A cyclic olefin copolymer and a method for preparing the same

Abstract

The present application relates to the technical field of new high-end polyolefin, in particular to a cyclic olefin copolymer and a preparation method thereof. The cyclic olefin copolymer has the structure shown in formula I: the refractive index of the cyclic olefin copolymer can be up to 1.72, and the light transmittance is more than 90%. By adjusting the type and proportion of the cyclic olefin monomer in the copolymer, the cyclic olefin copolymer with the refractive index ranging from 1.64 to 1.72 and the Abbe number ranging from 12 to 20 can be obtained. The glass transition temperature of the cyclic olefin copolymer is between 170 DEG C and 201 DEG C, and 5% thermal decomposition occurs above 420 DEG C, indicating that the cyclic olefin copolymer has high heat resistance. In addition, the water absorption of the cyclic olefin copolymer is less than 0.01%, which shows excellent low moisture absorption. With the ultra-high refractive index, excellent transparency, high heat resistance and low moisture absorption, the cyclic olefin copolymer shows great application potential in the high-end optical field.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of new high-end polyolefin technology, in particular to a cyclic olefin copolymer and a preparation method thereof. BACKGROUND

[0002] As an amorphous, highly pure transparent resin, the cyclic olefin copolymer has excellent optical properties. In the case of comparable transparency, the heat resistance of the cyclic olefin copolymer is significantly better than that of PMMA. In the case of comparable heat resistance, its transparency is significantly better than that of PC material. Due to its unique optical properties and heat resistance, it has been widely used in the field of optics.

[0003] However, with the continuous improvement of the performance requirements of materials in the field of optics, the refractive index of the existing cyclic olefin copolymer has gradually failed to meet the needs of emerging technologies. Especially in high-refractive applications such as high-end optical lenses, display screens, sensors, etc., the refractive index requirement of the material has exceeded 1.70, and even reached 1.72. However, increasing the refractive index usually compromises other properties such as transparency, heat resistance, or low moisture absorption, resulting in poor overall performance and difficulty in meeting the demand for multiple properties in actual applications.

[0004] Therefore, how to break through the limit of 1.72 refractive index in the cyclic olefin copolymer while considering transparency, heat resistance and low moisture absorption has become a major technical problem in current material development. An innovative material is urgently needed to fill this key gap and provide new solutions for the field of optics and electronics. SUMMARY

[0005] Based on the above, the present application provides a high-refractive, transparent cyclic olefin copolymer and a preparation method thereof. The refractive index of the cyclic olefin copolymer breaks through 1.72, while having high transparency, high heat resistance and low moisture absorption.

[0006] To achieve the above-mentioned purpose, the present application provides the following solutions:

[0007] One of the technical solutions of the present application is a cyclic olefin copolymer having the structure shown in formula I:

[0008]

[0009] In formula I, x and y are the degree of polymerization, 20≤x≤1000, 0≤y≤1000, but not a block copolymer; the dotted line represents a bond or no bond; i is the number of rings, i is 0 or 1; m and n are the number of carbon atoms, 0≤m≤10, 0≤n≤4; R1 and R2 are each independently selected from one of hydrogen atom, alkyl and alkenyl, and R1 and R2 can be bonded or not bonded.

[0010] The second aspect of the present application is a preparation method of the cyclic olefin copolymer, comprising the following steps:

[0011] carrying out ring-opening metathesis polymerization of the monomers in the presence of a catalyst under a protective atmosphere to obtain a polymerization product;

[0012] carrying out hydrogenation of the polymerization product to obtain the cyclic olefin copolymer;

[0013] The monomers comprise at least one compound of Formula II and at least one compound of Formula III.

[0014] The compound of Formula II has the following structural formula:

[0015]

[0016] In Formula II, m is the number of carbon atoms, and 0≤m≤10.

[0017] The compound of Formula III has the following structural formula:

[0018]

[0019] In Formula III, the dotted line represents a bond or no bond; i is the number of rings, and i is 0 or 1; n is the number of carbon atoms, and 0≤n≤4; R1 and R2 are each independently selected from one of a hydrogen atom, an alkyl group and an alkenyl group, wherein R1 and R2 can form a bond or no bond.

[0020] In a preferred embodiment of the present application, the compound of Formula II is selected from at least one of the structures of HM1-HM5:

[0021]

[0022] wherein m is the number of carbon atoms, and 0≤m≤10.

[0023] In a preferred embodiment of the present application, the compound of Formula III is selected from at least one of the structures of M1-M10:

[0024]

[0025] The source of the cyclic olefin monomers of Formula II and Formula III is not particularly limited in the present application, and can be obtained by using a preparation method well known to those skilled in the art, or by a commercially available route.

[0026] In the present application, the cycloolefin monomer is dissolved in a solvent, and then subjected to subsequent ring-opening metathesis polymerization; the solvent is a hydrocarbon compound, a halogenated hydrocarbon compound, a cyclic hydrocarbon compound or an aromatic hydrocarbon compound; preferably, it is cyclopentane, hexane, cyclohexane, decane, isododecane, benzene, toluene, xylene, ethylbenzene, chlorobenzene, dichloromethane or chloroform; more preferably, it is benzene, toluene, xylene, chlorobenzene, dichloromethane, chloroform or cyclohexane. The present application does not have special restrictions on the source of the solvent, and the above-mentioned types of solvents known to those skilled in the art can be used, which can be obtained by commercial means. The present application does not have special restrictions on the amount of the solvent, and the amount of the solvent used in the polymerization reaction known to those skilled in the art can be used. The present application does not have special restrictions on the dissolution method, for example, stirring dissolution, and the stirring method known to those skilled in the art can be used. In the present application, the stirring time is preferably 4 min to 10 min, more preferably 4 min to 8 min, and most preferably 5 min.

[0027] In a preferred embodiment of the present application, the catalyst is a ruthenium catalyst, a molybdenum catalyst or a tungsten catalyst; further preferably, it is a ruthenium catalyst.

[0028] In the present application, the ruthenium catalyst is preferably one of the structures shown in Formula IV:

[0029]

[0030] In Formula IV, PCy3 is tricyclohexylphosphine; Mes is 2,4,6-trimethylphenyl.

[0031] The above-mentioned catalyst has the advantages of high activity and good polymerization tolerance, and in the process of preparing the high-refractive cycloolefin polymer of the present application, it does not need to add any cocatalyst, has a fast initiation rate, the catalytic conversion rate reaches 100%, and no crosslinking side reaction occurs. The present application does not have special restrictions on the source of the catalyst having the structure shown in Formula IV, which can be obtained by commercial means.

[0032] In the present application, the ruthenium catalyst is dissolved in a solvent, and then catalyzes the ring-opening metathesis polymerization of the monomer compound; the solvent is consistent with the above-mentioned solvent (the solvent used for dissolving the cycloolefin monomer), and specifically, it is a hydrocarbon compound, a halogenated hydrocarbon compound, a cyclic hydrocarbon compound or an aromatic hydrocarbon compound; preferably, it is cyclopentane, hexane, cyclohexane, decane, isododecane, benzene, toluene, xylene, ethylbenzene, chlorobenzene, dichloromethane or chloroform; more preferably, it is benzene, toluene, xylene, chlorobenzene, dichloromethane, chloroform, cyclohexane. The present application does not have special restrictions on the source of the solvent, and the above-mentioned types of solvents known to those skilled in the art can be used, which can be obtained by commercial means.

[0033] In a preferred embodiment of the present application, the molar ratio of the monomer to the catalyst is (100-2000):1; preferably (200-1000):1, more preferably (200-800):1, preferably 30-150 min, more preferably 60-120 min.

[0034] In a preferred embodiment of the present application, the temperature of the ring-opening metathesis polymerization is 25-80°C, preferably 25-60°C, more preferably 25-40°C; the time of the ring-opening metathesis polymerization is 4-240 min.

