ligands; R3 and R4 are each independently selected from hydrogen, hydrocarbon group, substituted hydrocarbon group, heteroatom-containing hydrocarbon group, substituted heteroatom-containing hydrocarbon group, and any one or more substituents in R3 and R4 must contain one or more polar functional groups; any two or more ligands in X1, X2, L1, L2, R3 and R4 can be linked together to form a cyclic group, or any one or more ligands in X1, X2, L1, L2, R3 and R4 can be attached to the support.

[0014] Based on the preparation method described above, the structure of the quencher is shown in Formula 6:

[0015]

[0016] R1 is selected from one of C1-C20 alkyl, C2-C20 alkenyl, and C6-C20 aryl; R2 is selected from one of substituted or unsubstituted benzenesulfonyl, ester, and carbonyl.

[0017] According to the preparation method described above, in Formula 7, the polar functional group is selected from oxygen-containing polar functional groups, nitrogen-containing functional groups, halogen-containing functional groups, silicon-containing functional groups, and functional groups similar to the above functional groups.

[0018] According to the preparation method described above, in Formula 7, the oxygen-containing polar functional groups are carboxyl, sulfonic acid, phosphate, and hydroxyl groups.

[0019] According to the preparation method described above, in Formula 7, the nitrogen-containing functional group is cyano, primary amine, secondary amine, or amide.

[0020] According to the preparation method described above, in Formula 7, the halogen-containing functional groups are fluorine, chlorine, bromine, and halogenated hydrocarbons with 1 to 12 carbons.

[0021] According to the preparation method described above, in Formula 7, the silicon-containing functional group is trimethoxysilane, triethoxysilane, or methyldiethoxysilane.

[0022] According to the preparation method described above, the molar ratio of cyclic olefin monomer to catalyst is 500,000-200:1, preferably 100,000-500:1.

[0023] According to the preparation method described above, the amount of quencher used is 1-10 times the molar amount of the catalyst.

[0024] The polymerization reaction is carried out in an organic solvent by the preparation method described above, and the concentration of the cyclic olefin monomer is 0.01-10 mol / L; preferably, the concentration of the cyclic olefin monomer is not higher than 5 mol / L.

[0025] The polymerization reaction temperature is 0-50℃ according to the preparation method described above.

[0026] The cyclic olefin monomers prepared by the above method are olefins containing carbon-carbon double bonds with 5-20 carbon atoms.

[0027] The cyclic olefin monomers prepared by the above method are selected from one or more of the cyclic olefins shown in Formulas 1-5 below;

[0028]

[0029] Where n = 1, 3, 4 or 8.

[0030] This invention functionalizes the end groups of linear polyolefins in metathesis reaction products by using catalysts and quenchers with polar groups, thereby creating a difference in chemical properties between linear and cyclic polyolefins. This allows cyclic polyolefins to be separated from the products, resulting in high-topological-purity cyclic polyolefins. This method is of great significance for obtaining high-molecular-weight, high-topological-purity cyclic polyolefin products. Attached Figure Description

[0031] Figure 1 The starting material (E)-N-(3-(4-(hydroxymethyl)phenyl)allyl)-4-methyl-N-(prop-2-yn-1-yl)benzenesulfonamide for the synthesis of catalyst G3-OH1 H NMR spectrum;

[0032] Figure 2 The starting material G3 for the synthesis of catalyst G3-OH 1 H NMR spectrum;

[0033] Figure 3 For catalyst G3-OH 1 H NMR spectrum;

[0034] Figure 4 The polyolefin obtained in Example 1 1 H NMR spectrum;

[0035] Figure 5 The matrix-assisted laser desorption / ionization time-of-flight mass spectrometry of the polyolefin obtained in Example 1. Detailed Implementation

[0036] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions in the embodiments of this invention will be clearly and completely described below in conjunction with the embodiments of this invention. Obviously, the described embodiments are only some embodiments of this invention, not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0037] The linear and cyclic products generated by conventional ring-opening metathesis polymerization of polyolefins are difficult to separate due to their similar chemical properties, making it extremely difficult to obtain high-topological-purity, high-molecular-weight cyclic polyolefin products. Therefore, developing a method to separate linear and cyclic polyolefins is of great significance for obtaining high-purity, high-molecular-weight cyclic polyolefin products. Based on this, this invention has discovered that when using catalysts and quenchers containing polar groups to polymerize cyclic polyolefin products, highly polar functional groups can be introduced into the end groups of linear polyolefins, increasing the overall polarity of the linear polyolefin and enabling its separation from the cyclic polyolefin. This allows for the preparation of high-purity cyclic polyolefins through olefin metathesis polymerization. Furthermore, by adjusting the reaction conditions, cyclic polyolefins with different molecular weights and yields can be obtained. Moreover, after optimizing the reaction conditions, this method can yield cyclic polyolefins with higher molecular weights than previously reported.

