Cycloolefin copolymer, process for its preparation, use in optical materials

Abstract

The present application relates to the technical field of new high-end polyolefin, in particular to a kind of cycloolefin copolymer and its preparation method, the use in optical material.The cycloolefin copolymer has the structure shown in formula I: The present application introduces high polarizability sulfur-containing group in polymer molecular structure, so that the prepared cycloolefin copolymer realizes high refractive index of 1.62~1.66, while having abbe number of 22~25, and exhibits excellent optical performance.The light transmittance of the material is more than 90%, the moisture absorption is lower, and has glass transition temperature of 130 DEG C~175 DEG C, and shows good thermal stability.With these excellent properties, the material has wide application prospect in high refractive index optical element, optical coating and high-end optical equipment.

Description

Technical Field

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

[0002] With the rapid development of optical technology, the demand for high-refractive-index polymer materials is increasing in fields such as optical components, optical coatings, display devices, fiber optic communications, and sensors. High-refractive-index materials can significantly improve the performance of optical devices, such as improving image quality, enhancing light focusing effects, and reducing device size and weight. Therefore, developing polymer materials that combine high refractive index, excellent light transmittance, and thermal stability has become a research hotspot.

[0003] Cycloolefin copolymers have wide applications in the optical field due to their high transparency, low birefringence, excellent mechanical properties, and thermal stability. However, their refractive index is usually low (about 1.53 to 1.55), which makes it difficult to meet the ever-growing demand for high-performance optical materials. Therefore, improving the refractive index of cycloolefin copolymers has become an important research direction.

[0004] Sulfur, as a highly polarizable element, can significantly improve the refractive index of polymers upon introduction. For example, sulfur-containing groups (such as thioethers, thiophenes, and benzothiophenes) can enhance the electronic polarizability of materials, thereby increasing the refractive index. Introducing sulfur-containing groups into the structure of cyclic olefin polymers can simultaneously improve the refractive index of the material, providing a new approach for developing high-performance optical polymers.

[0005] Existing technologies disclose the use of crosslinking groups to introduce sulfur-containing units to improve the refractive index of polymers. However, while introducing high refractive index units, this method also causes the polymer to exhibit different colors, and after crosslinking, it becomes a thermosetting plastic that cannot be further processed and reused. Therefore, providing a thermoplastic with a soluble and fusible linear polymer structure that simultaneously possesses high refractive index and high transparency is of great significance for the field of novel high-end polyolefin technology. Summary of the Invention

[0006] Based on the above, this invention provides a cyclic olefin copolymer, its preparation method, and its application in optical materials. The cyclic olefin copolymer of this invention has a soluble and fusible linear polymer structure, while also possessing high refractive index, transparency, good heat resistance, and low moisture absorption.

[0007] To achieve the above objectives, the present invention provides the following solution:

[0008] One of the technical solutions of the present invention is a cyclic olefin copolymer having the structure shown in Formula I:

[0009]

[0010] In Formula I, x and y are the degree of polymerization, 50≤x≤850, 0≤y≤750, but do not represent block copolymers; the dashed line indicates bonding or non-bonding; i and j are the number of rings, i is 0 or 1, j is 0 or 1; m and n are the number of carbon atoms, 0≤m≤10, 0≤n≤4;

[0011] In Formula I, R1 is selected from one of the following S1-S5:

[0012]

[0013] In Formula I, R2 and R3 are each independently selected from one of hydrogen atoms, alkyl groups and alkenyl groups, and R2 and R3 may or may not be bonded to each other.

[0014] The second technical solution of the present invention is a method for preparing the aforementioned cyclic olefin copolymer, comprising the following steps:

[0015] In the presence of a catalyst, the monomer undergoes a ring-opening metathesis polymerization reaction under a protective atmosphere to obtain the polymerization product.