[0035] The ring-opening metathesis polymerization of the present application is preferably carried out under anhydrous and anaerobic conditions. In the present application, a standard Schlenk flask is used under the protection of nitrogen. The ring-opening metathesis polymerization of the present application is preferably carried out under stirring, and the stirring method of the polymerization reaction is not particularly limited in the present application, and a stirring method known to those skilled in the art can be used.

[0036] In the present application, after the completion of the ring-opening metathesis polymerization, a step of terminating the ring-opening metathesis polymerization and separating the reaction product is further included; the termination of the ring-opening metathesis polymerization is preferably carried out by using a termination agent; the separation is specifically carried out by mixing the polymerization reaction solution with a precipitant to obtain a precipitated product, and then filtering, washing, and drying the precipitated product to obtain the polymerization reaction product.

[0037] The type and source of the termination agent are not particularly limited in the present application, and a termination agent known to those skilled in the art can be used. In the preparation of a cyclic olefin copolymer, the termination agent can be obtained by a commercial route. In the present application, the termination agent is preferably vinyl ethyl ether. The molar ratio of the termination agent to the catalyst is preferably (100-800):1, more preferably (200-400):1, and most preferably 300:1; the time of terminating the polymerization reaction is preferably 20-60 min, more preferably 30-35 min.

[0038] The method of filtering, washing, and drying the precipitated product is not particularly limited in the present application, and a method known to those skilled in the art can be used. Ethanol is preferably used as the washing reagent, and the number of washing times is preferably 1-5 times, more preferably 3 times. The drying method is preferably vacuum drying, the drying temperature is preferably 20-60°C, more preferably 30-50°C, and most preferably 40°C. The drying time is preferably 12-24 h, more preferably 14-20 h, and most preferably 16-18 h.

[0039] In the present application, after obtaining the polymerization product, the polymerization product and a hydrogen source are subjected to a hydrogenation reaction to obtain a cyclic olefin copolymer. The hydrogenation reaction in the present application is preferably carried out in the presence of a protective gas. In the present application, the protective gas for the hydrogenation reaction is preferably nitrogen. The method for the hydrogenation reaction in the present application is not particularly limited, and a hydrogenation reaction technique known to those skilled in the art can be used.

[0040] The kind of the hydrogen source in the present application is not particularly limited, and the hydrogen source is preferably a hydrazine compound or hydrogen gas.

[0041] In the present application, when the hydrogen source is a hydrazine compound, the hydrogenation reaction is preferably carried out according to the following method to obtain a cyclic olefin copolymer: the polymerization product and the hydrazine compound are subjected to a hydrogenation reaction in a solvent to obtain a cyclic olefin copolymer. In the present application, the hydrazine compound is preferably p-toluenesulfonyl hydrazide. The ratio of the number of moles of double bonds in the polymerization product to the number of moles of the hydrazine compound is 1 : (3 to 7), and is preferably 1 : (5 to 6). The solvent is a hydrocarbon compound, a halogenated hydrocarbon compound, a cyclic hydrocarbon compound, or an aromatic hydrocarbon compound; preferably, cyclopentane, hexane, cyclohexane, decane, isododecane, benzene, toluene, xylene, ethylbenzene, chlorobenzene, dichloromethane, or chloroform; more preferably, benzene, toluene, xylene, chlorobenzene, dichloromethane, or chloroform; and most preferably, toluene, xylene, or chlorobenzene. The amount of the solvent used in the present application is not particularly limited, as long as it can provide a liquid environment for the hydrogenation reaction. The aid for the hydrogenation reaction is an amine compound, and is preferably tri-n-propylamine. A free radical scavenger is also included in the reaction system, and the kind and source of the free radical scavenger are not particularly limited, and a commercially available free radical scavenger can be used. The free radical scavenger in the present application is preferably 2,6-di-tert-butyl-4-methylphenol, and the amount used is 0.05 eqv to 3 eqv relative to the number of moles of the catalyst. The temperature for the hydrogenation reaction is 100°C to 150°C, preferably 110°C to 130°C, and more preferably 120°C. The reaction time is 12 to 24 hours, and is preferably 14 to 18 hours. After the hydrogenation reaction is completed, the obtained hydrogenation reaction product is preferably mixed with ethanol, and is subjected to filtration, washing, and drying to obtain a hydrogenated cyclic olefin copolymer. The purity of the ethanol is preferably 95% to 99%. The method for drying is preferably vacuum drying, the drying time is preferably 12 to 24 hours, and is more preferably 16 to 20 hours. The drying temperature is preferably 50°C to 70°C, more preferably 55°C to 65°C, and most preferably 60°C.

[0042] In the present application, when the hydrogen source is hydrogen, the present application preferably produces the cycloolefin copolymer by the following hydrogenation reaction: the polymerization reaction product is subjected to a hydrogenation reaction with hydrogen and a catalyst in a solvent to produce the cycloolefin copolymer. In the present application, the catalyst is a platinum catalyst, a palladium catalyst, a rhodium catalyst or a nickel catalyst, preferably a palladium catalyst or a nickel catalyst. The solvent is a hydrocarbon compound, a halogenated hydrocarbon compound, a cyclic hydrocarbon compound or an aromatic hydrocarbon compound; preferably cyclopentane, hexane, cyclohexane, decane, isododecane, benzene, toluene, xylene, ethylbenzene, chlorobenzene, dichloromethane or chloroform; more preferably benzene, toluene, xylene, chlorobenzene, dichloromethane or chloroform; most preferably toluene, xylene or chlorobenzene. The present application does not have a particular limitation on the amount of the solvent, as long as it can provide a liquid environment for the hydrogenation reaction. The temperature of the hydrogenation reaction is 60°C to 150°C, preferably 110°C to 130°C, more preferably 120°C; the reaction time is 10 to 20 hours, preferably 12 to 15 hours. After the hydrogenation reaction is completed, the present application preferably mixes the obtained hydrogenation reaction product with ethanol, filters, washes and dries to obtain the hydrogenated cycloolefin copolymer. The purity of the ethanol is preferably between 95% and 99%; the method of drying is preferably vacuum drying, the drying time is preferably 12 to 24 hours, more preferably 16 to 20 hours; the drying temperature is preferably 50°C to 70°C, more preferably 55°C to 65°C, most preferably 60°C.

[0043] The third technical solution of the present application is an optical material, which comprises the cycloolefin copolymer.

[0044] The present application discloses the following technical effects:

[0045] The present application provides a cycloolefin copolymer with excellent performance. The prepared cycloolefin copolymer has a light transmittance of greater than 90%. By adjusting the types of copolymerized cycloolefin monomers and the ratios therebetween, a cycloolefin copolymer with a refractive index of 1.64 to 1.72 and an Abbe number of 12 to 20 can be obtained, and the water absorption rate is less than 0.01%, which exhibits excellent low moisture absorption. The glass transition temperature of the cycloolefin copolymer is 170°C to 201°C, and the 5wt% thermal weight loss temperature is all above 420°C, indicating that it has high heat resistance. With ultra-high refractive index, excellent transparency, high heat resistance and low moisture absorption, the cycloolefin copolymer exhibits extraordinary application potential in high-end optical fields. BRIEF DESCRIPTION OF DRAWINGS

[0046] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the accompanying drawings needed in the embodiments will be briefly introduced as follows. Obviously, the accompanying drawings in the following description only only some embodiments of the present application, and for those skilled in the art, other drawings can be obtained based on these drawings without creative labor.

[0047] Figure 1 NMR spectrum of the cycloolefin monomer obtained in Example 3 of the present application 1 H-NMR spectrum;

[0048] Figure 2 NMR spectrum of the cycloolefin monomer obtained in Example 3 of the present application 13 C-NMR spectrum;

[0049] Figure 3 NMR spectrum of the cycloolefin copolymer obtained in Example 11 of the present application 1 H-NMR spectrum;

[0050] Figure 4 NMR spectrum of the cycloolefin copolymer obtained in Example 11 of the present application 13 C-NMR spectrum;

[0051] Figure 5 Differential scanning calorimetry curve of the cycloolefin copolymer obtained in Example 9 of the present application;

[0052] Figure 6 Refractive index curve of the cycloolefin copolymer obtained in Example 11 of the present application;

[0053] Figure 7 Thermogravimetric curve of the cycloolefin copolymer obtained in Example 14 of the present application in nitrogen;

[0054] Figure 8 Transmittance curve of the cycloolefin copolymer obtained in Example 19 of the present application. DETAILED DESCRIPTION

[0055] Various exemplary embodiments of the present application will now be described in detail, which should not be considered as limiting the present application, but should be understood as a more detailed description of some aspects, characteristics and embodiments of the present application.

