High refractive index, transparent cyclic olefin copolymer and method for its preparation

Abstract

The present application relates to the technical field of new high-end polyolefin, in particular to a kind of high refractive index, transparent cycloolefin copolymer and preparation method thereof.Cycloolefin copolymer of the present application has the structure shown in formula I: The cycloolefin copolymer prepared by the present application has a refractive index of 1.63-1.70 and an Abbe number of 14-23, and the material has a light transmittance of more than 90%, while maintaining low moisture absorption.The glass transition temperature of the material is 161-185 DEG C, and the 5% thermal weight loss is all above 415 DEG C, showing excellent thermal stability.In addition, using commercial catalyst, monomer conversion rate of up to 99% or more can be achieved, without crosslinking and other side reactions.These excellent properties show that the material has wide application prospects in the field of optics.

Description

Technical Field

[0001] This invention relates to the field of novel high-end polyolefin technology, and in particular to a high-refractive-index, transparent cyclic olefin copolymer and its preparation method. Background Technology

[0002] Cyclic olefin copolymers are a novel type of polymer that has attracted much attention in the field of high-performance polymer materials in recent years. They are mainly formed by the copolymerization of cyclic olefin monomers with other monomers through specific reactions. Due to their unique molecular structure and excellent physicochemical properties, they have been widely used in many fields such as electronics, optics, medicine, and packaging. The excellent optical properties, good heat resistance, low moisture absorption, and excellent dimensional stability of cyclic olefin copolymers give them significant advantages in many situations where traditional materials are inadequate.

[0003] Refractive index, as a crucial parameter determining the performance of these materials in optical applications, has received widespread attention. Commercial cyclic olefin copolymers, with refractive indices ranging from approximately 1.53 to 1.55, exhibit both low birefringence and high transparency, resulting in excellent optical transparency and image quality in optical lenses, MR / AR systems, and optical panels. However, with the ever-increasing demands in the optical field, the refractive indices of existing materials are no longer sufficient to meet the requirements of new applications, leading to an increasingly urgent need for materials with higher refractive indices that also possess transparency, heat resistance, and low hygroscopicity.

[0004] Therefore, how to further improve the refractive index of cyclic olefin copolymers while taking into account transparency, heat resistance and low moisture absorption has become the main challenge and problem in current research. Summary of the Invention

[0005] To address the above problems, this invention provides a high-refractive-index, transparent cyclic olefin copolymer and its preparation method. This cyclic olefin copolymer exhibits a high refractive index while also possessing high transparency, high heat resistance, and low hygroscopicity.

[0006] To achieve the above objectives, the present invention provides the following solution:

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

[0008]

[0009] In Formula I, x and y represent the degree of polymerization, 10≤x≤800, 0≤y≤700, but do not necessarily represent block copolymers; dashed lines indicate bonding or non-bonding; i and j represent the number of rings, i is 0 or 1, j is 0 or 1; m and n represent the number of carbon atoms, 0≤m≤10, 0≤n≤4; R1 to R6 are each independently selected from hydrogen atoms, alkyl groups, and alkenyl groups; R1 and R2 can form a benzene ring structure together with adjacent carbon atoms through bonding, or they can exist independently without bonding; R3 and R4 can form a benzene ring structure together with adjacent carbon atoms through bonding, or they can exist independently without bonding; R5 and R6 can form a bond or not.

[0010] The second technical solution of the present invention provides a method for preparing the cyclic olefin copolymer, comprising the following steps:

[0011] In the presence of a catalyst, the monomer undergoes a ring-opening metathesis polymerization reaction under a protective atmosphere to obtain the polymerization product.

[0012] The polymerization product is subjected to hydrogenation to obtain the cyclic olefin copolymer;

[0013] The monomer includes at least one compound of formula II and at least one compound of formula III;

[0014] The structure of the compound shown in Formula II is as follows:

[0015]

[0016] In Formula II, i is the number of rings, i is 0 or 1; m is the number of carbon atoms, 0≤m≤10; R1 to R4 are each independently selected from one of hydrogen atoms, alkyl and alkenyl groups, wherein R1 and R2, and R3 and R4 can form a benzene ring structure together with adjacent carbon atoms through bonding, or they can exist independently without bonding.

[0017] The structure of the compound shown in Formula III is as follows:

[0018]

[0019] In Formula III, the dashed line indicates whether or not a bond is formed; j is the ring number, which is 0 or 1; n is the number of carbon atoms, where 0 ≤ n ≤ 4; R5 and R6 are each independently selected from one of hydrogen atoms, alkyl groups, and alkenyl groups, and R5 and R6 may or may not be bonded to each other.

[0020] In a preferred embodiment of the present invention, the compound represented by Formula II is selected from at least one of the HM1-HM8 structures:

[0021]

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

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

[0024]

[0025] The present invention does not impose any special restrictions on the source of the cyclic olefin monomers with the structures shown in Formula II and Formula III, which can be obtained by preparation methods well known to those skilled in the art or through commercial channels.

[0026] In this invention, cyclic olefin monomers are dissolved in a solvent before 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 cyclopentane, hexane, cyclohexane, decane, isododecane, benzene, toluene, xylene, ethylbenzene, chlorobenzene, dichloromethane, or chloroform; more preferably benzene, toluene, xylene, chlorobenzene, dichloromethane, chloroform, or cyclohexane. This invention does not impose any special restrictions on the source of the solvent; solvents of the above types known to those skilled in the art can be used and are commercially available. This invention does not impose any special restrictions on the amount of solvent used; the amount of solvent used in polymerization reactions known to those skilled in the art can be used. This invention does not impose any special restrictions on the method of dissolution; for example, stirring dissolution can be performed, and stirring techniques known to those skilled in the art can be used. In this invention, 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 invention, the catalyst is a ruthenium catalyst, a molybdenum catalyst, or a tungsten catalyst, preferably a ruthenium catalyst.

[0028] The ruthenium catalyst is preferably one of the structures shown in Formula IV:

[0029]

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

[0031] The catalyst used in this invention has the advantages of high activity and good polymerization tolerance. In the preparation of the cyclic olefin copolymer of this invention, it has the advantages of requiring no co-catalyst, rapid initiation rate, 100% catalytic conversion, and no cross-linking or other side reactions. This invention does not have any special restrictions on the source of the catalyst having the structure shown in Formula IV; it can be purchased commercially.

[0032] In this invention, the ruthenium catalyst is dissolved in a solvent before the catalytic monomer compound undergoes ring-opening metathesis polymerization. The solvent is consistent with the solvent described above (the solvent used to dissolve the cyclic olefin monomer), specifically 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, chloroform, or cyclohexane. This invention does not impose any special restrictions on the source of the solvent; solvents of the types described above, well-known to those skilled in the art, can be used and are commercially available.

[0033] In a preferred embodiment of the present invention, the molar ratio of the monomer to the catalyst is (100-1500):1; preferably (200-1000):1, and more preferably (200-800):1.

[0034] In a preferred embodiment of the present invention, the temperature of the ring-opening metathesis polymerization reaction is 25–80°C, preferably 25–60°C, and more preferably 25–40°C; the time of the ring-opening metathesis polymerization reaction is 4–240 min, preferably 30–150 min, and more preferably 60–120 min.

[0035] The ring-opening metathesis polymerization of this invention is preferably carried out under anhydrous and oxygen-free conditions. In this invention, a standard Schlenk flask is used under nitrogen protection. The ring-opening metathesis polymerization reaction is preferably carried out under stirred conditions. This invention does not impose any special restrictions on the stirring method of the polymerization reaction; stirring techniques well-known to those skilled in the art can be used.

[0036] In this invention, after the ring-opening metathesis polymerization reaction is completed, the process further includes terminating the ring-opening metathesis polymerization reaction and separating the reaction products; preferably, the ring-opening metathesis polymerization reaction is terminated by using a terminating agent; the separation specifically involves mixing the polymerization reaction solution and a precipitating agent to obtain a precipitated product, and then filtering, washing, and drying the precipitated product to obtain the polymerization reaction product.

[0037] This invention does not impose any special restrictions on the type and source of the terminator; any terminator well known to those skilled in the art can be used. When preparing cyclic olefin copolymers, the terminator can be purchased commercially. In this invention, the terminator is preferably vinyl ethyl ether. The molar ratio of the terminator to the catalyst is preferably (100–800):1, more preferably (200–400):1, and most preferably 300:1; the time for terminating the polymerization reaction is preferably 20–60 minutes, more preferably 30–35 minutes.