[0038] The present invention first provides a method for preparing high-purity cyclic polyolefins. The method includes at least the steps of using a metathesis catalyst containing polar groups to catalyze the polymerization of cyclic olefin monomers at a temperature not higher than 60°C and for a polymerization time not exceeding 30 min, using a quencher containing polar groups to quench the reaction, and separating the cyclic polyolefins in the product.

[0039] In the above method, by using metathesis catalysts containing polar groups and quenchers containing polar groups, highly polar functional groups can be introduced into the end groups of linear polymer polyolefins, increasing the overall polarity of the linear polyolefins. Then, the polarity difference between the two can be used to separate cyclic polyolefins and finally obtain cyclic polyolefins with high topological purity.

[0040] It is worth noting that in this invention, when the polymerization reaction temperature is higher than 60°C or the polymerization time exceeds 30 min, it will promote the decomposition of the metathesis catalyst during the polymerization process, affect the reaction with the quencher, and thus affect the functionalization degree of the linear polymer end groups. This will result in the appearance of incompletely functionalized linear polyolefins in the polymerization product. These linear polyolefins without polar groups cannot be separated from the cyclic polyolefins, thereby affecting the purity of the obtained cyclic polyolefins.

[0041] In this invention, the separation of cyclic polyolefins in the product is based on the polarity difference between cyclic and linear polyolefins. Therefore, any method that relies on polarity differences to separate cyclic and linear polyolefins is applicable to the separation of cyclic polyolefins in this application. For example, in some specific embodiments, column chromatography or sedimentation separation is used to separate cyclic polyolefins. When using column chromatography, the stationary phase is silica gel or alumina, and the mobile phase is one or more combinations of straight-chain aliphatic hydrocarbons, cyclic aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, and tetrahydrofuran. When using sedimentation separation, both good and poor solvents are one or more combinations of straight-chain aliphatic hydrocarbons, cyclic aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, and tetrahydrofuran.

[0042] In some embodiments of the present invention, the structure of the metathesis catalyst is shown in Formula 7: Wherein, M is ruthenium or osmium; m is 0, 1 or 2; X1 and X2 are anionic ligands; L1 and L2 are neutral electron-donating ligands; R3 and R4 are each independently selected from hydrogen, hydrocarbon group, substituted hydrocarbon group, heteroatom-containing hydrocarbon group, substituted heteroatom-containing hydrocarbon group, and any one or more substituents in R3 and R4 must contain one or more polar functional groups; any two or more ligands in X1, X2, L1, L2, R3 and R4 can be linked together to form a cyclic group, or any one or more ligands in X1, X2, L1, L2, R3 and R4 can be attached to the support.

[0043] Furthermore, in Formula 7, the polar functional group is selected from oxygen-containing polar functional groups, nitrogen-containing functional groups, halogen-containing functional groups, silicon-containing functional groups, and functional groups similar to the above-mentioned functional groups. For example, the oxygen-containing polar functional group is a carboxyl group, a sulfonic acid group, a phosphoric acid group, a hydroxyl group, or a similar functional group; the nitrogen-containing functional group is a cyano group, a primary amine, a secondary amine, an amide, or a similar functional group; the halogen-containing functional group is fluorine, chlorine, bromine, a halogenated hydrocarbon with 1 to 12 carbons such as trifluoromethyl, pentafluoroethyl, or a similar functional group; and the silicon-containing functional group is trimethoxysilane, triethoxysilane, methyldiethoxysilane, or a similar functional group.

[0044] In some specific embodiments of the present invention, the structure of the quenching agent is shown in Formula 6: R1 is selected from one of C1-C20 alkyl, C2-C20 alkenyl, and C6-C20 aryl; R2 is selected from one of substituted or unsubstituted benzenesulfonyl, ester, and carbonyl.

[0045] In this invention, the molar ratio of the cyclic olefin monomer to the catalyst and the amount of quencher can be determined according to conventional methods in the art. Typically, the molar ratio of the cyclic olefin monomer to the catalyst is controlled at 1,000,000-10:1, or it can be controlled at 500,000-200:1, or 100,000-500:1. The amount of quencher is typically 1-10 times the molar amount of the catalyst.