[0016] The polymerization product is subjected to hydrogenation to obtain the cyclic olefin copolymer;

[0017] The monomer includes at least one compound of formula II and at least one compound of formula III;

[0018] The structure of the compound shown in Formula II is as follows:

[0019]

[0020] In Formula II, i is the number of rings, i is 0 or 1; m is the number of carbon atoms, 0≤m≤10;

[0021] In Formula II, R1 is the same as the R1 mentioned above, and is selected from one of the following S1-S5.

[0022]

[0023] The structure of the compound shown in Formula III is as follows:

[0024]

[0025] 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; R2 and R3 are each independently selected from one of hydrogen atoms, alkyl groups, and alkenyl groups, and R2 and R3 may or may not be bonded to each other.

[0026] In a preferred embodiment of the present invention, the compound represented by Formula II is selected from at least one of the HM1-HM10 structures:

[0027]

[0028] Where m is the number of carbon atoms, 0≤m≤10.

[0029] 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:

[0030]

[0031] The present invention does not impose any special restrictions on the source of cyclic olefin monomers with structures as shown in Formula II and Formula III, and they can be obtained using preparation techniques well known to those skilled in the art.

[0032] The compound shown in Formula II of this invention, after ring-opening and metathesis, can be further hydrogenated to yield a cyclic olefin polymer. The polymer is reproducible through repeated dissolution and processing, and is colorless and transparent.

[0033] 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.

[0034] 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.

[0035] In this invention, the ruthenium catalyst is preferably one of the structures shown in Formula IV:

[0036]

[0037] In Formula IV, PCy3 is tricyclohexylphosphine, and Mes is 2,4,6-trimethylphenyl.

[0038] 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 special restrictions on the source of the catalyst having the structure shown in Formula IV; it can be purchased commercially.

[0039] In this invention, the ruthenium catalyst is dissolved in a solvent before catalyzing the ring-opening metathesis polymerization of the monomer compound. The solvent is consistent with the solvent mentioned above (the solvent used to dissolve the cycloolefin monomer), specifically a hydrocarbon compound, a halogenated hydrocarbon compound, a cyclohydrocarbon 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 mentioned above well known to those skilled in the art can be used and can be purchased commercially.

[0040] In a preferred embodiment of the present invention, the molar ratio of the monomer to the catalyst is (100-1600):1, preferably (200-1000):1, and more preferably (200-800):1.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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. In the preparation of 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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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℃.

[0049] 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.

[0050] The third technical solution of the present invention is an optical material, the raw material of which includes the aforementioned cyclic olefin copolymer.

[0051] The present invention discloses the following technical effects:

[0052] This invention provides a random or gradient copolymer of cyclic olefins with excellent properties, including high refractive index, transparency, good 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 the cyclic olefin copolymer of this invention has a refractive index range of 1.62–1.66 and an Abbe number range of 22–25, demonstrating excellent optical properties; its glass transition temperature is 130℃–175℃, exhibiting good thermal stability; its light transmittance is greater than 90%, and its water absorption rate is less than 0.01%, indicating low hygroscopicity. With these excellent properties, this cyclic olefin copolymer has broad application prospects in high-refractive-index optical components, optical coatings, and high-end optical equipment.

[0053] The cyclic olefin copolymer of the present invention has a soluble and fusible linear polymer structure, which can be used in different processing methods such as injection molding, extrusion, blow molding, coating, and doping to process the material into optical lenses, optical films and other products to meet the needs of different application fields, and can be repeatedly processed and reused.

[0054] This patent eliminates unsaturated double bonds through hydrogenation, avoiding residual sulfur molecules in the cross-linked network and UV-induced yellowing. The material exhibits colorless and transparent optical properties and better stability. Simultaneously, the elimination of unsaturated double bonds through hydrogenation significantly improves the polymer's thermal stability and weather resistance. Attached Figure Description

[0055] 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.