[0038] This invention does not impose particular limitations on the methods for filtering, washing, and drying the precipitated products, and can employ techniques well-known to those skilled in the art. Ethanol is preferably used as the washing reagent, and the number of washing cycles is preferably 1 to 5, more preferably 3. Vacuum drying is preferred as the drying method, and the drying temperature is preferably 20°C to 60°C, more preferably 30°C to 50°C, and most preferably 40°C. The drying time is preferably 12 to 24 hours, more preferably 14 to 20 hours, and most preferably 16 hours.

[0039] In this invention, after obtaining the polymerization product, the polymerization product is subjected to a hydrogenation reaction with a hydrogen source to obtain a cyclic olefin copolymer. Preferably, the hydrogenation reaction is carried out under a protective gas condition. In this invention, the protective gas for the hydrogenation reaction is preferably nitrogen. This invention does not impose any special limitations on the method of the hydrogenation reaction; any hydrogenation reaction technique well known to those skilled in the art can be used.

[0040] The present invention does not impose any special restrictions on the type of hydrogen source, but the hydrogen source is preferably a hydrazine compound or hydrogen gas.

[0041] In this invention, when the hydrogen source is a hydrazine compound, the cyclic olefin copolymer is preferably prepared by hydrogenation reaction according to the following method: the polymerization product and the hydrazine compound are hydrogenated in a solvent to obtain the cyclic olefin copolymer. In this invention, the hydrazine compound is preferably p-toluenesulfonylhydrazine. The ratio of the molar number of double bonds in the polymerization product to the molar number of the hydrazine compound is 1:(3-7), preferably 1:(5-6). 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; most preferably toluene, xylene, or chlorobenzene. This invention does not have a particular limitation on the amount of solvent used, as long as it can provide a liquid environment for the hydrogenation reaction. The auxiliary agent used in the hydrogenation reaction is an amine compound, preferably tri-n-propylamine. The reaction system also includes a free radical scavenger. This invention does not have special requirements regarding the type and source of the free radical scavenger; commercially available free radical scavengers are acceptable. In this invention, the preferred free radical scavenger is 2,6-di-tert-butyl-4-methylphenol, and its amount used can be between 0.05 eqv and 3 eqv relative to the catalyst. The hydrogenation reaction temperature is 100℃~150℃, preferably 110℃~130℃, more preferably 120℃; the reaction time is 12~24 hours, preferably 14~18 hours. After the hydrogenation reaction is completed, this invention preferably mixes the obtained hydrogenation reaction product with ethanol, and after filtration, washing, and drying, obtains a hydrogenated cyclic olefin copolymer. The purity of the ethanol is preferably between 95% and 99%; the drying method is preferably vacuum drying, the drying time is preferably 12~24 hours, more preferably 16~20 hours; the drying temperature is preferably 50℃~70℃, more preferably 55℃~65℃, and most preferably 60℃.

[0042] In this invention, when the hydrogen source is hydrogen gas, the hydrogenation reaction is preferably carried out by the following method to prepare the cyclic olefin copolymer: the polymerization product is hydrogenated with hydrogen gas and a catalyst in a solvent to obtain the cyclic olefin copolymer. In this invention, the catalyst is a platinum catalyst, palladium catalyst, rhodium catalyst, or 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. This invention does not have a particular limitation on the amount of solvent used, as long as it can provide a liquid environment for the hydrogenation reaction. The temperature of the hydrogenation reaction is 60℃~150℃, preferably 110℃~130℃, more preferably 120℃; the reaction time is 10~20 hours, preferably 12~15 hours. After the hydrogenation reaction is completed, the present invention preferably mixes the obtained hydrogenation product with ethanol, and then filters, washes and dries it to obtain a hydrogenated cyclic olefin copolymer. The purity of the ethanol is preferably between 95% and 99%; the drying method 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, and most preferably 60°C.

[0043] The third technical solution of the present invention is an optical material, the raw material of which includes the aforementioned cyclic olefin copolymer.

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

[0045] This invention provides a cyclic olefin copolymer with excellent properties, including high refractive index, high transparency, high heat resistance, and low hygroscopicity. Furthermore, the cyclic olefin copolymer of this invention exhibits adjustable refractive index, Abbe number, and heat resistance. Experimental results show that, through specific molecular structure selection, the cyclic olefin copolymer obtained by this invention possesses a refractive index of 1.63–1.70 and an Abbe number of 14–23, with a light transmittance exceeding 90% while maintaining low hygroscopicity. The material has a glass transition temperature of 161°C–185°C, and a 5% thermal weight loss is above 415°C, demonstrating excellent thermal stability. Moreover, using a commercial catalyst, a monomer conversion rate of over 99% can be achieved without crosslinking or other side reactions. These superior properties indicate that this material has broad application prospects in the optical field. Attached Figure Description

[0046] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0047] Figure 1 NMR spectra of the cycloolefin monomers obtained in Example 1 of this invention 1 H-NMR spectrum;

[0048] Figure 2 NMR spectra of the cycloolefin monomers obtained in Example 1 of this invention 13 C-NMR spectrum;

[0049] Figure 3 NMR of the cyclic olefin copolymer obtained in Example 11 of this invention 1 H-NMR spectrum;

[0050] Figure 4 NMR of the cyclic olefin copolymer obtained in Example 11 of this invention 13 C-NMR spectrum;

[0051] Figure 5 The differential scanning calorimetry curve of the cyclic olefin copolymer obtained in Example 11 of the present invention;

[0052] Figure 6 The refractive index curve of the cyclic olefin copolymer obtained in Example 12 of the present invention;

[0053] Figure 7 The thermogravimetric curve of the cyclic olefin copolymer obtained in Example 15 of this invention in nitrogen gas;

[0054] Figure 8 The transmittance curve of the cyclic olefin copolymer obtained in Example 18 of the present invention is shown. Detailed Implementation

[0055] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0056] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any stated value or intermediate value within a stated range, as well as each smaller range between any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0057] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0058] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0059] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0060] In this embodiment of the invention, the prepared cyclic olefin copolymer was measured using the following method:

[0061] Conversion rate: The polymerization conversion rate of the polymerization reaction is tested by weighing the product in this invention.

[0062] Nuclear magnetic resonance characterization: The present invention uses a Bruker 400MHz nuclear magnetic resonance spectrometer for characterization, with deuterated chloroform (CDCl3) or deuterated tetrachloroethane (C2D2Cl4) as solvents and tetramethylsilane (TMS) as an internal standard.

[0063] Glass transition temperature: The glass transition temperature of the cyclic olefin copolymer was obtained by differential thermal analysis in this invention. The detection method was to use a DSC Q200-TA differential scanning calorimeter for differential thermal analysis. The heating and cooling rates were both 10℃ / min, and two scans were performed.

[0064] Thermogravimetric analysis: Thermogravimetric analysis was performed using an E1mer Pyris1 instrument with a heating rate of 10℃ / min.

[0065] Refractive index: This invention uses a SE-VE-L type ellipsometer to measure the refractive index in the wavelength range of 400-1000nm, and selects the refractive index corresponding to the wavelength of 589nm.

[0066] Abbe number: The Abbe number is calculated based on the refractive index at three wavelengths. This invention uses the Abbe number defined by the following formula: νd=(nd-1) / (nF-nC), where nd, nF, and nC represent the refractive index at wavelengths of 589nm, 486nm, and 656nm, respectively.

[0067] Transparency: The transparency of the cyclic olefin copolymers obtained in this invention was tested using a Shimadzu UV-3600i UV-Vis spectrophotometer at wavelengths of 400nm to 800nm.

[0068] Water absorption rate: The test method is to prepare a sample with a thickness of 1-3 mm, immerse it in water at 23°C for 24 hours according to ASTM-D 570 standard, and calculate the water absorption rate by measuring the change in mass of the sample.

[0069] Unless otherwise specified, the technical solutions described in this invention are all conventional solutions in the field. Unless otherwise specified, the reagents or raw materials used can be prepared by methods well known to those skilled in the art or can be obtained through commercial channels.

[0070] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0071] Example 1

[0072] Synthesis of cycloolefin monomer HM1 (with 1 carbon atom in the side chain)

[0073]

[0074] Under a nitrogen atmosphere, 11H-benzo[a]carbazole (76 g, 0.35 mol) and sodium hydride (15 g, 0.62 mol) were mixed and stirred in anhydrous N,N-dimethylformamide for 2 h. Then, 5-(iodomethyl)bicyclo[2.2.1]hept-2-ene (98 g, 0.41 mol) was added dropwise, and the reaction was carried out at 120 °C for 24 h. The mixture was extracted three times with ethyl acetate, purified by rotary evaporation and column chromatography with gradient elution. 乙酸乙酯 :V 石油醚 =0~1:6, vacuum dried at 60℃ for 10 hours, to obtain 96g of white solid (yield 85%).