[0046] In this invention, the polymerization step can be carried out in a solvent-free system, but for ease of reaction control, the polymerization reaction is usually carried out in an organic solvent. There are no particular limitations on the organic solvent, as long as it can disperse or dissolve the generated polyolefin without significantly affecting the polymerization reaction. Specific usable organic solvents include aliphatic hydrocarbons, such as cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicyclohepten, tricyclodecane, hexahydroindene, and cyclooctane; aromatic hydrocarbons, such as benzene, toluene, and xylene; halogenated aliphatic hydrocarbons, such as dichloromethane, chloroform, and 1,2-dichloroethane; halogenated aromatic hydrocarbons, such as chlorobenzene and dichlorobenzene; nitrogen-containing solvents, such as nitromethane, nitrobenzene, and acetonitrile; ethers, such as diethyl ether and tetrahydrofuran; and aromatic ethers, such as anisole and phenethyl ether. Among these solvents, aromatic hydrocarbons, ethers, and aromatic ether solvents are preferred.

[0047] When polymerization is carried out in an organic solvent, there are no special restrictions on the monomer concentration, which is usually controlled to be no higher than 20 mol / L, such as 0.01-10 mol / L. However, when the monomer concentration is too low, the production efficiency will decrease, and when the monomer concentration is too high, the viscosity of the reaction solution after polymerization will be too high, leading to difficulties in subsequent processing. Therefore, the preferred monomer concentration range is no higher than 5 mol / L.

[0048] In existing technologies, to obtain cyclic polyolefins with high topological purity, the monomer concentration is typically controlled within a low range to avoid the formation of linear polyolefins during the reaction. For example, with 1,5-cyclooctadiene and cyclopentene, to obtain cyclic polyolefins free of linear polyolefins, the monomer concentration is typically controlled below 0.2 mol / L. However, using the method described in this application, because the resulting linear polyolefins contain polar functional groups at their ends, their properties can be effectively distinguished from and separated from cyclic polyolefins. Therefore, the monomer concentration in this application can be maintained at a higher concentration (far exceeding that of existing technologies), and the resulting cyclic polyolefins also have a higher molecular weight.

[0049] In this invention, the decomposition of the metathesis catalyst will not occur when the polymerization reaction temperature is not higher than 60°C. However, the operation is more difficult when the polymerization temperature is too low. Therefore, the preferred polymerization temperature is 0-60°C.

[0050] In this invention, the cyclic olefin monomer is typically selected from olefins containing carbon-carbon double bonds with 5-20 carbon atoms. In some specific embodiments, the cyclic olefin monomer is selected from one or more of the cyclic olefins shown in Formulas 1-5 below.

[0051]

[0052] Where n = 1, 3, 4 or 8.

[0053] The present invention will now be described in detail with reference to specific embodiments.

[0054] In the following examples, number-average molecular weight, weight-average molecular weight, and molecular weight distribution coefficient were measured using a size-exclusion gel electrophoresis system. This instrument consisted of an Agilent 1260 liquid pump, two Agilent PLgel MIXED-B 300×7.5 mm columns connected in series, a Wyatt 18-angle DAWN HELEOS optical dispersion detector, and a Wyatt Optilab rEX differential refractive index detector. Tetrahydrofuran was used as the solvent and mobile phase at a concentration of 1 g / L and a flow rate of 1 mL / min. NMR spectra were measured in deuterated benzene or deuterated chloroform using a Bruker Ascend 400 MHz or Varian Inova 500 MHz spectrometer. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry was performed using a Bruker Autoflex.

[0055] The synthesis of catalyst G3-OH in the following examples and comparative examples:

[0056] The synthesis of Methyl(E)-4-(3-((4-methyl-N-(prop-2-yn-1-yl)phenyl)sulfonamido)prop-1-en-1-yl)benzoate (the compound shown in Formula 8) was based on the literature report Macromolecules 2018, 51, 6497-6503.

[0057] Synthesis of (E)-N-(3-(4-(hydroxymethyl)phenyl)allyl)-4-methyl-N-(prop-2-yn-1-yl)benzenesulfonamide: Under argon protection, 6.1 g of methyl(E)-4-(3-((4-methyl-N-(prop-2-yn-1-yl)phenyl)sulfonamido)prop-1-en-1-yl)benzoate (Formula 8) was dissolved in 150 mL of dichloromethane. The solution was cooled to -78°C, and 36 mL of a 1.1 mol / L solution of diisobutylaluminum cyclohexane was added dropwise. After the addition was complete, the solution was slowly restored to room temperature. After 30 minutes, the reaction was quenched using a Roche salt and stirred for 10 hours. The solution was diluted with 100 mL of dichloromethane, washed with saturated brine, and dried over sodium sulfate to remove the solvent. The product was purified by silica gel column chromatography (1:2 ethyl acetate:hexane as eluent) to give 5.15 g of a yellow oily product. 1H NMR spectroscopy showed no impurities. Figure 1 ).

[0058]

[0059] The synthesis of compound G3, shown in Formula 9, is based on the literature report "A Practical and Highly Active Ruthenium-Based Catalyst that Effects the Cross Metathesis of Acrylonitrile." Angew. Chem. Int. Ed. 41:4035-4037.