[0056] Figure 1 NMR spectra of the cycloolefin monomers obtained in Example 1 of this invention 1 H-NMR spectrum;

[0057] Figure 2 NMR spectra of the cycloolefin monomers obtained in Example 1 of this invention 13 C-NMR spectrum;

[0058] Figure 3 NMR of the cyclic olefin copolymer obtained in Example 6 of this invention 1 H-NMR spectrum;

[0059] Figure 4 NMR of the cyclic olefin copolymer obtained in Example 6 of this invention 13 C-NMR spectrum;

[0060] Figure 5 The refractive index curve of the cyclic olefin copolymer obtained in Example 6 of the present invention;

[0061] Figure 6 The differential scanning calorimetry curve of the cyclic olefin copolymer obtained in Example 8 of the present invention;

[0062] Figure 7 The transmittance curve of the cyclic olefin copolymer obtained in Example 10 of the present invention is shown. Detailed Implementation

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] 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.

[0068] The present invention uses the following method to determine the cyclic olefin copolymers prepared:

[0069] Conversion rate: The polymerization conversion rate of the polymerization reaction is tested by weighing the product in this invention.

[0070] 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.

[0071] 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.

[0072] 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.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] Unless otherwise specified, the technical solutions described in this invention are all conventional solutions in the field, and the reagents or raw materials used, unless otherwise specified, can be prepared by methods well known to those skilled in the art or purchased from the market.

[0077] 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.

[0078] Example 1

[0079] Synthesis of the cyclic olefin monomer HM7 (with 1 carbon atom in the side chain)

[0080]

[0081] Under a nitrogen atmosphere, 63 g (0.35 mol) of 4H-dithienro[3,2-b:2',3'-d]pyrrole and 15 g (0.62 mol) of sodium hydride were mixed and stirred in anhydrous DMF for 2 h. 5-(iodomethyl)bicyclo[2.2.1]hept-2-ene (122 g (0.52 mol)) was added dropwise, and the reaction was carried out at 120 °C for 24 h. The mixture was extracted 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 67g of white solid (yield 67%).

[0082] Example 2

[0083] Synthesis of the cycloolefin monomer HM7 (with 4 carbon atoms in the side chain)

[0084]

[0085] Under a nitrogen atmosphere, 63 g (0.35 mol) of 4H-dithienro[3,2-b:2',3'-d]pyrrole and 15 g (0.62 mol) of sodium hydride were mixed and stirred in anhydrous DMF for 2 h. Then, 119 g (0.52 mol) of 5-(4-bromobutyl)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 =0~1:20, vacuum dried at 60℃ for 10 hours, to obtain 92g of white solid (yield 80%).

[0086] Example 3

[0087] Synthesis of the cycloolefin monomer HM8 (with 1 carbon atom in the side chain)

[0088]

[0089] Under a nitrogen atmosphere, 4H-dithieno[3,2-b:2',3'-d]pyrrole (63 g, 0.35 mol) and sodium hydride (15 g, 0.62 mol) were mixed and stirred in anhydrous DMF for 2 h. Then, 2-(iodomethyl)-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylnaphthalene (156 g, 0.52 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 =0~1:10, vacuum dried at 60℃ for 10 hours, yielding 86g of white solid (yield 70%).

[0090] Example 4

[0091] Synthesis of the cyclic olefin monomer HM4 (with 2 carbon atoms in the side chain)

[0092]

[0093] Under a nitrogen atmosphere, 7H-dithieno[2,3-b:3',2'-d] (63 g, 0.35 mol) and sodium hydride (15 g, 0.62 mol) were mixed and stirred in anhydrous DMF for 2 h. Then, 2-(2-iodoethyl)-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylnaphthalene (163 g, 0.52 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 =0~1:10, vacuum dried at 60℃ for 10 hours, to obtain 91g of white solid (yield 72%).