[0075] Example 2

[0076] Synthesis of the cyclic olefin monomer HM5 (with 1 carbon atom in the side chain)

[0077]

[0078] Under a nitrogen atmosphere, 7H-benzo[c]carbazole (76 g, 0.35 mol) and sodium hydride (15 g, 0.62 mol) were mixed and stirred in anhydrous N,N-dimethylformamide for 2 h. Then, 5-bromomethylbicyclo[2.2.1]hept-2-ene (76 g, 0.41 mol) was added dropwise, and the reaction was carried out at 120 °C for 24 h. The mixture was extracted three times with ethyl acetate, purified by rotary evaporation and column chromatography with gradient elution. 乙酸乙酯 :V 石油醚 =0~1:6, vacuum dried at 60℃ for 10 hours, yielding 74g of white solid (yield 65%).

[0079] Example 3

[0080] Synthesis of the cyclic olefin monomer HM3 (with 3 carbon atoms in the side chain)

[0081]

[0082] Under a nitrogen atmosphere, 76 g (0.35 mol) of 5H-benzo[b]carbazole and 15 g (0.62 mol) of sodium hydride were mixed and stirred in anhydrous N,N-dimethylformamide for 2 h. 107 g (0.41 mol) of 5-(3-iodopropyl)bicyclo[2.2.1]hept-2-ene was added dropwise, and the reaction was carried out at 120 °C for 24 h. The mixture was extracted three times with ethyl acetate, purified by rotary evaporation and column chromatography with gradient elution. 乙酸乙酯 :V 石油醚 =0~1:10, vacuum dried at 60℃ for 10 hours, to obtain 104g of white solid (yield 85%).

[0083] Example 4

[0084] Synthesis of the cyclic olefin monomer HM5 (with 2 carbon atoms in the side chain)

[0085]

[0086] Under a nitrogen atmosphere, 7H-benzo[c]carbazole (76 g, 0.35 mol) and sodium hydride (15 g, 0.62 mol) were mixed and stirred in anhydrous N,N-dimethylformamide for 2 h. Then, 5-(2-bromoethyl)bicyclo[2.2.1]hept-2-ene (82 g, 0.41 mol) was added dropwise, and the reaction was carried out at 120 °C for 24 h. The mixture was extracted three times with ethyl acetate, purified by rotary evaporation and column chromatography with gradient elution. 乙酸乙酯 :V 石油醚 =0~1:6, vacuum dried at 60℃ for 10 hours, to obtain 96g of white solid (yield 82%).

[0087] Example 5

[0088] Synthesis of the cyclic olefin monomer HM5 (with 4 carbon atoms in the side chain)

[0089]

[0090] 7-(hex-5-en-1-yl)-7H-benzo[c]carbazole (180 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 vessel under a nitrogen atmosphere, pressurized to 5 MPa, and stirred at 200 °C for 20 hours. After cooling, the mixture was purified by column chromatography with gradient elution. 乙酸乙酯 :V 石油醚 =0~1:10, vacuum dried at 60℃ for 10 hours, to obtain 40g of white solid (yield 54%).

[0091] Example 6

[0092] Synthesis of cycloolefin monomer HM5 (with 0 carbon atoms in the side chain)

[0093]

[0094] Under a nitrogen atmosphere, 7H-benzo[c]carbazole (76 g, 0.35 mol) and sodium hydride (15 g, 0.62 mol) were mixed and stirred in anhydrous N,N-dimethylformamide for 2 h. Then, 5-bromobicyclo[2.2.1]hept-2-ene (71 g, 0.41 mol) was added dropwise, and the reaction was carried out at 120 °C for 24 h. The mixture was extracted three times with ethyl acetate, purified by rotary evaporation and column chromatography with gradient elution. 乙酸乙酯 :V 石油醚 =0~1:5, vacuum dried at 60℃ for 10 hours, yielding 65g of white solid (yield 60%).

[0095] Example 7

[0096] Synthesis of the cyclic olefin monomer HM4 (with 1 carbon atom in the side chain)

[0097]

[0098] Under a nitrogen atmosphere, 76 g (0.35 mol) of 5H-benzo[b]carbazole and 15 g (0.62 mol) of sodium hydride were mixed and stirred in anhydrous N,N-dimethylformamide for 2 h. 123 g (0.41 mol) of 2-(iodomethyl)-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylnaphthalene (123 g, 0.41 mol) was added dropwise, and the reaction was carried out at 120 °C for 24 h. The mixture was extracted three times with ethyl acetate, evaporated to dryness, purified by column chromatography with gradient elution, and V... 乙酸乙酯 :V 石油醚 =0~1:4, vacuum dried at 60℃ for 10 hours, yielding 102g of white solid (yield 75%).

[0099] Example 8

[0100] Synthesis of the cycloolefin monomer HM6 (with 1 carbon atom in the side chain)

[0101]

[0102] Under a nitrogen atmosphere, 7H-benzo[c]carbazole (76 g, 0.35 mol) and sodium hydride (15 g, 0.62 mol) were mixed and stirred in anhydrous N,N-dimethylformamide for 2 h. Then, 2-(iodomethyl)-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylnaphthalene (104 g, 0.41 mol) was added dropwise, and the reaction was carried out at 120 °C for 24 h. The mixture was extracted three times with ethyl acetate, evaporated to dryness, purified by column chromatography with gradient elution, and V... 乙酸乙酯 :V 石油醚 =0~1:4, vacuum dried at 60℃ for 10 hours, yielding 114g of white solid (yield 84%).

[0103] Example 9

[0104] Synthesis of cycloolefin monomer HM3 (with 5 carbon atoms in the side chain)

[0105]

[0106] 5-(hept-6-en-1-yl)-5H-benzo[b]carbazole (188 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 vessel under a nitrogen atmosphere, pressurized to 5 MPa, and stirred at 200 °C for 20 hours. After cooling, the mixture was purified by column chromatography with gradient elution. 乙酸乙酯 :V 石油醚 =0~1:10, vacuum dried at 60℃ for 10 hours, to obtain 50g of white solid (yield 65%).

[0107] Example 10

[0108] Synthesis of cycloolefin monomer HM1 (6 carbons in the side chain)

[0109]

[0110] 11-(oct-7-en-1-yl)-11H-benzo[a]carbazole (188 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 vessel under a nitrogen atmosphere, pressurized to 5 MPa, and stirred at 200 °C for 20 hours. After cooling, the mixture was purified by column chromatography with gradient elution. 乙酸乙酯 :V 石油醚=0~1:10, vacuum dried at 60℃ for 10 hours, to obtain 47g of white solid (yield 60%).

[0111] Example 11

[0112] The structural formula of the cyclic olefin copolymer is:

[0113]

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

[0115] At room temperature, 20.01 g (0.062 mol) of monomer HM1 prepared in Example 1 was added to a dry polymerization flask. Then, 500 mL of dry, degassed chlorobenzene solvent was added, and the mixture was magnetically stirred for 5 min to obtain a homogeneous solution. Subsequently, 0.110 g (0.124 mmol) of catalyst (G3) was dissolved in 20 mL of chlorobenzene and then rapidly injected into a round-bottom flask. After reacting at room temperature under a nitrogen atmosphere for 2 hours, 300 eqv of vinyl ethyl ether (relative to the molar amount of catalyst) was added to terminate the reaction, and the mixture was stirred for 30 min. The polymer solution was precipitated in 1000 mL of anhydrous ethanol, filtered and washed, and the collected product was dried under vacuum at 40 °C for 16 hours to obtain the polymerization product.

[0116] The polymerization product was added to a round-bottom flask equipped with a condenser along with 57.62 g of p-toluenesulfonyl hydrazine and 48.81 g of tri-n-propylamine. 0.027 g of 2,6-di-tert-butyl-4-methylphenol (BHT) was added, followed by the addition of chlorobenzene solvent and stirring to dissolve the product. The system was then subjected to vacuum purging followed by nitrogen purging, and the reaction was carried out at 120 °C for 16 hours under a nitrogen atmosphere. The polymer solution was precipitated in anhydrous ethanol, filtered, washed, and dried under vacuum at 60 °C for 18 hours to obtain the hydrogenated product, which is the cyclic olefin copolymer.