[0056] It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present application. In addition, where a range of values is provided, it is understood that each intervening value, to the upper and lower limit of the range is also specifically disclosed. Each smaller range between any stated value or intervening value in the stated range and any other stated or intervening value in that stated range is encompassed. The upper and lower limits of these smaller ranges can independently be included or excluded in the range.

[0057] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Although preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application. All documents mentioned herein are incorporated by reference to disclose and describe in detail the methods and / or materials which are related to the present application. In case of conflict, the content of the present specification will control.

[0058] Many modifications and variations of the present application described in the specification are possible without departing from the scope or spirit of the application. Other embodiments of the application will be apparent to those skilled in the art from consideration of the specification and practice of the application disclosed herein. The specification and examples given are exemplary only.

[0059] As used herein, the terms "comprise", "comprising", "include", "including", "have", "having" and the like are open-ended and do not exclude additional elements or steps.

[0060] As used herein, the term "room temperature" means 20-30°C, unless otherwise specified.

[0061] In the embodiments of the present application, the prepared cyclic olefin copolymer is determined by the following methods:

[0062] Conversion rate: The product weighing method is used in the present application to test the polymerization conversion rate of the polymerization reaction.

[0063] NMR characterization: The present application is characterized by using a Bruker 400MHz nuclear magnetic resonance spectrometer, deuterated chloroform (CDCl3) or deuterated tetrachloroethane (C2D2Cl4) is selected as the solvent, and tetramethylsilane (TMS) is used as the internal standard.

[0064] Glass transition temperature: The glass transition temperature of the cyclic olefin copolymer is obtained by differential thermal analysis method, the detection method is to use DSC Q200-TA differential scanning calorimeter to perform differential thermal analysis determination, the heating and cooling rate is 10℃ / min, and the second scanning is performed.

[0065] Thermal gravimetric analysis: The thermal gravimetric analysis was measured by using an E1mer Pyris 1 instrument at a heating rate of 10°C / min.

[0066] Refractive index: The refractive index was measured by using an SE-VE-L ellipsometer in the wavelength range of 400-1000 nm, and the refractive index corresponding to the wavelength of 589 nm was selected.

[0067] Abbe number: The Abbe number was calculated according to the refractive index at three wavelengths. The Abbe number defined by the following formula was used in the present application: νd = (nd - 1) / (nF - nC), wherein nd, nF and nC represent the refractive index at the wavelength of 589 nm, 486 nm and 656 nm, respectively.

[0068] Transparency: The transparency of the cycloolefin copolymer was tested by using a Shimadzu UV-3600i ultraviolet-visible spectrophotometer, and the test wavelength was 400 nm-800 nm.

[0069] Water absorption rate: The determination method was as follows: after preparing a sample with a thickness of 1-3 mm, the sample was immersed in water at 23°C for 24 hours according to the ASTM-D 570 standard, and the water absorption rate was calculated by measuring the mass change of the sample.

[0070] The technical solutions described in the present application are conventional solutions in the art if not specifically stated, and the reagents or raw materials used are obtained by methods well known to those skilled in the art or purchased on the market if not specifically stated.

[0071] The technical solutions provided by the present application will be described in detail below in conjunction with examples, but they should not be understood as limiting the scope of protection of the present application.

[0072] Example 1

[0073] Synthesis of cycloolefin monomer HM1 (side chain carbon number is 1)

[0074]

[0075] Under a nitrogen atmosphere, 7H-dibenzo[a,g]carbazole (94 g, 0.35 mol) was mixed with sodium hydride (15 g, 0.62 mol) in anhydrous N,N-dimethylformamide and stirred for 2 h, 5-(iodomethyl)bicyclo[2.2.1]hept-2-ene (96 g, 0.41 mol) was added dropwise, and the reaction was carried out at 120°C for 24 h. Ethyl acetate was extracted three times, and the column was purified by gradient elution, V 乙酸乙酯 :V 石油醚 = 0-1:5, vacuum dried at 60°C for 10 hours, and 104 g of white solid was obtained (yield 80%).

[0076] Example 2

[0077] Synthesis of cycloalkene monomer HM2 (1 carbon in side chain)

[0078]

[0079] 7H-dibenzo[b,g]carbazole (94 g, 0.35 mol) was mixed with sodium hydride (15 g, 0.62 mol) in dry N,N-dimethylformamide under nitrogen atmosphere and stirred for 2 h. 5-(Iodomethyl)bicyclo[2.2.1]hept-2-ene (77 g, 0.41 mol) was added dropwise and reacted at 120 °C for 24 h. Extracted with ethyl acetate three times, spin dried and purified by column chromatography with gradient elution, V 乙酸乙酯 :V 石油醚 = 0-1 : 4, dried at 60 °C under vacuum for 10 h to obtain 85 g of white solid (65% yield).

[0080] Example 3

[0081] Synthesis of cycloalkene monomer HM3 (1 carbon in side chain)

[0082]

[0083] 7H-dibenzo[c,g]carbazole (94 g, 0.35 mol) was mixed with sodium hydride (15 g, 0.62 mol) in dry N,N-dimethylformamide under nitrogen atmosphere and stirred for 2 h. 5-(Iodomethyl)bicyclo[2.2.1]hept-2-ene (77 g, 0.41 mol) was added dropwise and reacted at 120 °C for 24 h. Extracted with ethyl acetate three times, spin dried and purified by column chromatography with gradient elution, V 乙酸乙酯 :V 石油醚 = 0-1 : 5, dried at 60 °C under vacuum for 10 h to obtain 107 g of white solid (82% yield).

[0084] Example 4

[0085] Synthesis of cycloalkene monomer HM1 (3 carbons in side chain)

[0086]

[0087] 7H-dibenzo[a,g]carbazole (94 g, 0.35 mol) was mixed with sodium hydride (15 g, 0.62 mol) in dry N,N-dimethylformamide under nitrogen atmosphere and stirred for 2 h. 5-(3-bromopropyl)bicyclo[2.2.1]hept-2-ene (88 g, 0.41 mol) was added dropwise and reacted at 120 °C for 24 h. Extracted with ethyl acetate three times, spin dried and purified by column chromatography with gradient elution, V 乙酸乙酯 :V 石油醚 = 0-1 : 6, dried at 60 °C under vacuum for 10 h to obtain 112 g of white solid (80% yield).

[0088] Example 5

[0089] Synthesis of cycloalkene monomer HM3 (side chain carbon number 2)

[0090]

[0091] 7H-dibenzo[c,g]carbazole (94 g, 0.35 mol) and sodium hydride (15 g, 0.62 mol) were stirred in anhydrous N,N-dimethylformamide under nitrogen atmosphere for 2 h, and 5-(2-iodoethyl)bicyclo[2.2.1]hept-2-ene (102 g, 0.41 mol) was added dropwise, and reacted at 120°C for 24 h. It was extracted with ethyl acetate three times, and column-purified, and gradient eluted, V 乙酸乙酯 :V 石油醚 = 0~1:6, 60°C vacuum dried for 10 hours to obtain 112 g (yield 82%) of white solid.

[0092] Example 6

[0093] Synthesis of cycloalkene monomer HM3 (side chain carbon number 0)

[0094]

[0095] 7H-dibenzo[c,g]carbazole (94 g, 0.35 mol) and sodium hydride (15 g, 0.62 mol) were stirred in anhydrous N,N-dimethylformamide under nitrogen atmosphere for 2 h, and 5-bromobicyclo[2.2.1]hept-2-ene (71 g, 0.41 mol) was added dropwise, and reacted at 120°C for 24 h. It was extracted with ethyl acetate three times, and column-purified, and gradient eluted, V 乙酸乙酯 :V 石油醚 = 0~1:5, 60°C vacuum dried for 10 hours to obtain 75 g (yield 60%) of white solid.