[0060] Synthesis of catalyst G3-OH: Under argon protection, 727 mg of G3 was dissolved in 10 mL of benzene, and 1.065 g of (E)-N-(3-(4-(hydroxymethyl)phenyl)allyl)-4-methyl-N-(prop-2-yn-1-yl)benzenesulfonamide was added. The mixture was stirred for 30 minutes. At this point, the 1H NMR spectrum showed that G3 was converted to G3-OH. Figure 2 , Figure 3 ).

[0061]

[0062] The quencher 1(E)-N-(3-(2-(dodecylthio)phenyl)allyl)-4-(hydroxymethyl)-N-(prop-2-yn-1-yl)benzenesulfonamide in the following examples and comparative examples was synthesized according to the literature Relay Conjugation of Living Metathesis Polymers. J. Am. Chem. Soc. 2018, 140, 38, 12181–12188.

[0063] Example 1

[0064] Under argon protection at 20°C, benzene and 300 mg of 1,5-cyclooctadiene were added sequentially to a benzene solution containing 20 mg of G3-OH while stirring, bringing the concentration of 1,5-cyclooctadiene to 1.1 mol / L. After 30 minutes, 44 mg of quencher 1 was added to the solution and stirred for 1 minute. 2 g of silica gel was added to the reaction solution, and the benzene was evaporated to remove it. The silica gel was then added to a glass column containing 10 g of silica gel, and the column was washed with an eluent prepared from 100 mL of hexane and 30 mL of dichloromethane. The products were collected in four fractions, and the solvent was evaporated to remove the solvent. The following fractions were obtained: the first fraction had a mass of 48 mg and a weight-average molecular weight of 2002 g / mol; the second fraction had a mass of 13 mg and a weight-average molecular weight of 1650 g / mol; the third fraction had a mass of 21 mg and a weight-average molecular weight of 1870 g / mol; and the fourth fraction had a mass of 6 mg and a weight-average molecular weight of 4120 g / mol. The four products were combined to yield 87 mg of cyclic polycyclooctadiene. The weight-average molecular weight of the product was 2200 g / mol. 1H NMR spectroscopy showed no peaks in the 6–6.5 ppm range (Figure 1), indicating the absence of linear polymers in the product. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry showed a peak value of 54.11 x + 106.25, indicating the absence of linear polymers. Figure 5 ).

[0065] Example 2

[0066] Under argon protection at 20°C, benzene and 300 mg of 1,5-cyclooctadiene were added sequentially to a benzene solution containing 20 mg of G3-OH while stirring, bringing the concentration of 1,5-cyclooctadiene to 1.1 mol / L. After 30 minutes, 44 mg of quencher 1 was added to the solution and stirred for 1 minute. A solution was prepared in a beaker by mixing 100 mL of hexane and 10 mL of dichloromethane, and the polymer solution obtained from the polymerization reaction was poured into the beaker. The solid was removed by filtration, and the resulting liquid was collected and the solvent was removed to obtain 82 mg of cyclic polycyclooctadiene. The weight-average molecular weight of the product was 2100 g / mol. ¹H NMR spectroscopy showed no peaks in the 6–6.5 ppm range, indicating the absence of linear polymers in the product. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry showed a peak value of 54.11 x + 106.25, indicating the absence of linear polymers.

[0067] Example 3

[0068] Under argon protection at 20°C, benzene and 305 mg of cyclooctene were added sequentially to a benzene solution containing 20 mg of G3-OH while stirring, bringing the concentration of cyclooctene to 1.1 mol / L. After 30 minutes, 44 mg of quencher 1 was added to the solution and the mixture was stirred for 1 minute. 2 g of silica gel was added to the reaction solution, and the benzene was evaporated to remove it. The silica gel was then added to a glass column containing 10 g of silica gel, and the column was washed with an eluent prepared from 100 mL of hexane and 30 mL of dichloromethane. The product was collected, and the solvent was evaporated to remove it, yielding 37 mg of cyclic polycyclooctene. The weight-average molecular weight of the product was 3100 g / mol. The 1H NMR spectrum showed no peaks in the 6–6.5 ppm range, indicating the absence of a linear polymer in the product.

[0069] Example 4

[0070] Under argon protection at 20°C, benzene and 190 mg of cyclopentene were added sequentially to a benzene solution containing 20 mg of G3-OH while stirring, bringing the concentration of cyclopentene to 1.1 mol / L. After 30 minutes, 44 mg of quencher 1 was added to the solution and the mixture was stirred for 1 minute. 2 g of silica gel was added to the reaction solution, and the benzene was evaporated to remove it. The silica gel was then added to a glass column containing 10 g of silica gel, and the column was washed with an eluent prepared from 100 mL of hexane and 30 mL of dichloromethane. The product was collected, and the solvent was evaporated to remove it, yielding 21 mg of cyclic polycyclopentene. The weight-average molecular weight of the product was 1700 g / mol. The 1H NMR spectrum showed no peaks in the 6–6.5 ppm range, indicating the absence of a linear polymer in the product.