[0117] The polymerization method provided in this embodiment achieves a monomer conversion rate greater than 99%, and the hydrogenation method achieves a main-chain double bond hydrogenation rate greater than 99%. The final cyclic olefin copolymer has a refractive index of 1.67, an Abbe number of 17, and a T0. g The temperature is 180℃, the 5wt% thermal weight loss is 418℃, the water absorption rate is less than 0.01%, and the visible light transmittance is greater than 90%.

[0118] Example 12

[0119] The structural formula of the cyclic olefin copolymer is:

[0120]

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

[0122] At room temperature, 20.01 g (0.062 mol) of monomer HM5 prepared in Example 2 was added to a dry polymerization flask. Then, 500 mL of dry, degassed chlorobenzene solvent was added, and the mixture was magnetically stirred for 5 min to obtain a homogeneous solution. Subsequently, 0.110 g (0.124 mmol) of catalyst (G3) was dissolved in 20 mL of chlorobenzene and then rapidly injected into a round-bottom flask. After reacting at room temperature under a nitrogen atmosphere for 2 hours, 300 eqv of vinyl ethyl ether (relative to the molar amount of catalyst) was added to terminate the reaction, and the mixture was stirred for 30 min. The polymer solution was precipitated in 1000 mL of anhydrous ethanol, filtered and washed, and the collected product was dried under vacuum at 40 °C for 16 hours to obtain the polymerization product.

[0123] The polymerization product was added to a round-bottom flask equipped with a condenser along with 57.62 g of p-toluenesulfonyl hydrazine and 48.81 g of tri-n-propylamine. 0.027 g of 2,6-di-tert-butyl-4-methylphenol (BHT) was added, followed by the addition of chlorobenzene solvent and stirring to dissolve the product. The system was then subjected to vacuum purging followed by nitrogen purging, and the reaction was carried out at 120 °C for 16 hours under a nitrogen atmosphere. The polymer solution was precipitated in anhydrous ethanol, filtered, washed, and dried under vacuum at 60 °C for 18 hours to obtain the hydrogenated product, which is the cyclic olefin copolymer.

[0124] The polymerization method provided in this embodiment achieves a monomer conversion rate greater than 99%, and the hydrogenation method achieves a main-chain double bond hydrogenation rate greater than 99%. The final cyclic olefin copolymer has a refractive index of 1.70, an Abbe number of 14, and a T0. g The temperature is 175℃, the 5wt% thermal weight loss is 436℃, the water absorption rate is less than 0.01%, and the visible light transmittance is greater than 90%.

[0125] Example 13

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

[0127]

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

[0129] At room temperature, 18.28 g (0.052 mol) of monomer HM3 prepared in Example 3 and 1.74 g (0.013 mol) of monomer M2 were added to a dry polymerization flask. Then, 500 mL of dry, degassed chlorobenzene solvent was added, and the mixture was magnetically stirred for 5 min to obtain a homogeneous solution. Subsequently, 0.108 g (0.128 mmol) of catalyst (G2) was dissolved in 20 mL of chlorobenzene and then rapidly injected into a round-bottom flask. After reacting at room temperature under a nitrogen atmosphere for 2 hours, 300 eqv of vinyl ethyl ether (relative to the molar amount of catalyst) was added to terminate the reaction, and the mixture was stirred for 30 min. The polymer solution was precipitated in 1000 mL of anhydrous ethanol, filtered and washed, and the collected product was dried under vacuum at 40 °C for 16 hours to obtain the polymerization product.

[0130] The polymerization product was added to a round-bottom flask equipped with a condenser along with 59.52 g of p-toluenesulfonyl hydrazine and 50.33 g of tri-n-propylamine. 0.028 g of 2,6-di-tert-butyl-4-methylphenol (BHT) was added, followed by the addition of chlorobenzene solvent and stirring to dissolve the product. The system was then subjected to vacuum purging followed by nitrogen purging, and the reaction was carried out at 120°C for 16 hours under a nitrogen atmosphere. The polymer solution was precipitated in anhydrous ethanol, filtered, washed, and dried under vacuum at 60°C for 18 hours to obtain the hydrogenated product, which is the cyclic olefin copolymer.

[0131] The polymerization method provided in this embodiment achieves a monomer conversion rate greater than 99%, and the hydrogenation method achieves a main-chain double bond hydrogenation rate greater than 99%. The final cyclic olefin copolymer has a refractive index of 1.66, an Abbe number of 18, and a T0. g The temperature is 165℃, the 5wt% thermal weight loss is 432℃, the water absorption rate is less than 0.01%, and the visible light transmittance is greater than 90%.

[0132] Example 14

[0133] The structural formula of the cyclic olefin copolymer is:

[0134]

[0135] Where the degree of polymerization x = 400 and y = 200, the synthesis steps are as follows:

[0136] At room temperature, 18.28 g (0.052 mol) of monomer HM3 prepared in Example 3 and 3.48 g (0.026 mol) of monomer M2 were added to a dry polymerization flask. Then, 500 mL of dry, degassed chlorobenzene solvent was added, and the mixture was magnetically stirred for 5 min to obtain a homogeneous solution. Subsequently, 0.108 g (0.128 mmol) of catalyst (G2) was dissolved in 20 mL of chlorobenzene and then rapidly injected into a round-bottom flask. After reacting at room temperature under a nitrogen atmosphere for 2 hours, 300 eqv of vinyl ethyl ether (relative to the molar amount of catalyst) was added to terminate the reaction, and the mixture was stirred for 30 min. The polymer solution was precipitated in 1000 mL of anhydrous ethanol, filtered and washed, and the collected product was dried under vacuum at 40 °C for 16 hours to obtain the polymerization product.

[0137] The polymerization product was added to a round-bottom flask equipped with a condenser along with 71.61 g of p-toluenesulfonyl hydrazine and 60.56 g of tri-n-propylamine. 0.028 g of 2,6-di-tert-butyl-4-methylphenol (BHT) was added, followed by the addition of chlorobenzene solvent and stirring to dissolve the polymer. The system was then subjected to vacuum purging followed by nitrogen purging, and the reaction was carried out at 120°C for 16 hours under a nitrogen atmosphere. The polymer solution was precipitated in anhydrous ethanol, filtered, washed, and dried under vacuum at 60°C for 18 hours to obtain the hydrogenated product, which is the cyclic olefin copolymer.

[0138] The polymerization method provided in this embodiment achieves a monomer conversion rate greater than 99%, and the hydrogenation method achieves a main-chain double bond hydrogenation rate greater than 99%. The final cyclic olefin copolymer has a refractive index of 1.65, an Abbe number of 19, and a T0. g The temperature is 162℃, the temperature at which the weight loss is 5wt% is 434℃, the water absorption rate is less than 0.01%, and the visible light transmittance is greater than 90%.

[0139] Example 15

[0140] The structural formula of the cyclic olefin copolymer is:

[0141]

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

[0143] At room temperature, 19.91 g (0.059 mol) of monomer HM5 prepared in Example 4 and 4.75 g (0.030 mol) of monomer M3 were added to a dry polymerization flask. Then, 500 mL of dry, degassed chlorobenzene solvent was added, and the mixture was magnetically stirred for 5 min to obtain a homogeneous solution. Subsequently, 0.126 g (0.148 mmol) of catalyst (G2) was dissolved in 20 mL of chlorobenzene and then rapidly injected into a round-bottom flask. After reacting at room temperature under a nitrogen atmosphere for 2 hours, 300 eqv of vinyl ethyl ether (relative to the molar amount of catalyst) was added to terminate the reaction, and the mixture was stirred for 30 min. The polymer solution was precipitated in 1000 mL of anhydrous ethanol, filtered and washed, and the collected product was dried under vacuum at 40 °C for 16 hours to obtain the polymerization product.

[0144] The polymerization product was added to a round-bottom flask equipped with a condenser along with 82.77 g of p-toluenesulfonyl hydrazine and 69.98 g of tri-n-propylamine. 0.028 g of 2,6-di-tert-butyl-4-methylphenol (BHT) was added, followed by the addition of chlorobenzene solvent and stirring to dissolve the product. The system was then subjected to vacuum purging followed by nitrogen purging, and the reaction was carried out at 120 °C for 16 hours under a nitrogen atmosphere. The polymer solution was precipitated in anhydrous ethanol, filtered, washed, and dried under vacuum at 60 °C for 18 hours to obtain the hydrogenated product, which is the cyclic olefin copolymer.

[0145] The polymerization method provided in this embodiment achieves a monomer conversion rate greater than 99%, and the hydrogenation method achieves a main-chain double bond hydrogenation rate greater than 99%. The final cyclic olefin copolymer has a refractive index of 1.65, an Abbe number of 19, and a T0. g The temperature is 163℃, the 5wt% thermal weight loss is 436℃, the water absorption rate is less than 0.01%, and the visible light transmittance is greater than 90%.