[0096] Example 7

[0097] Synthesis of cycloalkene monomer HM3 (side chain carbon number 5)

[0098]

[0099] 7-(hept-6-en-1-yl)-7H-dibenzo[c,g]carbazole (218 g, 0.60 mol), dicyclopentadiene (13 g, 0.10 mol), and 2,6-di-tert-butyl-p-cresol (0.5 g, 2.3 mmol) were added to a 250 ml reaction kettle, and stirred at 200°C for 20 hours under nitrogen atmosphere, and pressurized to 5 MPa. After cooling, it was column-purified, and gradient eluted, V 乙酸乙酯 :V 石油醚= 0~1:10, 60°C vacuum drying for 10 hours, white solid 53g (yield 60%).

[0100] Example 8

[0101] Synthesis of cycloolefin monomer HM1 (6 carbon atoms in side chain)

[0102]

[0103] 7-(oct-7-en-1-yl)-7H-dibenzo[a,g]carbazole (227g, 0.60mol), dicyclopentadiene (13g, 0.10mol) and 2,6-di-tert-butyl-p-cresol (0.5g, 2.3mmol) were added to a 250ml reaction kettle, nitrogen atmosphere, pressurized to 5MPa, stirred at 200°C for 20 hours. After cooling, column purification, gradient elution, V 乙酸乙酯 :V 石油醚 = 0~1:10, 60°C vacuum drying for 10 hours, white solid 53g (yield 60%).

[0104] Example 9

[0105] The structure of the cycloolefin copolymer is as follows:

[0106]

[0107] wherein the polymerization degree x = 500, the synthesis steps are as follows:

[0108] At room temperature, 20.91g (0.056mol) of monomer HM1 prepared in Example 1 was added to a dry polymerization reaction bottle. Then 500mL of dry and degassed chlorobenzene solvent was added, and a uniform solution was obtained by magnetic stirring for 5min. Then 0.099g (0.112mmol) of catalyst (G3) was dissolved in 20mL of chlorobenzene, and then quickly injected into the round-bottom flask. After 2 hours of reaction at room temperature under a nitrogen atmosphere, 300eqv of vinyl ether (relative to the number of moles of catalyst) was added to terminate the reaction, and stirred for 30min. The polymer solution was precipitated in 1000mL of anhydrous ethanol, filtered and washed, and the collected product was vacuum dried at 40°C for 16 hours to obtain the polymerization product.

[0109] The above polymerization product was added to a round-bottom flask equipped with a condenser tube with 51.84g of p-methylbenzenesulfonyl hydrazide and 43.92g of tri-n-propylamine, 0.024g of 2,6-di-tert-butyl-4-methylphenol was added, chlorobenzene solvent was added and stirred to dissolve, then the system was vacuumed and replaced with nitrogen, and reacted at 120°C for 16 hours under a nitrogen atmosphere. The polymer solution was precipitated in anhydrous ethanol, filtered and washed, and vacuum dried at 60°C for 18 hours to obtain the hydrogenation product, which is a cycloolefin copolymer.

[0110] The polymerization method provided in the embodiment makes the conversion rate of monomers greater than 99%, and the hydrogenation method provided makes the hydrogenation rate of main chain double bonds greater than 99%. The final prepared cycloolefin copolymer has a refractive index of 1.71, an Abbe number of 13, a glass transition temperature of 201°C, a 5wt% thermal weight loss temperature of 422°C, a water absorption rate of less than 0.01%, and a visible light transmittance of greater than 90%.

[0111] Example 10

[0112] The structural formula of the cycloolefin copolymer is:

[0113]

[0114] The polymerization degree x = 500, and the synthesis steps are as follows:

[0115] At room temperature, 20.91 g (0.056 mol) of the monomer HM2 prepared in Example 2 was added into a dry polymerization reaction bottle. Then 500 mL of dry and degassed chlorobenzene solvent was added, and a uniform solution was obtained by magnetic stirring for 5 min. Then 0.099 g (0.112 mmol) of the catalyst (G3) was dissolved in 20 mL of chlorobenzene, and then quickly injected into the round-bottom flask. After reaction at room temperature for 2 hours under a nitrogen atmosphere, 300 eqv of vinyl ether (relative to the number of moles of catalyst) was added to terminate the reaction, and stirred for 30 min. The polymer solution was precipitated in 1000 mL of anhydrous ethanol, filtered and washed, and the collected product was dried at 40°C under vacuum for 16 hours to obtain the polymerization reaction product.

[0116] The above polymerization reaction product was added to a round-bottom flask equipped with a condenser tube together with 51.84 g of p-methylbenzenesulfonyl hydrazide and 43.92 g of tri-n-propylamine, 0.024 g of 2,6-di-tert-butyl-4-methylphenol was added, chlorobenzene solvent was added for stirring and dissolution, and then the system was subjected to vacuum-purging nitrogen replacement treatment, and reacted at 120°C for 16 hours under a nitrogen atmosphere. The polymer solution was precipitated in anhydrous ethanol, filtered and washed, and vacuum dried at 60°C for 18 hours to obtain the hydrogenation product, i.e. the cycloolefin copolymer.

[0117] The polymerization method provided in the embodiment makes the conversion rate of monomers greater than 99%, and the hydrogenation method provided makes the hydrogenation rate of main chain double bonds greater than 99%. The final prepared cycloolefin copolymer has a refractive index of 1.71, an Abbe number of 12, a glass transition temperature of 198°C, a 5wt% thermal weight loss temperature of 435°C, a water absorption rate of less than 0.01%, and a visible light transmittance of greater than 90%.

[0118] Example 11

[0119] The structural formula of the cycloolefin copolymer is:

[0120]

[0121] wherein the polymerization degree x = 500, and the synthesis steps are as follows:

[0122] At room temperature, 23.15 g (0.062 mol) of monomer HM3 prepared in Example 3 was added into a dry polymerization flask. Then 500 mL of dry and degassed chlorobenzene solvent was added, and a uniform solution was obtained by magnetic stirring for 5 min. Subsequently, 0.110 g (0.124 mmol) of catalyst (G3) was dissolved in 20 mL of chlorobenzene, and then quickly injected into the round-bottom flask. After reaction at room temperature for 2 hours under a nitrogen atmosphere, the reaction was terminated by adding 300 eqv of vinyl ethyl ether (relative to the number of moles of catalyst), and stirring for 30 min. The polymer solution was precipitated in 1000 mL of anhydrous ethanol, filtered and washed, and the collected product was dried at 40 °C under vacuum for 16 hours to obtain the polymerization product.

[0123] The above polymerization product was added into a round-bottom flask equipped with a condenser tube together with 57.62 g of p-methylbenzenesulfonyl hydrazide and 48.81 g of tri-n-propylamine, 0.027 g of 2,6-di-tert-butyl-4-methylphenol was added, chlorobenzene solvent was added for stirring and dissolution, and then the system was subjected to vacuum-purging nitrogen replacement treatment, and reacted at 120 °C for 16 hours under a nitrogen atmosphere. The polymer solution was precipitated in anhydrous ethanol, filtered and washed, and dried at 60 °C under vacuum for 18 hours to obtain the hydrogenation product, which is a cyclic olefin copolymer.

[0124] The polymerization method provided in this example has a monomer conversion rate of greater than 99%, and the hydrogenation method provided has a hydrogenation rate of main chain double bonds of greater than 99%. The final cyclic olefin copolymer has a refractive index of 1.72, an Abbe number of 12, a glass transition temperature of 200 °C, a 5 wt% thermal weight loss temperature of 447 °C, a water absorption rate of less than 0.01%, and a visible light transmittance of greater than 90%.