[0094] Example 5

[0095] Synthesis of the cyclic olefin monomer HM3 (with 6 carbon atoms in the side chain)

[0096]

[0097] Under a nitrogen atmosphere, 7H-dithienro[2,3-b:3',2'-d] (63 g, 0.35 mol) and sodium hydride (15 g, 0.62 mol) were mixed and stirred in anhydrous DMF for 2 h. Then, 5-(6-bromohexyl)bicyclo[2.2.1]hept-2-ene (134 g, 0.52 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 =0~1:4, vacuum dried at 60℃ for 10 hours, to obtain 100g of white solid (yield 80%).

[0098] Example 6

[0099] The structural formula of the cyclic olefin copolymer is:

[0100]

[0101] Where the degree of polymerization x = 900 and y = 100, the synthesis steps are as follows:

[0102] At room temperature, 28.21 g (0.099 mol) of monomer HM7 prepared in Example 1 and 1.76 g (0.011 mol) of monomer M3 were added to a dry polymerization flask. Then, 500 mL of dry, degassed dichloromethane solvent was added, and the mixture was magnetically stirred for 5 min to obtain a homogeneous solution. Subsequently, 0.094 g (0.110 mmol) of catalyst (G2) was dissolved in 20 mL of dichloromethane 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, washed, and the collected product was dried under vacuum at 40 °C for 16 hours to obtain the polymerization product.

[0103] 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 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.

[0104] 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 resulting cyclic olefin copolymer has a refractive index of 1.66, an Abbe number of 22, a glass transition temperature of 132°C, a water absorption rate of less than 0.01%, and a visible light transmittance greater than 90%.

[0105] Example 7

[0106] The structural formula of the cyclic olefin copolymer is:

[0107]

[0108] Where the degree of polymerization x = 400 and y = 200, the synthesis steps are as follows:

[0109] At room temperature, 17.01 g (0.052 mol) of monomer HM7 prepared in Example 2 and 5.20 g (0.026 mol) of monomer M5 were added to a dry polymerization flask. Then, 500 mL of dry, degassed dichloromethane solvent was added, and the mixture was magnetically stirred for 5 min to obtain a homogeneous solution. Subsequently, 0.110 g (0.130 mmol) of catalyst (G2) was dissolved in 20 mL of dichloromethane 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, washed, and the collected product was dried under vacuum at 40 °C for 16 hours to obtain the polymerization product.

[0110] 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 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.

[0111] 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 resulting cyclic olefin copolymer has a refractive index of 1.63, an Abbe number of 25, a glass transition temperature of 138°C, a water absorption rate of less than 0.01%, and a visible light transmittance greater than 90%.

[0112] Example 8

[0113] The structural formula of the cyclic olefin copolymer is:

[0114]

[0115] Where the degree of polymerization x = 500 and y = 100, the synthesis steps are as follows:

[0116] At room temperature, 19.31 g (0.055 mol) of monomer HM8 prepared in Example 3 and 0.75 g (0.011 mol) of monomer M7 were added to a dry polymerization flask. Then, 500 mL of dry, degassed dichloromethane solvent was added, and the mixture was magnetically stirred for 5 min to obtain a homogeneous solution. Subsequently, 0.097 g (0.110 mmol) of catalyst (G3) was dissolved in 20 mL of dichloromethane 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, washed, and the collected product was dried under vacuum at 40 °C for 16 hours to obtain the polymerization product.

[0117] The polymerization product was added to a round-bottom flask equipped with a condenser along with 61.38 g of p-toluenesulfonyl hydrazine and 51.91 g of tri-n-propylamine. 0.029 g of 2,6-di-tert-butyl-4-methylphenol 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.

[0118] 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 resulting cyclic olefin copolymer has a refractive index of 1.63, an Abbe number of 24, a glass transition temperature of 173°C, a water absorption rate of less than 0.01%, and a visible light transmittance greater than 90%.