[0071] Example 5

[0072] Under argon protection at 0°C, benzene and 300 mg of 1,5-cyclooctadiene were added sequentially to a benzene solution containing 20 mg of G3-OH while stirring, resulting in a 1.1 mol / L concentration of 1,5-cyclooctadiene. After 30 minutes, 44 mg of quencher 1 was added to the solution and the mixture was stirred for 1 minute. 2 g of silica gel was added to the reaction solution, and the benzene was evaporated to remove it. The silica gel was then added to a glass column containing 10 g of silica gel, and the column was washed with an eluent prepared from 100 mL of hexane and 30 mL of dichloromethane. The product was collected, and the solvent was evaporated to remove it, yielding 60 mg of cyclic polycyclooctadiene. The weight-average molecular weight of the product was 1000 g / mol. The 1H NMR spectrum showed no peaks in the 6–6.5 ppm range, indicating the absence of a linear polymer in the product.

[0073] Example 6

[0074] Under argon protection at 50°C, benzene and 300 mg of 1,5-cyclooctadiene were added sequentially to a benzene solution containing 20 mg of G3-OH while stirring, resulting in a 1.1 mol / L concentration of 1,5-cyclooctadiene. After 30 minutes, 44 mg of quencher 1 was added to the solution and stirred for 1 minute. 2 g of silica gel was added to the reaction solution, and the benzene was evaporated to remove it. The silica gel was then added to a glass column containing 10 g of silica gel, and the column was washed with an eluent prepared from 100 mL of hexane and 30 mL of dichloromethane. The product was collected, and the solvent was evaporated to remove it, yielding 102 mg of cyclic polycyclooctadiene. The weight-average molecular weight of the product was 3500 g / mol. The 1H NMR spectrum showed no peaks in the 6–6.5 ppm range, indicating the absence of a linear polymer in the product.

[0075] Example 7

[0076] Under argon protection at 20°C, benzene and 300 mg of 1,5-cyclooctadiene were added sequentially to a benzene solution containing 20 mg of G3-OH while stirring, resulting in a 1,5-cyclooctadiene concentration of 0.27 mol / L. After 30 minutes, 44 mg of quencher 1 was added to the solution and the mixture was stirred for 1 minute. 2 g of silica gel was added to the reaction solution, and the benzene was evaporated to remove it. The silica gel was then added to a glass column containing 10 g of silica gel, and the column was washed with an eluent prepared from 100 mL of hexane and 30 mL of dichloromethane. The product was collected, and the solvent was evaporated to remove it. 192 mg of cyclic polycyclooctadiene was obtained. The weight-average molecular weight of the product was 1400 g / mol. The 1H NMR spectrum showed no peaks in the 6–6.5 ppm range, indicating the absence of a linear polymer in the product.

[0077] Example 8

[0078] Under argon protection at 20°C, benzene and 300 mg of 1,5-cyclooctadiene were added sequentially to a benzene solution containing 20 mg of G3-OH while stirring, bringing the concentration of 1,5-cyclooctadiene to 0.1 mol / L. After 30 minutes, 44 mg of quencher 1 was added to the solution and stirred for 1 minute. 2 g of silica gel was added to the reaction solution, and the benzene was evaporated to remove it. The silica gel was then added to a glass column containing 10 g of silica gel, and the column was washed with an eluent prepared from 100 mL of hexane and 30 mL of dichloromethane. The product was collected, and the solvent was evaporated to remove it. 276 mg of cyclic polycyclooctadiene was obtained. The weight-average molecular weight of the product was 800 g / mol. The 1H NMR spectrum showed no peaks in the 6–6.5 ppm range, indicating that the product contained no linear polymer.

[0079] Example 9

[0080] Under argon protection at 20°C, benzene and 300 mg of 1,5-cyclooctadiene were added sequentially to a benzene solution containing 20 mg of G3-OH while stirring, bringing the concentration of 1,5-cyclooctadiene to 1.1 mol / L. After 5 minutes, 44 mg of quencher 1 was added to the solution and the mixture was stirred for 1 minute. 2 g of silica gel was added to the reaction solution, and the benzene was evaporated to remove it. The silica gel was then added to a glass column containing 10 g of silica gel, and the column was washed with an eluent prepared from 100 mL of hexane and 30 mL of dichloromethane. The product was collected, and the solvent was evaporated to remove it, yielding 66 mg of cyclic polycyclooctadiene. The weight-average molecular weight of the product was 3000 g / mol. The 1H NMR spectrum showed no peaks in the 6–6.5 ppm range, indicating the absence of a linear polymer in the product.