[0125] Example 12

[0126] The structural formula of the cyclic olefin copolymer is:

[0127]

[0128] wherein the polymerization degree x = 400, y = 100, and the synthesis steps are as follows:

[0129] In a dry polymerization flask, 20.88 g (0.052 mol) of monomer HM1 prepared in Example 4 and 1.74 g (0.013 mol) of monomer M2 were added at room temperature. Then 500 mL of dry and degassed chlorobenzene solvent was added, and a uniform solution was obtained by magnetic stirring for 5 min. Subsequently, 0.108 g (0.128 mmol) of catalyst (G2) was dissolved in 20 mL of chlorobenzene, and then rapidly injected into the round-bottom flask. After the reaction was terminated by adding 300 eqv of vinyl ethyl ether (relative to the number of moles of catalyst) and stirring for 30 min at room temperature under a nitrogen atmosphere, the polymer solution was precipitated in 1000 mL of anhydrous ethanol, filtered and washed, and the collected product was dried at 40°C under vacuum for 16 hours to obtain the polymerization product.

[0130] The above polymerization product was added to a round-bottom flask equipped with a condenser tube along with 59.52 g of p-tolylsulfonyl hydrazine and 50.33 g of tri-n-propylamine, 0.028 g of 2,6-di-tert-butyl-4-methylphenol was added, chlorobenzene solvent was added and dissolved by stirring, and then the system was subjected to vacuum-purging nitrogen replacement treatment, and reacted at 120°C for 16 hours under a nitrogen atmosphere. The polymer solution was precipitated in anhydrous ethanol, filtered and washed, and dried at 60°C under vacuum for 18 hours to obtain the hydrogenation product, which is a cyclic olefin copolymer.

[0131] The polymerization method provided in this example has a monomer conversion rate of greater than 99%, and the hydrogenation method provided has a hydrogenation rate of main chain double bonds of greater than 99%. The final cyclic olefin copolymer has a refractive index of 1.69, an Abbe number of 16, a glass transition temperature of 181°C, a 5wt% thermal weight loss temperature of 424°C, a water absorption rate of less than 0.01%, and a visible light transmittance of greater than 90%.

[0132] Example 13

[0133] The structure of the cyclic olefin copolymer is as follows:

[0134]

[0135] wherein the polymerization degree x = 300, y = 300, and the synthesis steps are as follows:

[0136] In a dry polymerization flask, 15.66 g (0.039 mol) of monomer HM1 prepared in Example 4 and 5.23 g (0.039 mol) of monomer M2 were added at room temperature. Then 500 mL of dry and degassed chlorobenzene solvent was added, and a uniform solution was obtained by magnetic stirring for 5 min. Subsequently, 0.108 g (0.128 mmol) of catalyst (G2) was dissolved in 20 mL of chlorobenzene, and then quickly injected into the round-bottom flask. After the reaction was terminated by adding 300 eqv of vinyl ethyl ether (relative to the number of moles of catalyst) and stirring for 30 min at room temperature under a nitrogen atmosphere, the polymer solution was precipitated in 1000 mL of anhydrous ethanol, filtered and washed, and the collected product was dried at 40°C under vacuum for 16 hours to obtain the polymerization product.

[0137] The above polymerization product was added to a round-bottom flask equipped with a condenser tube along with 71.61 g of p-tolylsulfonyl hydrazine and 60.56 g of tri-n-propylamine, 0.028 g of 2,6-di-tert-butyl-4-methylphenol was added, chlorobenzene solvent was added and dissolved by stirring, and then the system was subjected to vacuum-purging nitrogen replacement treatment, and reacted at 120°C for 16 hours under a nitrogen atmosphere. The polymer solution was precipitated in anhydrous ethanol, filtered and washed, and dried at 60°C under vacuum for 18 hours to obtain the hydrogenation product, which is a cyclic olefin copolymer.

[0138] The polymerization method provided in this example has a monomer conversion rate of greater than 99%, and the hydrogenation method provided has a hydrogenation rate of main chain double bonds of greater than 99%. The final cyclic olefin copolymer has a refractive index of 1.64, an Abbe number of 20, a glass transition temperature of 170°C, a 5wt% thermal weight loss temperature of 426°C, a water absorption rate of less than 0.01%, and a visible light transmittance of greater than 90%.

[0139] Example 14

[0140] The structure of the cyclic olefin copolymer is as follows:

[0141]

[0142] wherein the polymerization degree x = 400 and y = 200, and the synthesis steps are as follows:

[0143] In a dry polymerization flask, 23.25 g (0.060 mol) of monomer HM3 prepared in Example 5 and 4.81 g (0.030 mol) of monomer M3 were added at room temperature. Then 500 mL of dry and degassed chlorobenzene solvent was added, and a uniform solution was obtained by magnetic stirring for 5 min. Subsequently, 0.126 g (0.148 mmol) of catalyst (G2) was dissolved in 20 mL of chlorobenzene, and then quickly injected into the round-bottom flask. After the reaction was terminated by adding 300 eqv of vinyl ethyl ether (relative to the number of moles of catalyst) and stirring for 30 min at room temperature under a nitrogen atmosphere, the polymer solution was precipitated in 1000 mL of anhydrous ethanol, filtered and washed, and the collected product was dried at 40°C under vacuum for 16 hours to obtain the polymerization product.

[0144] The above polymerization product was added to a round-bottom flask equipped with a condenser tube along with 82.77 g of p-methylbenzenesulfonyl hydrazide and 69.98 g of tri-n-propylamine, 0.028 g of 2,6-di-tert-butyl-4-methylphenol was added, chlorobenzene solvent was added and dissolved by stirring, and then the system was subjected to vacuum-purging nitrogen replacement treatment, and reacted at 120°C for 16 hours under a nitrogen atmosphere. The polymer solution was precipitated in anhydrous ethanol, filtered and washed, and dried at 60°C under vacuum for 18 hours to obtain the hydrogenation product, which is a cyclic olefin copolymer.

[0145] The polymerization method provided in this example has a monomer conversion rate of greater than 99%, and the hydrogenation method provided has a hydrogenation rate of main chain double bonds of greater than 99%. The final cyclic olefin copolymer has a refractive index of 1.67, an Abbe number of 17, a glass transition temperature of 182°C, a 5wt% thermal weight loss temperature of 442°C, a water absorption rate of less than 0.01%, and a visible light transmittance of greater than 90%.

[0146] Example 15

[0147] The structure of the cyclic olefin copolymer is as follows:

[0148]

[0149] wherein the polymerization degree x = 300, y = 300, and the synthesis steps are as follows:

[0150] In a dry polymerization flask, 17.03 g (0.044 mol) of monomer HM3 prepared in Example 5 and 7.04 g (0.044 mol) of monomer M3 were added at room temperature. Then 500 mL of dry and degassed chlorobenzene solvent was added, and a uniform solution was obtained by magnetic stirring for 5 min. Subsequently, 0.126 g (0.148 mmol) of catalyst (G2) was dissolved in 20 mL of chlorobenzene, and then quickly injected into the round-bottom flask. After the reaction at room temperature for 2 hours under a nitrogen atmosphere, the reaction was terminated by adding 300 eqv of vinyl ethyl ether (relative to the number of moles of catalyst), and stirring for 30 min. The polymer solution was precipitated in 1000 mL of anhydrous ethanol, filtered and washed, and the collected product was dried at 40°C under vacuum for 16 hours to obtain the polymerization product.

[0151] The above polymerization product was added to a round-bottom flask equipped with a condenser tube together with 82.77 g of p-tolylsulfonyl hydrazine and 69.98 g of tri-n-propylamine, 0.028 g of 2,6-di-tert-butyl-4-methylphenol was added, chlorobenzene solvent was added and dissolved by stirring, and then the system was subjected to vacuum-purging nitrogen replacement treatment, and reacted at 120°C for 16 hours under a nitrogen atmosphere. The polymer solution was precipitated in anhydrous ethanol, filtered and washed, and dried at 60°C under vacuum for 18 hours to obtain the hydrogenation product, which is a cyclic olefin copolymer.