[0146] Example 16

[0147] The structural formula of the cyclic olefin copolymer is:

[0148]

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

[0150] At room temperature, 14.85 g (0.044 mol) of monomer HM5 prepared in Example 4 and 7.04 g (0.044 mol) of monomer M3 were added to a dry polymerization flask. Then, 500 mL of dry, degassed chlorobenzene solvent was added, and the mixture was magnetically stirred for 5 min to obtain a homogeneous solution. Subsequently, 0.126 g (0.148 mmol) of catalyst (G2) was dissolved in 20 mL of chlorobenzene and then rapidly injected into a round-bottom flask. After reacting at room temperature under a nitrogen atmosphere for 2 hours, 300 eqv of vinyl ethyl ether (relative to the molar amount of catalyst) was added to terminate the reaction, and the mixture was stirred for 30 min. The polymer solution was precipitated in 1000 mL of anhydrous ethanol, filtered and washed, and the collected product was dried under vacuum at 40 °C for 16 hours to obtain the polymerization product.

[0151] The polymerization product was added to a round-bottom flask equipped with a condenser along with 82.77 g of p-toluenesulfonyl hydrazine and 69.98 g of tri-n-propylamine. 0.028 g of 2,6-di-tert-butyl-4-methylphenol (BHT) was added, followed by the addition of chlorobenzene solvent and stirring to dissolve the product. The system was then subjected to vacuum purging followed by nitrogen purging, and the reaction was carried out at 120 °C for 16 hours under a nitrogen atmosphere. The polymer solution was precipitated in anhydrous ethanol, filtered, washed, and dried under vacuum at 60 °C for 18 hours to obtain the hydrogenated product, which is the cyclic olefin copolymer.

[0152] The polymerization method provided in this embodiment achieves a monomer conversion rate greater than 99%, and the hydrogenation method achieves a main-chain double bond hydrogenation rate greater than 99%. The final cyclic olefin copolymer has a refractive index of 1.64, an Abbe number of 20, and a T0. g The temperature is 161℃, the 5wt% thermal weight loss is 432℃, the water absorption rate is less than 0.01%, and the visible light transmittance is greater than 90%.

[0153] Example 17

[0154] The structural formula of the cyclic olefin copolymer is:

[0155]

[0156] Where the degree of polymerization x = 250 and y = 250, the synthesis steps are as follows:

[0157] At room temperature, 14.62 g (0.040 mol) of monomer HM5 prepared in Example 5 and 8.01 g (0.040 mol) of monomer M5 were added to a dry polymerization flask. Then, 500 mL of dry, degassed chlorobenzene solvent was added, and the mixture was magnetically stirred for 5 min to obtain a homogeneous solution. Subsequently, 0.135 g (0.160 mmol) of catalyst (G2) was dissolved in 20 mL of chlorobenzene and then rapidly injected into a round-bottom flask. After reacting at room temperature under a nitrogen atmosphere for 2 hours, 300 eqv of vinyl ethyl ether (relative to the molar amount of catalyst) was added to terminate the reaction, and the mixture was stirred for 30 min. The polymer solution was precipitated in 1000 mL of anhydrous ethanol, filtered and washed, and the collected product was dried under vacuum at 40 °C for 16 hours to obtain the polymerization product.

[0158] The polymerization product was added to a round-bottom flask equipped with a condenser along with 74.40 g of p-toluenesulfonyl hydrazine and 62.92 g of tri-n-propylamine. 0.035 g of 2,6-di-tert-butyl-4-methylphenol (BHT) was added, followed by the addition of chlorobenzene solvent and stirring to dissolve the product. The system was then subjected to vacuum purging followed by nitrogen purging, and the reaction was carried out at 120 °C for 16 hours under a nitrogen atmosphere. The polymer solution was precipitated in anhydrous ethanol, filtered, washed, and dried under vacuum at 60 °C for 18 hours to obtain the hydrogenated product, which is the cyclic olefin copolymer.

[0159] The polymerization method provided in this embodiment achieves a monomer conversion rate greater than 99%, and the hydrogenation method achieves a main-chain double bond hydrogenation rate greater than 99%. The final cyclic olefin copolymer has a refractive index of 1.63, an Abbe number of 23, and a T0. g The temperature is 170℃, the 5wt% thermal weight loss is 433℃, the water absorption rate is less than 0.01%, and the visible light transmittance is greater than 90%.

[0160] Example 18

[0161] The structural formula of the cyclic olefin copolymer is:

[0162]

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

[0164] At room temperature, 18.56 g (0.060 mol) of monomer HM5 prepared in Example 6 and 1.02 g (0.015 mol) of monomer M7 were added to a dry polymerization flask. Then, 500 mL of dry, degassed chlorobenzene solvent was added, and the mixture was magnetically stirred for 5 min to obtain a homogeneous solution. Subsequently, 0.133 g (0.150 mmol) of catalyst (G3) was dissolved in 20 mL of chlorobenzene and then rapidly injected into a round-bottom flask. After reacting at room temperature under a nitrogen atmosphere for 2 hours, 300 eqv of vinyl ethyl ether (relative to the molar amount of catalyst) was added to terminate the reaction, and the mixture was stirred for 30 min. The polymer solution was precipitated in 1000 mL of anhydrous ethanol, filtered and washed, and the collected product was dried under vacuum at 40 °C for 16 hours to obtain the polymerization product.

[0165] The polymerization product was added to a round-bottom flask equipped with a condenser along with 69.75 g of p-toluenesulfonyl hydrazine and 58.98 g of tri-n-propylamine. 0.033 g of 2,6-di-tert-butyl-4-methylphenol (BHT) was added, followed by the addition of chlorobenzene solvent and stirring to dissolve the product. The system was then subjected to vacuum purging followed by nitrogen purging, and the reaction was carried out at 120 °C for 16 hours under a nitrogen atmosphere. The polymer solution was precipitated in anhydrous ethanol, filtered, washed, and dried under vacuum at 60 °C for 18 hours to obtain the hydrogenated product, which is the cyclic olefin copolymer.

[0166] The polymerization method provided in this embodiment achieves a monomer conversion rate greater than 99%, and the hydrogenation method achieves a main-chain double bond hydrogenation rate greater than 99%. The final cyclic olefin copolymer has a refractive index of 1.69, an Abbe number of 15, and a T0. g The temperature is 168℃, the 5wt% thermal weight loss is 435℃, the water absorption rate is less than 0.01%, and the visible light transmittance is greater than 90%.

[0167] Example 19

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

[0169]

[0170] Where the degree of polymerization x = 700 and y = 100, the synthesis steps are as follows:

[0171] At room temperature, 19.49 g (0.063 mol) of monomer HM5 prepared in Example 6 and 0.99 g (0.009 mol) of monomer M10 were added to a dry polymerization flask. Then, 500 mL of dry, degassed chlorobenzene solvent was added, and the mixture was magnetically stirred for 5 min to obtain a homogeneous solution. Subsequently, 0.078 g (0.090 mmol) of catalyst (G3) was dissolved in 20 mL of chlorobenzene and then rapidly injected into a round-bottom flask. After reacting at room temperature under a nitrogen atmosphere for 2 hours, 300 eqv of vinyl ethyl ether (relative to the molar amount of catalyst) was added to terminate the reaction, and the mixture was stirred for 30 min. The polymer solution was precipitated in 1000 mL of anhydrous ethanol, filtered and washed, and the collected product was dried under vacuum at 40 °C for 16 hours to obtain the polymerization product.

[0172] The polymerization product was added to a round-bottom flask equipped with a condenser along with 66.03 g of p-toluenesulfonyl hydrazine and 55.84 g of tri-n-propylamine. 0.020 g of 2,6-di-tert-butyl-4-methylphenol (BHT) was added, followed by the addition of chlorobenzene solvent and stirring to dissolve the product. The system was then subjected to vacuum purging followed by nitrogen purging, and the reaction was carried out at 120°C for 16 hours under a nitrogen atmosphere. The polymer solution was precipitated in anhydrous ethanol, filtered, washed, and dried under vacuum at 60°C for 18 hours to obtain the hydrogenated product, which is the cyclic olefin copolymer.

[0173] The polymerization method provided in this embodiment achieves a monomer conversion rate greater than 99%, and the hydrogenation method achieves a main-chain double bond hydrogenation rate greater than 99%. The final cyclic olefin copolymer has a refractive index of 1.69, an Abbe number of 15, and a T0. g The temperature is 165℃, the 5wt% thermal weight loss is 430℃, the water absorption rate is less than 0.01%, and the visible light transmittance is greater than 90%.