[0119] Example 9

[0120] The structural formula of the cyclic olefin copolymer is:

[0121]

[0122] Where the degree of polymerization x = 480 and y = 80, the synthesis steps are as follows:

[0123] At room temperature, 26.28 g (0.072 mol) of monomer HM4 prepared in Example 4 and 1.61 g (0.012 mol) of monomer M2 were added to a dry polymerization flask. Then, 500 mL of dry, degassed dichloromethane 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 dichloromethane 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, washed, and the collected product was dried under vacuum at 40 °C for 16 hours to obtain the polymerization product.

[0124] The polymerization product was added to a round-bottom flask equipped with a condenser along with 61.38 g of p-toluenesulfonyl hydrazine and 51.91 g of tri-n-propylamine. 0.029 g of 2,6-di-tert-butyl-4-methylphenol 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.

[0125] 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 resulting cyclic olefin copolymer has a refractive index of 1.62, an Abbe number of 25, a glass transition temperature of 175°C, a water absorption rate of less than 0.01%, and a visible light transmittance greater than 90%.

[0126] Example 10

[0127] The structural formula of the cyclic olefin copolymer is:

[0128]

[0129] Where the degree of polymerization x = 400 and y = 100, the synthesis steps are as follows:

[0130] At room temperature, 21.06 g (0.060 mol) of monomer HM8 prepared in Example 3 and 1.65 g (0.015 mol) of monomer M10 were added to a dry polymerization flask. Then, 500 mL of dry, degassed dichloromethane 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 dichloromethane 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, washed, and the collected product was dried under vacuum at 40 °C for 16 hours to obtain the polymerization product.

[0131] The polymerization product was added to a round-bottom flask equipped with a condenser along with 68.82 g of p-toluenesulfonyl hydrazine and 58.20 g of tri-n-propylamine. 0.029 g of 2,6-di-tert-butyl-4-methylphenol 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.

[0132] 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 resulting cyclic olefin copolymer has a refractive index of 1.62, an Abbe number of 25, a glass transition temperature of 170°C, a water absorption rate of less than 0.01%, and a visible light transmittance greater than 90%.

[0133] Example 11

[0134] The structural formula of the cyclic olefin copolymer is:

[0135]

[0136] Where the degree of polymerization x1 = 100 and x2 = 500, the synthesis steps are as follows:

[0137] At room temperature, 6.04 g (0.017 mol) of monomer HM3 prepared in Example 5 and 29.84 g (0.085 mol) of monomer HM8 prepared in Example 3 were added to a dry polymerization flask. Then, 500 mL of dry, degassed dichloromethane solvent was added, and the mixture was magnetically stirred for 5 min to obtain a homogeneous solution. Subsequently, 0.150 g (0.170 mmol) of catalyst (G3) was dissolved in 20 mL of dichloromethane 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, washed, and the collected product was dried under vacuum at 40 °C for 16 hours to obtain the polymerization product.

[0138] The polymerization product was added to a round-bottom flask equipped with a condenser along with 93.04 g of p-toluenesulfonyl hydrazine and 79.44 g of tri-n-propylamine. 0.022 g of 2,6-di-tert-butyl-4-methylphenol 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.

[0139] 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 resulting cyclic olefin copolymer has a refractive index of 1.65, an Abbe number of 23, a glass transition temperature of 165°C, a water absorption rate of less than 0.01%, and a visible light transmittance greater than 90%.

[0140] Example 12

[0141] The structural formula of the cyclic olefin copolymer is:

[0142]

[0143] Where the degree of polymerization x1 = 150, x2 = 300, and y = 75, the synthesis steps are as follows:

[0144] At room temperature, 7.13 g (0.025 mol) of monomer HM7 prepared in Example 1, 17.55 g (0.050 mol) of monomer HM8 prepared in Example 3, and 0.85 g (0.0125 mol) of monomer M7 were added to a dry polymerization flask. Then, 500 mL of dry, degassed dichloromethane solvent was added, and the mixture was magnetically stirred for 5 min to obtain a homogeneous solution. Subsequently, 0.147 g (0.167 mmol) of catalyst (G3) was dissolved in 20 mL of dichloromethane 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, washed, and the collected product was dried under vacuum at 40 °C for 16 hours to obtain the polymerization product.