[0152] The polymerization method provided in this example has a monomer conversion rate of greater than 99%, and the hydrogenation method provided has a hydrogenation rate of main chain double bonds of greater than 99%. The final cyclic olefin copolymer has a refractive index of 1.65, an Abbe number of 19, a glass transition temperature of 180°C, a 5wt% thermal weight loss temperature of 439°C, a water absorption rate of less than 0.01%, and a visible light transmittance of greater than 90%.

[0153] Example 16

[0154] The structure of the cyclic olefin copolymer is as follows:

[0155]

[0156] wherein the polymerization degree x = 400, y = 100, and the synthesis steps are as follows:

[0157] In a dry polymerization flask, 21.54 g (0.060 mol) of monomer HM3 prepared in Example 6 and 1.02 g (0.015 mol) of monomer M7 were added at room temperature. Then 500 mL of dry and degassed chlorobenzene solvent was added, and a uniform solution was obtained by magnetic stirring for 5 min. Subsequently, 0.133 g (0.150 mmol) of catalyst (G3) was dissolved in 20 mL of chlorobenzene, and then quickly injected into the round-bottom flask. After the reaction was terminated by adding 300 eqv of vinyl ethyl ether (relative to the number of moles of catalyst) and stirring for 30 min at room temperature under a nitrogen atmosphere, the polymer solution was precipitated in 1000 mL of anhydrous ethanol, filtered and washed, and the collected product was dried at 40°C under vacuum for 16 hours to obtain the polymerization product.

[0158] The above polymerization product was added to a round-bottom flask equipped with a condenser tube along with 69.75 g of p-tolylsulfonyl hydrazine and 58.98 g of tri-n-propylamine, 0.033 g of 2,6-di-tert-butyl-4-methylphenol was added, chlorobenzene solvent was added and dissolved by stirring, and then the system was subjected to vacuum-purging nitrogen replacement treatment, and reacted at 120°C for 16 hours under a nitrogen atmosphere. The polymer solution was precipitated in anhydrous ethanol, filtered and washed, and dried at 60°C under vacuum for 18 hours to obtain the hydrogenation product, which is a cyclic olefin copolymer.

[0159] The polymerization method provided in this example has a monomer conversion rate of greater than 99%, and the hydrogenation method provided has a hydrogenation rate of main chain double bonds of greater than 99%. The final cyclic olefin copolymer has a refractive index of 1.71, an Abbe number of 13, a glass transition temperature of 189°C, a 5wt% thermal weight loss temperature of 440°C, a water absorption rate of less than 0.01%, and a visible light transmittance of greater than 90%.

[0160] Example 17

[0161] The structure of the cyclic olefin copolymer is as follows:

[0162]

[0163] wherein the polymerization degree x = 400, y = 100, and the synthesis steps are as follows:

[0164] Into a dry polymerization flask, 28.76 g (0.080 mol) of monomer HM3 prepared in Example 6 and 1.88 g (0.020 mol) of monomer M8 were added at room temperature. Then 500 mL of dry and degassed chlorobenzene solvent was added, and a homogeneous solution was obtained by stirring with a magnetic stirrer for 5 min. Subsequently, 0.173 g (0.200 mmol) of catalyst (G3) was dissolved in 20 mL of chlorobenzene, and then rapidly injected into the round-bottom flask. After the reaction was terminated by adding 300 eqv of vinyl ethyl ether (relative to the number of moles of catalyst) after stirring for 30 min at room temperature under a nitrogen atmosphere, the polymer solution was precipitated in 1000 mL of anhydrous ethanol, filtered and washed, and the collected product was dried at 40°C under vacuum for 16 hours to obtain the polymerization product.

[0165] The above polymerization product was added to a round-bottom flask equipped with a condenser tube together with 91.14 g of p-tolylsulfonyl hydrazine and 77.07 g of tri-n-propylamine, 0.043 g of 2,6-di-tert-butyl-4-methylphenol was added, chlorobenzene solvent was added and dissolved by stirring, and then the system was subjected to vacuum-purging nitrogen replacement treatment, and reacted at 120°C for 16 hours under a nitrogen atmosphere. The polymer solution was precipitated in anhydrous ethanol, filtered and washed, and dried at 60°C under vacuum for 18 hours to obtain the hydrogenation product, which is a cyclic olefin copolymer.

[0166] The polymerization method provided in this example has a monomer conversion rate of greater than 99%, and the hydrogenation method provided has a hydrogenation rate of main chain double bonds of greater than 99%. The cyclic olefin copolymer finally prepared has a refractive index of 1.70, an Abbe number of 14, a glass transition temperature of 188°C, a 5 wt% thermal weight loss temperature of 443°C, a water absorption rate of less than 0.01%, and a visible light transmittance of greater than 90%.

[0167] Example 18

[0168] The structural formula of the cyclic olefin copolymer is:

[0169]

[0170] wherein the polymerization degree x1 = 100 and x2 = 500, and the synthesis steps are as follows:

[0171] In a dry polymerization flask, 6.44 g (0.015 mol) of monomer HM3 prepared in Example 7 and 27.98 g (0.075 mol) of monomer HM2 prepared in Example 2 were added at room temperature. Then 500 mL of dry and degassed chlorobenzene solvent was added, and a uniform solution was obtained by magnetic stirring for 5 min. Subsequently, 0.117 g (0.132 mmol) of catalyst (G3) was dissolved in 20 mL of chlorobenzene, and then rapidly injected into the round-bottom flask. After the reaction was terminated by adding 300 eqv of vinyl ethyl ether (relative to the number of moles of catalyst) after stirring for 30 min at room temperature under a nitrogen atmosphere, the polymer solution was precipitated in 1000 mL of anhydrous ethanol, filtered and washed, and the collected product was dried at 40°C under vacuum for 16 hours to obtain the polymerization product.

[0172] The above polymerization product was added to a round-bottom flask equipped with a condenser tube together with 61.38 g of p-tolylsulfonyl hydrazine and 51.91 g of tri-n-propylamine, 0.029 g of 2,6-di-tert-butyl-4-methylphenol was added, chlorobenzene solvent was added and dissolved by stirring, and then the system was subjected to vacuum-purging nitrogen replacement treatment, and reacted at 120°C for 16 hours under a nitrogen atmosphere. The polymer solution was precipitated in anhydrous ethanol, filtered and washed, and dried at 60°C under vacuum for 18 hours to obtain the hydrogenation product, i.e., a cyclic olefin copolymer.

[0173] The polymerization method provided in this example achieves a monomer conversion rate of 100%, and the hydrogenation method provided achieves a hydrogenation rate of the main chain double bond of greater than 99%. The final cyclic olefin copolymer has a refractive index of 1.71, an Abbe number of 13, a glass transition temperature of 190°C, a 5wt% thermal weight loss temperature of 433°C, a water absorption rate of less than 0.01%, and a visible light transmittance of greater than 90%.

[0174] Example 19

[0175] The structure of the cyclic olefin copolymer is as follows:

[0176]

[0177] wherein the polymerization degree x1 = 100 and x2 = 500, and the synthesis steps are as follows:

[0178] In a dry polymerization flask, 6.66 g (0.015 mol) of monomer HMl prepared in Example 8 and 27.98 g (0.075 mol) of monomer HM3 prepared in Example 3 were added at room temperature. Then 500 mL of dry and degassed chlorobenzene solvent was added, and a homogeneous solution was obtained by magnetic stirring for 5 min. Subsequently, 0.117 g (0.132 mmol) of catalyst (G3) was dissolved in 20 mL of chlorobenzene, and then rapidly injected into the round-bottom flask. After the reaction was terminated by adding 300 eqv of vinyl ethyl ether (relative to the number of moles of catalyst) and stirring for 30 min at room temperature under a nitrogen atmosphere, the polymer solution was precipitated in 1000 mL of anhydrous ethanol, filtered and washed, and the collected product was dried at 40°C under vacuum for 16 hours to obtain the polymerization product.