[0174] Example 20

[0175] The structural formula of the cyclic olefin copolymer is:

[0176]

[0177] Where the degree of polymerization x = 400 and y = 100, the synthesis steps are as follows:

[0178] At room temperature, 24.75 g (0.080 mol) of monomer HM5 prepared in Example 6 and 1.88 g (0.020 mol) of monomer M8 were added to a dry polymerization flask. Then, 500 mL of dry, degassed chlorobenzene solvent was added, and the mixture was magnetically stirred for 5 min to obtain a homogeneous solution. Subsequently, 0.173 g (0.196 mmol) of catalyst (G3) was dissolved in 20 mL of chlorobenzene and then rapidly injected into a round-bottom flask. After reacting at room temperature under a nitrogen atmosphere for 2 hours, 300 eqv of vinyl ethyl ether (relative to the molar amount of catalyst) was added to terminate the reaction, and the mixture was stirred for 30 min. The polymer solution was precipitated in 1000 mL of anhydrous ethanol, filtered and washed, and the collected product was dried under vacuum at 40 °C for 16 hours to obtain the polymerization product.

[0179] The autoclave was pre-dried under vacuum for 5 hours. The polymerization product prepared above, 500 mL of chlorobenzene, and 13 g of Pd / Al₂O₃ catalyst were added to the autoclave. After three evacuation operations, hydrogen gas at 10 MPa was introduced into the autoclave, and a hydrogenation reaction was carried out at 120°C for 15 hours. The resulting hydrogenation reaction solution was filtered to recover the Pd / Al₂O₃ catalyst, yielding the hydrogenation reaction product. The hydrogenation reaction product was poured into ethanol to precipitate, filtered, washed, and the resulting precipitate was placed in a vacuum oven and dried at 60°C for 18 hours to obtain the cyclic olefin copolymer.

[0180] The polymerization method provided in this embodiment achieves a monomer conversion rate greater than 99%, and the hydrogenation method achieves a main-chain double bond hydrogenation rate greater than 99%. The final cyclic olefin copolymer has a refractive index of 1.68, an Abbe number of 15, and a T0. g The temperature is 173℃, the 5wt% thermal weight loss is 435℃, the water absorption rate is less than 0.01%, and the visible light transmittance is greater than 90%.

[0181] Example 21

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

[0183]

[0184] Where the degree of polymerization x = 480 and y = 80, the synthesis steps are as follows:

[0185] At room temperature, 25.71 g (0.066 mol) of monomer HM4 prepared in Example 7 and 1.21 g (0.011 mol) of monomer M10 were added to a dry polymerization flask. Then, 500 mL of dry, degassed chlorobenzene solvent was added, and the mixture was magnetically stirred for 5 min to obtain a homogeneous solution. Subsequently, 0.117 g (0.132 mmol) of catalyst (G3) was dissolved in 20 mL of chlorobenzene and then rapidly injected into a round-bottom flask. After reacting at room temperature under a nitrogen atmosphere for 2 hours, 300 eqv of vinyl ethyl ether (relative to the molar amount of catalyst) was added to terminate the reaction, and the mixture was stirred for 30 min. The polymer solution was precipitated in 1000 mL of anhydrous ethanol, filtered and washed, and the collected product was dried under vacuum at 40 °C for 16 hours to obtain the polymerization product.

[0186] The autoclave was pre-dried under vacuum for 5 hours. The polymerization product prepared above, 500 mL of chlorobenzene, and 13 g of Pd / Al₂O₃ catalyst were added to the autoclave. After three evacuation operations, hydrogen gas at 10 MPa was introduced into the autoclave, and a hydrogenation reaction was carried out at 120°C for 15 hours. The resulting hydrogenation reaction solution was filtered to recover the Pd / Al₂O₃ catalyst, yielding the hydrogenation reaction product. The hydrogenation reaction product was poured into ethanol to precipitate, filtered, washed, and the resulting precipitate was placed in a vacuum oven and dried at 60°C for 18 hours to obtain the cyclic olefin copolymer.

[0187] The polymerization method provided in this embodiment achieves a monomer conversion rate greater than 99%, and the hydrogenation method achieves a main-chain double bond hydrogenation rate greater than 99%. The final cyclic olefin copolymer has a refractive index of 1.66, an Abbe number of 18, and a T0. g The temperature is 185℃, the 5wt% thermal weight loss is 427℃, the water absorption rate is less than 0.01%, and the visible light transmittance is greater than 90%.

[0188] Example 22

[0189] The structural formula of the cyclic olefin copolymer is:

[0190]

[0191] Where the degree of polymerization x = 400 and y = 100, the synthesis steps are as follows:

[0192] At room temperature, 20.25 g (0.052 mol) of monomer HM6 prepared in Example 8 and 0.90 g (0.013 mol) of monomer M7 were added to a dry polymerization flask. Then, 500 mL of dry, degassed chlorobenzene solvent was added, and the mixture was magnetically stirred for 5 min to obtain a homogeneous solution. Subsequently, 0.117 g (0.132 mmol) of catalyst (G3) was dissolved in 20 mL of chlorobenzene and then rapidly injected into a round-bottom flask. After reacting at room temperature under a nitrogen atmosphere for 2 hours, 300 eqv of vinyl ethyl ether (relative to the molar amount of catalyst) was added to terminate the reaction, and the mixture was stirred for 30 min. The polymer solution was precipitated in 1000 mL of anhydrous ethanol, filtered and washed, and the collected product was dried under vacuum at 40 °C for 16 hours to obtain the polymerization product.

[0193] The autoclave was pre-dried under vacuum for 5 hours. The polymerization product prepared above, 500 mL of chlorobenzene, and 11 g of Pd / Al₂O₃ catalyst were added to the autoclave. After three evacuation operations, hydrogen gas at 20 MPa was introduced into the autoclave, and a hydrogenation reaction was carried out at 120 °C for 15 hours. The resulting hydrogenation reaction solution was filtered to recover the Pd / Al₂O₃ catalyst, yielding the hydrogenation reaction product. The hydrogenation reaction product was poured into ethanol to precipitate, filtered, washed, and the resulting precipitate was placed in a vacuum oven and dried at 60 °C for 18 hours to obtain the cyclic olefin copolymer.

[0194] The polymerization method provided in this embodiment achieves a monomer conversion rate greater than 99%, and the hydrogenation method achieves a main-chain double bond hydrogenation rate greater than 99%. The final cyclic olefin copolymer has a refractive index of 1.67, an Abbe number of 17, and a T0. g The temperature is 184℃, the 5wt% thermal weight loss is 432℃, the water absorption rate is less than 0.01%, and the visible light transmittance is greater than 90%.

[0195] Example 23

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

[0197]

[0198] Where the degree of polymerization x1 = 100 and x2 = 500, the synthesis steps are as follows:

[0199] At room temperature, 5.69 g (0.015 mol) of monomer HM3 prepared in Example 9 and 23.20 g (0.075 mol) of monomer HM5 prepared in Example 6 were added to a dry polymerization flask. Then, 500 mL of dry, degassed chlorobenzene solvent was added, and the mixture was magnetically stirred for 5 min to obtain a homogeneous solution. Subsequently, 0.117 g (0.132 mmol) of catalyst (G3) was dissolved in 20 mL of chlorobenzene and then rapidly injected into a round-bottom flask. After reacting at room temperature under a nitrogen atmosphere for 2 hours, 300 eqv of vinyl ethyl ether (relative to the molar amount of catalyst) was added to terminate the reaction, and the mixture was stirred for 30 min. The polymer solution was precipitated in 1000 mL of anhydrous ethanol, filtered and washed, and the collected product was dried under vacuum at 40 °C for 16 hours to obtain the polymerization product.

[0200] The autoclave was pre-dried under vacuum for 5 hours. The polymerization product prepared above, 500 mL of chlorobenzene, and 14 g of Pd / Al₂O₃ catalyst were added to the autoclave. After three evacuation operations, hydrogen gas at 20 MPa was introduced into the autoclave, and a hydrogenation reaction was carried out at 120 °C for 15 hours. The resulting hydrogenation reaction solution was filtered to recover the Pd / Al₂O₃ catalyst, yielding the hydrogenation reaction product. The hydrogenation reaction product was poured into ethanol to precipitate, filtered, washed, and the resulting precipitate was placed in a vacuum oven and dried at 60 °C for 18 hours to obtain the cyclic olefin copolymer.