[0145] The autoclave was pre-dried under vacuum for 5 hours. The polymerization product prepared above, 500 mL of chlorobenzene, and 12 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 filtered and dried in a vacuum oven at 60°C for 18 hours to obtain the cyclic olefin copolymer.

[0146] 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 resulting cyclic olefin copolymer has a refractive index of 1.65, an Abbe number of 23, a glass transition temperature of 162°C, a water absorption rate of less than 0.01%, and a visible light transmittance greater than 90%.

[0147] Example 13

[0148] The structural formula of the cyclic olefin copolymer is:

[0149]

[0150] Where the degree of polymerization x = 300, y1 = 75, y2 = 75, the synthesis steps are as follows:

[0151] At room temperature, 22.80 g (0.080 mol) of monomer HM7 prepared in Example 1, 4.01 g (0.020 mol) of monomer M5, and 1.36 g (0.020 mol) of monomer M7 were added to a dry polymerization flask. Then, 500 mL of dry, degassed dichloromethane solvent was added, and the mixture was magnetically stirred for 5 min to obtain a homogeneous solution. Subsequently, 0.236 g (0.267 mmol) of catalyst (G3) was dissolved in 20 mL of dichloromethane 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, washed, and the collected product was dried under vacuum at 40 °C for 16 hours to obtain the polymerization product.

[0152] 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 filtered and dried in a vacuum oven at 60 °C for 18 hours to obtain the cyclic olefin copolymer.

[0153] 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 resulting cyclic olefin copolymer has a refractive index of 1.63, an Abbe number of 24, a glass transition temperature of 130°C, a water absorption rate of less than 0.01%, and a visible light transmittance greater than 90%.

[0154] 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.

[0155] Figure 3 and Figure 4 NMR of the cyclic olefin copolymer obtained in Example 6 of this invention 1 H-NMR spectrum and 13 C-NMR spectrum; by Figure 3 and Figure 4It 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.

[0156] The products prepared in Examples 2-5 and 7-13 were subjected to NMR. 1 H-NMR spectrum and 13 C-NMR spectral analysis showed that all target products were successfully prepared.

[0157] Figure 5 The refractive index curve of the cyclic olefin copolymer obtained in Example 6 of this invention is shown. Figure 5 It can be seen that the cyclic olefin copolymer prepared in Example 6 has a high refractive index of up to 1.66 in the visible light range.

[0158] Figure 6 The differential scanning calorimetry (DSC) curve of the cyclic olefin copolymer obtained in Example 8 of this invention is shown below. Figure 6 It can be seen that the cyclic olefin copolymer prepared in Example 8 has a glass transition temperature as high as 173°C and exhibits high thermal stability.

[0159] Figure 7 The transmittance curve of the cyclic olefin copolymer obtained in Example 10 of this invention is shown below; Figure 7 It can be seen that the cyclic olefin copolymer prepared in Example 10 has a visible light transmittance of more than 90% and has high transparency.

[0160] 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 represent the degree of polymerization, 50≤x≤850, 0<y≤750, but do not necessarily indicate block copolymers; the dashed line indicates 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. In Formula I, R1 is selected from one of the following S1-S5: ； In Formula I, R2 and R3 are each independently selected from one of hydrogen atoms, alkyl groups and alkenyl groups, and R2 and R3 may or may not be bonded to each other.

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 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; In Formula II, R1 is the same as R1 in claim 1; 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; R2 and R3 are each independently selected from one of hydrogen atoms, alkyl groups and alkenyl groups, wherein R2 and R3 may or may not form a bond.

3. The method for preparing the 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-HM10 structures: ； Where m is the number of carbon atoms, 0≤m≤10.

4. The method for preparing the cyclic olefin copolymer according to claim 2, characterized in that, 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 (100~1600):

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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