[0179] The above polymerization product was added to a round-bottom flask equipped with a condenser tube along with 61.38 g of p-tolylsulfonyl hydrazide and 51.91 g of tri-n-propylamine, 0.029 g of 2,6-di-tert-butyl-4-methylphenol was added, chlorobenzene solvent was added and dissolved by stirring, and then the system was subjected to vacuum-purging nitrogen replacement treatment, and reacted at 120°C for 16 hours under a nitrogen atmosphere. The polymer solution was precipitated in anhydrous ethanol, filtered and washed, and dried at 60°C under vacuum for 18 hours to obtain the hydrogenation product, which is a cyclic olefin copolymer.

[0180] The polymerization method provided in this example achieves a monomer conversion rate of 100%, and the hydrogenation method provided achieves a hydrogenation rate of the main chain double bond of greater than 99%. The final cyclic olefin copolymer has a refractive index of 1.71, an Abbe number of 13, a glass transition temperature of 188°C, a 5 wt% thermal weight loss temperature of 432°C, a water absorption rate of less than 0.01%, and a visible light transmittance of greater than 90%.

[0181] Example 20

[0182] The structural formula of the cyclic olefin copolymer is:

[0183]

[0184] wherein the polymerization degree x = 300, yl = 75, and y2 = 75, and the synthesis steps are as follows:

[0185] Into a dry polymerization flask, 29.88 g (0.080 mol) of monomer HM3 prepared in Example 3, 3.20 g (0.020 mol) of monomer M3 and 1.36 g (0.020 mol) of monomer M7 were added at room temperature. Then 500 mL of dry and degassed chlorobenzene solvent was added, and a homogeneous solution was obtained by magnetic stirring for 5 min. Subsequently, 0.234 g (0.264 mmol) of catalyst (G3) was dissolved in 20 mL of chlorobenzene, and then quickly injected into the round-bottom flask. After the reaction was terminated by adding 300 eqv of vinyl ethyl ether (relative to the number of moles of catalyst) after 2 hours of reaction at room temperature under a nitrogen atmosphere, and stirring for 30 min. The polymer solution was precipitated in 1000 mL of anhydrous ethanol, filtered and washed, and the collected product was dried in a vacuum oven at 40 °C for 16 hours to obtain the polymerization product.

[0186] The polymerization product prepared above was added to a high-pressure autoclave together with 500 mL of chlorobenzene, and the high-pressure autoclave was subjected to 3 times of air replacement operation under vacuum. 0.063 g of nickel naphthenate and 1.12 mmol of triisobutylaluminum were taken into an ampoule, mixed with an appropriate amount of hydrogenation solvent, aged in a water bath set at a certain temperature, and then injected into the high-pressure autoclave using a syringe under nitrogen protection. The high-pressure autoclave was filled with 10 MPa of hydrogen, and the hydrogenation reaction was carried out at 120 °C for 15 h. The obtained hydrogenation product was precipitated in ethanol, filtered and washed, and the obtained precipitated product was placed in a vacuum oven and dried at 60 °C for 18 hours to obtain a cyclic olefin copolymer.

[0187] The polymerization method provided in this example has a monomer conversion rate of greater than 99%, and the hydrogenation method provided has a hydrogenation rate of main chain double bonds of greater than 99%. The final cyclic olefin copolymer has a refractive index of 1.70, an Abbe number of 14, a glass transition temperature of 186 °C, a 5 wt% thermal weight loss temperature of 438 °C, a water absorption rate of less than 0.01%, and a visible light transmittance of greater than 90%.

[0188] Example 21

[0189] The cyclic olefin copolymer has the following structural formula:

[0190]

[0191] wherein the polymerization degree x = 250, y1 = 125, and y2 = 62, and the synthesis steps are as follows:

[0192] Into a dry polymerization flask, 29.88 g (0.080 mol) of monomer HM3 prepared in Example 3, 6.40 g (0.040 mol) of monomer M3 and 1.36 g (0.020 mol) of monomer M7 were added at room temperature. Then 500 mL of dry and degassed chlorobenzene solvent was added, and a homogeneous solution was obtained by magnetic stirring for 5 min. Subsequently, 0.234 g (0.264 mmol) of catalyst (G3) was dissolved in 20 mL of chlorobenzene, and then quickly injected into the round-bottom flask. After the reaction was terminated by adding 300 eqv of vinyl ethyl ether (relative to the number of moles of catalyst) after 2 hours of reaction at room temperature under a nitrogen atmosphere, and stirring for 30 min. The polymer solution was precipitated in 1000 mL of anhydrous ethanol, filtered and washed, and the collected product was dried in a vacuum oven at 40 °C for 16 hours to obtain a polymerization product.

[0193] A high-pressure autoclave was pre-dried under vacuum for 5 hours, and the polymerization product prepared above and 500 mL of chlorobenzene were added to the high-pressure autoclave, and the high-pressure autoclave was subjected to 3 times of air replacement operation. 0.063 g of nickel naphthenate and 1.12 mmol of triisobutylaluminum were taken into an ampoule, mixed with an appropriate amount of hydrogenation solvent, aged in a water bath set to a certain temperature, and then injected into the high-pressure autoclave using a syringe under nitrogen protection. The high-pressure autoclave was filled with 15 MPa of hydrogen, and the hydrogenation reaction was carried out at 120 °C for 15 h. The obtained hydrogenation product was precipitated in ethanol, filtered and washed, and the obtained precipitated product was placed in a vacuum oven and dried at 60 °C for 18 hours to obtain a cyclic olefin copolymer.

[0194] The polymerization method provided in this example has a monomer conversion rate of greater than 99%, and the hydrogenation method provided has a hydrogenation rate of main chain double bonds of greater than 99%. The final cyclic olefin copolymer has a refractive index of 1.67, an Abbe number of 17, a glass transition temperature of 180 °C, a 5 wt% thermal weight loss temperature of 440 °C, a water absorption rate of less than 0.01%, and a visible light transmittance of greater than 90%.

[0195] Example 22

[0196] The structural formula of the cyclic olefin copolymer is:

[0197]

[0198] wherein the polymerization degree x1 = 150, x2 = 300, and y = 75, and the synthesis steps are as follows:

[0199] In a dry polymerization flask, 9.34 g (0.025 mol) of monomer HM2 prepared in Example 2, 18.68 g (0.050 mol) of monomer HM3 prepared in Example 3 and 1.38 g (0.0125 mol) of monomer M10 were added at room temperature. Then 500 mL of dry and degassed chlorobenzene solvent was added, and a homogeneous solution was obtained by magnetic stirring for 5 min. Subsequently, 0.145 g (0.164 mmol) of catalyst (G3) was dissolved in 20 mL of chlorobenzene, and then rapidly injected into the round-bottom flask. After the reaction was terminated by adding 300 eqv of vinyl ethyl ether (relative to the number of moles of catalyst) after 2 hours of reaction at room temperature under a nitrogen atmosphere, and stirring for 30 min. The polymer solution was precipitated in 1000 mL of anhydrous ethanol, filtered and washed, and the collected product was dried in a vacuum oven at 40°C for 16 hours to obtain a polymerization product.

[0200] The autoclave was pre-dried under vacuum for 5 hours, and the polymerization product prepared above, 500 mL of chlorobenzene and 10 g of Pd / A12O3 catalyst were added to the autoclave. After 3 times of air replacement operation of the autoclave, 10 MPa of hydrogen was filled into the autoclave, and a hydrogenation reaction was carried out at 120°C for 15 hours. The hydrogenation reaction solution was filtered to recover the Pd / A12O3 catalyst therein, and a hydrogenation product was obtained. The hydrogenation product was poured into ethanol to precipitate, filtered and washed, and the obtained precipitated product was placed in a vacuum oven and dried at 60°C for 18 hours to obtain a cyclic olefin copolymer.