[0201] The polymerization method provided in this embodiment achieves a monomer conversion rate greater than 99%, and the hydrogenation method achieves a main-chain double bond hydrogenation rate greater than 99%. The final cyclic olefin copolymer has a refractive index of 1.68, an Abbe number of 15, and a T0. g The temperature is 172℃, the 5wt% thermal weight loss is 430℃, the water absorption rate is less than 0.01%, and the visible light transmittance is greater than 90%.

[0202] Example 24

[0203] The structural formula of the cyclic olefin copolymer is:

[0204]

[0205] Where the degree of polymerization x1 = 100 and x2 = 500, the synthesis steps are as follows:

[0206] At room temperature, 6.69 g (0.017 mol) of monomer HM1 prepared in Example 10 and 26.30 g (0.085 mol) of monomer HM5 prepared in Example 6 were added to a dry polymerization flask. Then, 500 mL of dry, degassed chlorobenzene solvent was added, and the mixture was magnetically stirred for 5 min to obtain a homogeneous solution. Subsequently, 0.089 g (0.101 mmol) of catalyst (G3) was dissolved in 20 mL of chlorobenzene and then rapidly injected into a round-bottom flask. After reacting at room temperature under a nitrogen atmosphere for 2 hours, 300 eqv of vinyl ethyl ether (relative to the molar amount of catalyst) was added to terminate the reaction, and the mixture was stirred for 30 min. The polymer solution was precipitated in 1000 mL of anhydrous ethanol, filtered and washed, and the collected product was dried under vacuum at 40 °C for 16 hours to obtain the polymerization product.

[0207] The autoclave was pre-dried under vacuum for 5 hours. The polymerization product prepared above and 500 mL of chlorobenzene were added to the autoclave, and the autoclave was evacuated three times. 0.128 g of nickel naphthenate and 2.24 mmol of triisobutylaluminum were placed in an ampoule, and an appropriate amount of hydrogenation solvent was added and mixed thoroughly. The mixture was then placed in a water bath at a set temperature for aging. Under nitrogen protection, the mixture was injected into the autoclave using a syringe. Hydrogen gas at 10 MPa was introduced into the autoclave, and a hydrogenation reaction was carried out at 120 °C for 15 hours. The resulting hydrogenation product was poured into ethanol to precipitate, filtered, washed, and the precipitate was dried in a vacuum oven at 60 °C for 18 hours to obtain the cyclic olefin copolymer.

[0208] The polymerization method provided in this embodiment achieves a monomer conversion rate greater than 99%, and the hydrogenation method achieves a main-chain double bond hydrogenation rate greater than 99%. The final cyclic olefin copolymer has a refractive index of 1.68, an Abbe number of 15, and a T0. g The temperature is 170℃, the 5wt% thermal weight loss is 428℃, the water absorption rate is less than 0.01%, and the visible light transmittance is greater than 90%.

[0209] Example 25

[0210] The structural formula of the cyclic olefin copolymer is:

[0211]

[0212] Where the degree of polymerization x = 300, y1 = 75, y2 = 75, the synthesis steps are as follows:

[0213] At room temperature, 25.88 g (0.080 mol) of monomer HM5 prepared in Example 2, 3.20 g (0.020 mol) of monomer M3, and 1.36 g (0.020 mol) of monomer M7 were added to a dry polymerization flask. Then, 500 mL of dry, degassed chlorobenzene solvent was added, and the mixture was magnetically stirred for 5 min to obtain a homogeneous solution. Subsequently, 0.234 g (0.264 mmol) of catalyst (G3) was dissolved in 20 mL of chlorobenzene and then rapidly injected into a round-bottom flask. After reacting at room temperature under a nitrogen atmosphere for 2 hours, 300 eqv of vinyl ethyl ether (relative to the molar amount of catalyst) was added to terminate the reaction, and the mixture was stirred for 30 min. The polymer solution was precipitated in 1000 mL of anhydrous ethanol, filtered and washed, and the collected product was dried under vacuum at 40 °C for 16 hours to obtain the polymerization product.

[0214] The autoclave was pre-dried under vacuum for 5 hours. The polymerization product prepared above and 500 mL of chlorobenzene were added to the autoclave, and the autoclave was evacuated three times. 0.120 g of nickel naphthenate and 2.10 mmol of triisobutylaluminum were placed in an ampoule, and an appropriate amount of hydrogenation solvent was added and mixed thoroughly. The mixture was then placed in a water bath at a set temperature for aging. Under nitrogen protection, the mixture was injected into the autoclave using a syringe. Hydrogen gas at 10 MPa was introduced into the autoclave, and a hydrogenation reaction was carried out at 120 °C for 15 hours. The resulting hydrogenation product was poured into ethanol to precipitate, filtered, washed, and the precipitate was dried in a vacuum oven at 60 °C for 18 hours to obtain the cyclic olefin copolymer.

[0215] The polymerization method provided in this embodiment achieves a monomer conversion rate greater than 99%, and the hydrogenation method achieves a main-chain double bond hydrogenation rate greater than 99%. The final cyclic olefin copolymer has a refractive index of 1.67, an Abbe number of 17, and a T0. g The temperature is 164℃, the 5wt% thermal weight loss is 435℃, the water absorption rate is less than 0.01%, and the visible light transmittance is greater than 90%.

[0216] Example 26

[0217] The structural formula of the cyclic olefin copolymer is:

[0218]

[0219] Where the degree of polymerization x = 250, y1 = 125, and y2 = 62, the synthesis steps are as follows:

[0220] At room temperature, 25.88 g (0.080 mol) of monomer HM5 prepared in Example 2, 6.41 g (0.040 mol) of monomer M3, and 1.36 g (0.020 mol) of monomer M7 were added to a dry polymerization flask. Then, 500 mL of dry, degassed chlorobenzene solvent was added, and the mixture was magnetically stirred for 5 min to obtain a homogeneous solution. Subsequently, 0.283 g (0.320 mmol) of catalyst (G3) was dissolved in 20 mL of chlorobenzene and then rapidly injected into a round-bottom flask. After reacting at room temperature under a nitrogen atmosphere for 2 hours, 300 eqv of vinyl ethyl ether (relative to the molar amount of catalyst) was added to terminate the reaction, and the mixture was stirred for 30 min. The polymer solution was precipitated in 1000 mL of anhydrous ethanol, filtered and washed, and the collected product was dried under vacuum at 40 °C for 16 hours to obtain the polymerization product.

[0221] The autoclave was pre-dried under vacuum for 5 hours. The polymerization product prepared above and 500 mL of chlorobenzene were added to the autoclave, and the autoclave was evacuated three times. 0.132 g of nickel naphthenate and 3.52 mmol of triisobutylaluminum were placed in an ampoule, and an appropriate amount of hydrogenation solvent was added and mixed thoroughly. The mixture was then placed in a water bath at a set temperature for aging. Under nitrogen protection, the mixture was injected into the autoclave using a syringe. Hydrogen gas at 20 MPa was introduced into the autoclave, and a hydrogenation reaction was carried out at 120 °C for 15 hours. The resulting hydrogenation product was poured into ethanol to precipitate, filtered, washed, and the precipitate was dried in a vacuum oven at 60 °C for 18 hours to obtain the cyclic olefin copolymer.

[0222] The polymerization method provided in this embodiment achieves a monomer conversion rate greater than 99%, and the hydrogenation method achieves a main-chain double bond hydrogenation rate greater than 99%. The final cyclic olefin copolymer has a refractive index of 1.65, an Abbe number of 19, and a T0. g The temperature is 162℃, the 5wt% thermal weight loss is 436℃, the water absorption rate is less than 0.01%, and the visible light transmittance is greater than 90%.

[0223] Example 27

[0224] The structural formula of the cyclic olefin copolymer is:

[0225]

[0226] Where the degree of polymerization x1 = 150, x2 = 300, and y = 75, the synthesis steps are as follows:

[0227] At room temperature, 8.08 g (0.025 mol) of monomer HM1 prepared in Example 1, 16.17 g (0.050 mol) of monomer HM5 prepared in Example 2, and 0.85 g (0.0125 mol) of monomer M7 were added to a dry polymerization flask. Then, 500 mL of dry, degassed chlorobenzene solvent was added, and the mixture was magnetically 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 rapidly injected into a round-bottom flask. After reacting at room temperature under a nitrogen atmosphere for 2 hours, 300 eqv of vinyl ethyl ether (relative to the molar amount of catalyst) was added to terminate the reaction, and the mixture was stirred for 30 min. The polymer solution was precipitated in 1000 mL of anhydrous ethanol, filtered and washed, and the collected product was dried under vacuum at 40 °C for 16 hours to obtain the polymerization product.