[0081] Example 10

[0082] Under argon protection at 20°C, tetrahydrofuran and 300 mg of 1,5-cyclooctadiene were added sequentially to a tetrahydrofuran solution containing 20 mg of G3-OH while stirring, bringing the concentration of 1,5-cyclooctadiene to 1.1 mol / L. After 30 minutes, 44 mg of quencher 1 was added to the solution and the mixture was stirred for 1 minute. 2 g of silica gel was added to the reaction solution, and the tetrahydrofuran was evaporated to remove it. The silica gel was then added to a glass column containing 10 g of silica gel, and the column was washed with an eluent prepared from 100 mL of hexane and 30 mL of dichloromethane. The product was collected, and the solvent was evaporated to remove it, yielding 75 mg of cyclic polycyclooctadiene. The weight-average molecular weight of the product was 1000 g / mol. The 1H NMR spectrum showed no peaks in the 6–6.5 ppm range, indicating the absence of a linear polymer in the product.

[0083] Example 11

[0084] Under argon protection at 50°C, benzene and 305 mg of cyclooctene were added sequentially to a benzene solution containing 20 mg of G3-OH catalyst with stirring to achieve a cyclooctene concentration of 1.1 mol / L. After 30 minutes, 44 mg of quencher 1 was added to the solution and the mixture was stirred for 1 minute. 2 g of silica gel was added to the reaction solution, and the benzene was evaporated to remove it. The silica gel was then added to a glass column containing 10 g of silica gel, and the column was washed with an eluent prepared from 100 mL of hexane and 30 mL of dichloromethane. The product was collected, and the solvent was evaporated to remove it, yielding 34 mg of cyclic polycyclooctene. The weight-average molecular weight of the product was 4600 g / mol. The 1H NMR spectrum showed no peaks in the 6–6.5 ppm range, indicating the absence of a linear polymer in the product.

[0085] Example 12

[0086] Under argon protection at 20°C, benzene and 305 mg of cyclooctene were added sequentially to a benzene solution containing 20 mg of G3-OH catalyst with stirring to achieve a cyclooctene concentration of 0.27 mol / L. After 30 minutes, 44 mg of quencher 1 was added to the solution and the mixture was stirred for 1 minute. 2 g of silica gel was added to the reaction solution, and the benzene was evaporated to remove it. The silica gel was then added to a glass column containing 10 g of silica gel, and the column was washed with an eluent prepared from 100 mL of hexane and 30 mL of dichloromethane. The product was collected, and the solvent was evaporated to remove it, yielding 128 mg of cyclic polycyclooctene. The weight-average molecular weight of the product was 2800 g / mol. The 1H NMR spectrum showed no peaks in the 6–6.5 ppm range, indicating the absence of a linear polymer in the product.

[0087] Example 13

[0088] Under argon protection at 20°C, benzene and 305 mg of cyclooctene were added sequentially to a benzene solution containing 20 mg of G3-OH catalyst with stirring to achieve a cyclooctene concentration of 0.1 mol / L. After 30 minutes, 44 mg of quencher 1 was added to the solution and the mixture was stirred for 1 minute. 2 g of silica gel was added to the reaction solution, and the benzene was evaporated to remove it. The silica gel was then added to a glass column containing 10 g of silica gel, and the column was washed with an eluent prepared from 100 mL of hexane and 30 mL of dichloromethane. The product was collected, and the solvent was evaporated to remove it. 247 mg of cyclic polycyclooctene was obtained. The weight-average molecular weight of the product was 1800 g / mol. The 1H NMR spectrum showed no peaks in the 6–6.5 ppm range, indicating the absence of a linear polymer in the product.

[0089] Example 14

[0090] Under argon protection at 20°C, benzene and 305 mg of cyclooctene were added sequentially to a benzene solution containing 20 mg of G3-OH catalyst with stirring to achieve a cyclooctene concentration of 1.1 mol / L. After 5 minutes, 44 mg of quencher 1 was added to the solution and the mixture was stirred for 1 minute. 2 g of silica gel was added to the reaction solution, and the benzene was evaporated to remove it. The silica gel was then added to a glass column containing 10 g of silica gel, and the column was washed with an eluent prepared from 100 mL of hexane and 30 mL of dichloromethane. The product was collected, and the solvent was evaporated to remove it, yielding 37 mg of cyclic polycyclooctene. The weight-average molecular weight of the product was 3200 g / mol. The 1H NMR spectrum showed no peaks in the 6–6.5 ppm range, indicating the absence of a linear polymer in the product.