[0201] The polymerization method provided in this example has a monomer conversion rate of greater than 99%, and the hydrogenation method provided has a hydrogenation rate of main chain double bonds of greater than 99%. The final cyclic olefin copolymer has a refractive index of 1.71, an Abbe number of 13, a glass transition temperature of 188°C, a 5wt% thermal weight loss temperature of 438°C, a water absorption rate of less than 0.01%, and a visible light transmittance of greater than 90%.

[0202] Example 23

[0203] The structure of the cyclic olefin copolymer is as follows:

[0204]

[0205] wherein the polymerization degree x1 = 150, x2 = 300, and y = 75, and the synthesis steps are as follows:

[0206] Into a dry polymerization flask, 9.34 g (0.025 mol) of monomer HM1 prepared in Example 1, 18.68 g (0.050 mol) of monomer HM3 prepared in Example 3 and 1.38 g (0.0125 mol) of monomer M10 were added at room temperature. Then 500 mL of dry and degassed chlorobenzene solvent was added and stirred for 5 min to obtain a homogeneous solution. Subsequently, 0.145 g (0.164 mmol) of catalyst (G3) was dissolved in 20 mL of chlorobenzene and then quickly injected into the round bottom flask. After the reaction was terminated by adding 300 eqv of vinyl ethyl ether (relative to the number of moles of catalyst) after 2 hours of reaction at room temperature under nitrogen atmosphere and stirred for 30 min. The polymer solution was precipitated in 1000 mL of absolute ethanol, filtered and washed, and the collected product was dried in a vacuum oven at 40 °C for 16 hours to obtain the polymerization product.

[0207] The autoclave was pre-dried under vacuum for 5 hours, and the polymerization product prepared above, 500 mL of chlorobenzene and 10 g of Pd / A12O3 catalyst were added to the autoclave. After 3 times of air replacement operation, 20 MPa of hydrogen was filled into the autoclave, and the hydrogenation reaction was carried out at 120 °C for 15 h. The Pd / A12O3 catalyst in the obtained hydrogenation reaction solution was recovered by filtration to obtain the hydrogenation product. The hydrogenation product was precipitated by pouring into ethanol, filtered and washed, and the obtained precipitated product was placed in a vacuum oven and dried at 60 °C for 18 hours to obtain the cycloolefin copolymer.

[0208] The polymerization method provided in this example has a monomer conversion rate of greater than 99%, and the hydrogenation method provided has a main chain double bond hydrogenation rate of greater than 99%. The cycloolefin copolymer finally prepared has a refractive index of 1.71, an Abbe number of 13, a glass transition temperature of 186 °C, a 5 wt% thermal weight loss temperature of 433 °C, a water absorption rate of less than 0.01%, and a visible light transmittance of greater than 90%.

[0209] Figure 1 and Figure 2 NMR spectrum of the cycloolefin monomer obtained in Example 3 of the present application 1 H-NMR spectrum and 13 C-NMR spectrum; from Figure 1 and Figure 2 It can be seen that the characteristic peaks are consistent with the expected structure, proving that the cycloolefin monomer has been successfully prepared.

[0210] Figure 3 and Figure 4 NMR spectrum of the cycloolefin copolymer obtained in Example 11 of the present application 1 H-NMR spectrum and 13 C-NMR spectrum; from Figure 3 and Figure 4It can be seen that the characteristic peaks of the cycloolefin copolymer are consistent with the expected structure, and the double bond characteristic signal in the raw material has disappeared obviously, indicating that the hydrogenation reaction is successfully completed, and the target cycloolefin copolymer is prepared.

[0211] The products prepared in Examples 1-2, 4-10, 12-23 were subjected to nuclear magnetic resonance 1 H-NMR spectrum and 13 C-NMR spectrum analysis, the results show that the target product has been successfully prepared.

[0212] Figure 5 The differential scanning calorimetry curve of the cycloolefin copolymer obtained in Example 9 of the present application; from Figure 5 It can be seen that the glass transition temperature of the cycloolefin copolymer prepared in Example 9 is as high as 201℃, which has ultra-high thermal stability.

[0213] Figure 6 The refractive index curve of the cycloolefin copolymer obtained in Example 11 of the present application; from Figure 6 It can be seen that the refractive index of the cycloolefin copolymer prepared in Example 11 is as high as 1.72 in the visible light range, which has ultra-high refractive index.

[0214] Figure 7 The thermogravimetric curve of the cycloolefin copolymer obtained in Example 14 of the present application in nitrogen; from Figure 7 It can be seen that the 5wt% thermal decomposition temperature of the cycloolefin copolymer prepared in Example 14 is as high as 442℃, which has high heat resistance.

[0215] Figure 8 The light transmittance curve of the cycloolefin copolymer obtained in Example 19 of the present application; from Figure 8 It can be seen that the visible light transmittance of the cycloolefin copolymer prepared in Example 19 is greater than 90%, which has high transparency.

[0216] Comparative Examples 1-3 are common commercially available cycloolefin copolymers, see Table 1.

[0217] Table 1 Properties of common commercially available cycloolefin copolymers

[0218]

[0219] Note: T d5 is the 5wt% temperature of thermal weight loss.

[0220] A comparison of Table 1 and Examples 9-23 reveals that the cyclic olefin copolymers prepared in this invention exhibit remarkably significant advantages in both optical and thermal properties. Their refractive index ranges from 1.64 to 1.72, far exceeding that of the comparative commercial materials, demonstrating superior optical performance. Furthermore, the glass transition temperature of this material reaches 170°C to 201°C, and its thermal stability also far surpasses that of commercial materials. More importantly, while achieving a high refractive index, the material maintains a light transmittance exceeding 90%, ensuring excellent transparency. It also possesses a high thermal decomposition temperature (>420°C) and excellent low hygroscopicity (<0.01%). In summary, the material of this invention, through precise molecular structure design, achieves a comprehensive breakthrough in optical and thermal properties, providing a novel solution for the development of high-refractive-index optical materials.

[0221] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications and improvements made by those skilled in the art to the technical solutions of the present invention without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims

1. A cyclic olefin copolymer, characterized in that, It has the structure shown in Equation I: Formula I; In Formula I, x and y are the degree of polymerization, 20≤x≤1000, 0≤y≤1000, but do not represent block copolymers; the dashed line indicates bonding or non-bonding; i is the number of rings, i is 0 or 1; m and n are the number of carbon atoms, 0≤m≤10, 0≤n≤4; R1 and R2 are each independently selected from one of hydrogen atoms, alkyl and alkenyl groups, and R1 and R2 may or may not be bonded, specifically selected from Formulas (1) to (8): Equation (1), where x = 500; Equation (2), where x = 500; Equation (3), where x = 500; Equation (4), in which x=400, y=100; Equation (5), in which x=400, y=100; Equation (5), in which x1=100, x2=500; Equation (6), in which x1=100, x2=500; Equation (7), in which x1=150, x2=300, y=75; Equation (8), in which x1=150, x2=300, y=75.

2. A method for preparing the cyclic olefin copolymer according to claim 1, characterized in that, Includes the following steps: In the presence of a catalyst, the monomer is subjected to ring-opening metathesis polymerization under a protective atmosphere to obtain the polymerization product. The polymerization product is subjected to hydrogenation to obtain the cyclic olefin copolymer; The monomer includes at least one compound of formula II, or includes at least one compound of formula II and at least one compound of formula III; The compound structure shown in Formula II is selected from at least one of the HM1-HM3 structures: ； The compound structure shown in Formula III is selected from at least one of the structures M7, M8, and M10: 、 、 。 3. The method for preparing the cyclic olefin copolymer according to claim 2, characterized in that, The catalyst is a ruthenium catalyst, a molybdenum catalyst, or a tungsten catalyst.

4. The method for preparing the cyclic olefin copolymer according to claim 2, characterized in that, The ring-opening metathesis polymerization reaction is carried out at a temperature of 25~80℃ for a time of 4~240 min.

5. The method for preparing the cyclic olefin copolymer according to claim 2, characterized in that, The hydrogenation reaction is carried out at a temperature of 100-150°C for 12-24 hours.

6. An optical material, characterized in that, The raw materials include the cyclic olefin copolymer of claim 1.

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