[0228] The autoclave was pre-dried under vacuum for 5 hours. The polymerization product prepared above and 500 mL of chlorobenzene were added to the autoclave, and the autoclave was evacuated three times. 0.102 g of nickel naphthenate and 1.78 mmol of triisobutylaluminum were placed in an ampoule, and an appropriate amount of hydrogenation solvent was added and mixed thoroughly. The mixture was then placed in a water bath at a set temperature for aging. Under nitrogen protection, the mixture was injected into the autoclave using a syringe. Hydrogen gas at 20 MPa was introduced into the autoclave, and a hydrogenation reaction was carried out at 120 °C for 15 hours. The resulting hydrogenation product was poured into ethanol to precipitate, filtered, washed, and the precipitate was dried in a vacuum oven at 60 °C for 18 hours to obtain the cyclic olefin copolymer.

[0229] The polymerization method provided in this embodiment achieves a monomer conversion rate greater than 99%, and the hydrogenation method achieves a main-chain double bond hydrogenation rate greater than 99%. The final cyclic olefin copolymer has a refractive index of 1.68, an Abbe number of 15, and a T0. g The temperature is 172℃, the 5wt% thermal weight loss is 426℃, the water absorption rate is less than 0.01%, and the visible light transmittance is greater than 90%.

[0230] Comparative Example 1

[0231] The structural formula of the cyclic olefin copolymer is:

[0232]

[0233] The degree of polymerization x = 500, and the polymer synthesis steps adopted the same preparation method as in Example 12 above. The final polymer has a refractive index of 1.64, an Abbe number of 20, and a T0. g The temperature is 141℃, the 5wt% thermal weight loss is 435℃, the water absorption rate is less than 0.01%, and the visible light transmittance is greater than 90%.

[0234] Comparing Comparative Example 1 and Example 12, it can be seen that the cyclic olefin copolymer prepared by introducing a benzocarbazole group in this invention achieves a comprehensive improvement in both optical and thermal properties compared to the carbazole-based material in the comparative example. The polymer refractive index of Example 12 is as high as 1.70, an increase of 0.06 compared to 1.64 in the comparative example, demonstrating a qualitative breakthrough, especially suitable for the field of high-refractive-index optical materials. Furthermore, the glass transition temperature (Tg) of Example 12 is significantly higher than that of the comparative example. g The temperature reached 175℃, a significant increase compared to the 141℃ of the comparative example, indicating that the introduction of the benzocarbazole group also significantly improved the thermal stability of the material. Simultaneously, while achieving a high refractive index, the material of this invention still maintains excellent transparency (visible light transmittance >90%) and extremely low hygroscopicity (water absorption <0.01%). These combined properties far exceed those of Comparative Example 1.

[0235] Figure 1 and Figure 2 NMR spectra of the cycloolefin monomers obtained in Example 1 of this invention 1 H-NMR spectrum and 13 C-NMR spectrum; by Figure 1 and Figure 2 It can be seen that the characteristic peaks are consistent with the expected structure, proving that the cyclic olefin monomer has been successfully prepared.

[0236] Figure 3 and Figure 4 NMR of the cyclic olefin copolymer obtained in Example 11 of this invention 1 H-NMR spectrum and 13 C-NMR spectrum; by Figure 3 and Figure 4 It can be seen that the characteristic peaks of the cyclic olefin copolymer are consistent with the expected structure, and the double bond characteristic signal in the raw material has disappeared significantly, indicating that the hydrogenation reaction was successfully completed and the target cyclic olefin copolymer was obtained.

[0237] The products prepared in Examples 2-10 and 12-27 were subjected to NMR. 1 H-NMR spectrum and 13 C-NMR spectral analysis showed that all target products were successfully prepared.

[0238] Figure 5 The differential scanning calorimetry (DSC) curve of the cyclic olefin copolymer obtained in Example 11 of this invention is shown below. Figure 5 It can be seen that the cyclic olefin copolymer prepared in Example 11 has a glass transition temperature as high as 180°C and exhibits high thermal stability.

[0239] Figure 6 The refractive index curve of the cyclic olefin copolymer obtained in Example 12 of this invention is shown below; Figure 6It can be seen that the cyclic olefin copolymer prepared in Example 12 has a high refractive index of up to 1.70 in the visible light range.

[0240] Figure 7 The thermogravimetric curve of the cyclic olefin copolymer obtained in Example 15 of this invention in nitrogen gas; Figure 7 It can be seen that the cyclic olefin copolymer prepared in Example 15 has a thermal decomposition temperature as high as 436°C at 5 wt%, and exhibits high heat resistance.

[0241] Figure 8 The transmittance curve of the cyclic olefin copolymer obtained in Example 18 of this invention is shown. Figure 8 It can be seen that the cyclic olefin copolymer prepared in Example 18 has a visible light transmittance of more than 90% and has high transparency.

[0242] Comparative Examples 2-4 are common commercially available cyclic olefin copolymers, as detailed in Table 1.

[0243] Table 1. Properties of some commercially available cyclic olefin copolymers

[0244]

[0245]

[0246] Note: T d5 The temperature at which thermal weight loss is 5 wt%.

[0247] A comparison of Comparative Examples 2-4 and Examples 11-27 shows that the cyclic olefin copolymers of the present invention exhibit comprehensive superiority in performance. The refractive index of the material reaches 1.63–1.70, significantly higher than that of the commercial materials in the comparative examples. Simultaneously, the glass transition temperature reaches 161°C–185°C, and the thermal decomposition temperature exceeds 415°C, demonstrating excellent heat resistance. More notably, while maintaining a high refractive index, the material exhibits a light transmittance exceeding 90%, excellent transparency, and a water absorption rate of less than 0.01%, demonstrating outstanding environmental stability. Through a unique molecular structure design, the present invention significantly improves the optical and thermal properties of cyclic olefin copolymers, providing important technical support for the development of high-refractive-index optical materials.

[0248] 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 by, It has the structure shown in Equation I: Formula I; In Formula I, x and y represent the degree of polymerization, 10 ≤ x ≤ 800, 0 < y ≤ 700, but do not necessarily indicate block copolymers; dashed lines indicate bonding or non-bonding; i and j represent the number of rings, i is 0 or 1, j is 0 or 1; m and n represent the number of carbon atoms, 0 ≤ m ≤ 10, 0 ≤ n ≤ 4; and j and n are not both 0; R1 to R6 are each independently selected from hydrogen atoms, alkyl groups, and alkenyl groups; among them, R1 and R2, and R3 and R4 can form a benzene ring structure together with adjacent carbon atoms through bonding, or they can exist independently without bonding; R5 and R6 can form bonds or not.

2. A process for the preparation of the cyclic olefin copolymer according to claim 1, characterized in that, Includes the following steps: In the presence of a catalyst, the monomer undergoes a ring-opening metathesis polymerization reaction 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 and at least one compound of formula III; The structure of the compound shown in Formula II is as follows: Formula II; In Formula II, i is the number of rings, i is 0 or 1; m is the number of carbon atoms, 0≤m≤10; R1~R4 are each independently selected from one of hydrogen atoms, alkyl and alkenyl groups, wherein R1 and R2, and R3 and R4 can form a benzene ring structure together with adjacent carbon atoms through bonding, or they can exist independently without bonding. The structure of the compound shown in Formula III is as follows: Formula III; In Formula III, the dashed line indicates whether or not a bond is formed; j is the ring number, which is 0 or 1; n is the number of carbon atoms, where 0 ≤ n ≤ 4; and j and n are not both 0; R5 and R6 are each independently selected from one of hydrogen atoms, alkyl groups and alkenyl groups, wherein R5 and R6 may or may not form a bond.

3. The process for the preparation of a cyclic olefin copolymer according to claim 2, characterized in that, The compound shown in Formula II is selected from at least one of the HM1-HM8 structures: ； Where m is the number of carbon atoms, 0 ≤ m ≤ 10.

4. The method of claim 2, wherein the ring-opening metathesis polymerization is carried out in the presence of a catalyst selected from the group consisting of Grubbs catalyst, Hoveyda-Grubbs catalyst, and mixtures thereof. The compound shown in Formula III is selected from at least one of the structures M1-M10: 。 5. 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.

6. The method for preparing the cyclic olefin copolymer according to claim 2, characterized in that, The molar ratio of the monomer to the catalyst is (100~1500):

1.

7. 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.

8. 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 h.

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

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