[0091] Comparative Example 1

[0092] Under argon protection at 20°C, benzene and 300 mg of 1,5-cyclooctadiene were added sequentially to a benzene solution containing 23 mg of G2 catalyst (Formula 10) with stirring, resulting in a 1.1 mol / L concentration of 1,5-cyclooctadiene. After 30 minutes, 44 mg of quencher 1 was added to the solution and stirred for 1 minute. 2 g of silica gel was added to the reaction solution, and the benzene was evaporated to remove it. The silica gel was then added to a glass column containing 10 g of silica gel, and the column was washed with an eluent prepared from 100 mL of hexane and 30 mL of dichloromethane. The product was collected, and the solvent was evaporated to remove it. 78 mg of cyclic polycyclooctadiene was obtained. The weight-average molecular weight of the product was 4200 g / mol. ¹H NMR spectroscopy showed peaks in the range of 6–6.5 ppm, indicating the presence of a linear polymer in the product.

[0093] Structural formula of G2 catalyst:

[0094] Comparative Example 2

[0095] Under argon protection at 20°C, benzene and 300 mg of 1,5-cyclooctadiene were added sequentially to a benzene solution containing 19 mg of G3 catalyst with stirring to achieve a 1.1 mol / L concentration of 1,5-cyclooctadiene. After 30 minutes, 44 mg of quencher 1 was added to the solution and stirred for 1 minute. 2 g of silica gel was added to the reaction solution, and the benzene was evaporated to remove it. The silica gel was then added to a glass column containing 10 g of silica gel, and the column was washed with an eluent prepared from 100 mL of hexane and 30 mL of dichloromethane. The product was collected, and the solvent was evaporated to remove it, yielding 126 mg of cyclic polycyclooctadiene. The weight-average molecular weight of the product was 2900 g / mol. ¹H NMR spectroscopy showed peaks in the range of 6–6.5 ppm, indicating the presence of a linear polymer in the product.

[0096] Comparative Example 3

[0097] Under argon protection at 20°C, benzene and 300 mg of 1,5-cyclooctadiene were added sequentially to a benzene solution containing 20 mg of G3-OH catalyst with stirring, resulting in a 1.1 mol / L concentration of 1,5-cyclooctadiene. After 30 minutes, 1 mL of vinyl ether was added to the solution and the mixture was stirred for 10 minutes. 2 g of silica gel was added to the reaction solution, and the benzene was evaporated to remove it. The silica gel was then added to a glass column containing 10 g of silica gel, and the column was washed with an eluent prepared from 100 mL of hexane and 30 mL of dichloromethane. The product was collected, and the solvent was evaporated to remove it, yielding 120 mg of cyclic polycyclooctadiene. The weight-average molecular weight of the product was 3000 g / mol. ¹H NMR spectroscopy showed peaks in the range of 6–6.5 ppm, indicating the presence of a linear polymer in the product.

[0098] Comparative Example 4

[0099] Under argon protection at 20°C, benzene and 300 mg of cyclooctene were added sequentially to a benzene solution containing 19 mg of G3 catalyst with stirring to achieve a cyclooctene concentration of 1.1 mol / L. After 30 minutes, 44 mg of quencher 1 was added to the solution and stirred for 1 minute. 2 g of silica gel was added to the reaction solution, and the benzene was evaporated to remove it. The silica gel was then added to a glass column containing 10 g of silica gel, and the column was washed with an eluent prepared from 100 mL of hexane and 30 mL of dichloromethane. The product was collected, and the solvent was evaporated to remove it, yielding 58 mg of cyclic polycyclooctene. The weight-average molecular weight of the product was 3800 g / mol. ¹H NMR spectroscopy showed peaks in the range of 6–6.5 ppm, indicating the presence of a linear polymer in the product.

[0100] Comparative Example 5

[0101] Under argon protection at 70°C, benzene and 300 mg of 1,5-cyclooctadiene were added sequentially to a benzene solution containing 20 mg of G3-OH while stirring, resulting in a 1.1 mol / L concentration of 1,5-cyclooctadiene. After 30 minutes, 44 mg of quencher 1 was added to the solution and stirred for 1 minute. 2 g of silica gel was added to the reaction solution, and the benzene was evaporated to remove it. The silica gel was then added to a glass column containing 10 g of silica gel, and the column was washed with an eluent prepared from 100 mL of hexane and 30 mL of dichloromethane. The product was collected, and the solvent was evaporated to remove it, yielding 75 mg of cyclic polycyclooctadiene. The weight-average molecular weight of the product was 2000 g / mol. ¹H NMR spectroscopy showed peaks in the range of 6–6.5 ppm, indicating the presence of a linear polymer in the product.

[0102] Comparative Example 6

[0103] Under argon protection at 20°C, benzene and 300 mg of 1,5-cyclooctadiene were added sequentially to a benzene solution containing 20 mg of G3-OH while stirring, resulting in a 1.1 mol / L concentration of 1,5-cyclooctadiene. After 300 minutes, 44 mg of quencher 1 was added to the solution and the mixture was stirred for 1 minute. 2 g of silica gel was added to the reaction solution, and the benzene was evaporated to remove it. The silica gel was then added to a glass column containing 10 g of silica gel, and the column was washed with an eluent prepared from 100 mL of hexane and 30 mL of dichloromethane. The product was collected, and the solvent was evaporated to remove it, yielding 93 mg of cyclic polycyclooctadiene. The weight-average molecular weight of the product was 4100 g / mol. ¹H NMR spectroscopy showed peaks in the range of 6–6.5 ppm, indicating the presence of a linear polymer in the product.

[0104] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for producing a high purity cyclic polyolefin, characterized by, at least comprising the steps of catalyzing the polymerization of a cyclic olefin monomer at a temperature not higher than 60℃ for a time not longer than 30 minutes using a metathesis catalyst containing a polar group, and quenching the reaction using a quenching agent containing a polar group, and separating the cyclic polyolefin from the product.

2. The method for producing a high-purity cyclic polyolefin according to claim 1, characterized by, The method for separating the cyclic polyolefin from the product is column chromatography or sedimentation separation.

3. The method for producing a high-purity cyclic polyolefin according to claim 2, characterized by, When column chromatography is used, the stationary phase is silica gel or alumina, and the mobile phase is a combination of one or more of straight-chain aliphatic hydrocarbons, cyclic aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, and tetrahydrofuran; or When sedimentation separation is used, the good solvent and the poor solvent are both a combination of one or more of straight-chain aliphatic hydrocarbons, cyclic aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, and tetrahydrofuran.

4. The method for producing high-purity cyclic polyolefin according to any one of claims 1 to 3, characterized by, The structure of the metathesis catalyst is shown in Formula 7: wherein M is a metal ruthenium or osmium; m is 0, 1 or 2; X1 and X2 are anionic ligands; L1, L2 are neutral electron-donating ligands; R3 and R4 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and any one or more substituents of R3 and R4 must contain one or more polar functional groups; any two or more of X1, X2, L1, L2, R3 and R4 ligands can be linked together to form a cyclic group, or any one or more of X1, X2, L1, L2, R3 and R4 ligands can be linked to a support; and / or The structure of the quencher is shown in Formula 6: wherein R1 is selected from one of C1-C20 alkyl, C2-C20 alkenyl, C6-C20 aryl; R2 is selected from one of substituted or unsubstituted benzenesulfonyl, ester, carbonyl.

5. The method for producing a high-purity cyclic polyolefin according to claim 4, characterized by, In formula 7, the polar functional group is selected from oxygen-containing polar functional groups, nitrogen-containing functional groups, halogen-containing functional groups, silicon-containing functional groups, and functional groups similar to the above-mentioned functional groups.

6. The method for producing a high-purity cyclic polyolefin according to claim 5, characterized by, In formula 7, the oxygen-containing polar functional group is carboxyl, sulfonic acid group, phosphoric acid group, hydroxyl; and / or The nitrogen-containing functional group is cyano, primary amine, secondary amine, amide; and / or The halogen-containing functional group is fluorine, chlorine, bromine, halogenated hydrocarbon of 1 to 12 carbons; and / or The silicon-containing functional group is trimethoxysilane, triethoxysilane, methyldiethoxysilane.

7. The method for producing a high-purity cyclic polyolefin according to any one of claims 1 to 3, characterized by, The molar ratio of the cyclic olefin monomer to the catalyst is 500000-200:1; and / or The molar ratio of the cyclic olefin monomer to the catalyst is 100000-500:1; and / or The amount of the quenching agent is 1-10 times the molar amount of the catalyst.

8. The method for producing a high-purity cyclic polyolefin according to any one of claims 1 to 3, characterized by, The polymerization reaction is carried out in an organic solvent, and the concentration of the cyclic olefin monomer is 0.01-10 mol / L; preferably, the concentration of the cyclic olefin monomer is not higher than 5 mol / L.

9. The method for producing a high-purity cyclic polyolefin according to claim 8, characterized by, The temperature of the polymerization reaction is 0-60℃.

10. The method for producing a high-purity cyclic polyolefin according to any one of claims 1 to 3, characterized by, The cyclic olefin monomer is an olefin containing a carbon-carbon double bond with a carbon atom number of 5-20; and / or The cyclic olefin monomer is selected from one or more of the cyclic olefins shown in the following formulas 1-5; wherein n = 1, 3, 4 or 8.

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