Cycloolefin copolymer, preparation method thereof, optical product and electronic equipment

Abstract

The embodiment of the invention provides a cycloolefin copolymer, a preparation method thereof, an optical product and electronic equipment. Wherein the chemical formula of the cycloolefin copolymer is # imgabs0 #, x is the monomer number of a nitrogen-containing heterocyclic ring polymeric monomer, y is the monomer number of norbornene, n is 3 or 4, and R is a nitrogen-containing heterocyclic ring group and comprises at least one of pyridyl, quinolyl and acridinyl. According to the preparation method of the cycloolefin copolymer in the embodiment of the invention, the cycloolefin copolymer with high refractive index can be provided.

Description

Technical Field

[0001] The embodiments of the present application relate to the technical field of cyclic olefin copolymers. Specifically, the embodiments of the present application relate to a cyclic olefin copolymer, a method for preparing a cyclic olefin copolymer, an optical product, and an electronic device. Background Art

[0002] High refractive index materials have important application prospects in the fields of optical lenses, optical fibers, display technology and sensors. Traditional polymer materials such as polycarbonate (PC) and polymethyl methacrylate (PMMA) often have defects such as high water absorption and high stress, and cannot meet the special requirements of some high-end optical devices (such as optical lenses and optical waveguides) for high refractive index materials.

[0003] Cyclic olefin copolymer (COC) is a thermoplastic with excellent properties such as high transparency, excellent heat resistance, outstanding chemical resistance, low density and minimized dispersion. However, the refractive index of existing cyclic olefin copolymers is generally not high, resulting in a mismatch between their refractive index and other optical materials, which in turn limits the application of the cyclic olefin copolymers in the optical field.

[0004] Therefore, it is necessary to provide a new technical solution to solve the above technical problems. Summary of the invention

[0005] The purpose of the present application is to provide a new technical solution for a cycloolefin copolymer and a preparation method thereof, optical products and electronic devices.

[0006] In a first aspect, the present invention provides a cycloolefin copolymer, wherein the chemical formula of the cycloolefin copolymer is:

[0007]

[0008] Wherein, x is the number of monomers of the nitrogen-containing heterocyclic polymerization monomer, y is the number of monomers of norbornene, n is 3 or 4, and R is a nitrogen-containing heterocyclic group, including at least one of a pyridyl group, a quinolyl group and an acridinyl group.

[0009] Optionally, the raw materials for preparing the cycloolefin copolymer include at least a nitrogen-containing heterocyclic polymer monomer and norbornene, and the nitrogen-containing heterocyclic polymer monomer and the norbornene are polymerized in a first solvent.

[0010] Optionally, the first solvent includes at least one of acetonitrile, toluene, ethyl acetate, distilled water, hydrochloric acid and ethanol.

[0011] Optionally, the raw materials for preparing the nitrogen-containing heterocyclic polymer monomer include a first monomer and a second monomer, and the first monomer and the second monomer are polymerized in a second solvent;

[0012] The first monomer includes at least one of pyridine, quinoline and acridine;

[0013] The second monomer includes at least one of 4-bromo-1-butene, 4-bromo-1-pentene, 5-bromo-1-butene and 5-bromo-1-pentene;

[0014] The second solvent includes acetonitrile or ethyl acetate.

[0015] Optionally, the nitrogen-containing heterocyclic polymer monomer and the norbornene are polymerized under the catalytic action of a catalyst;

[0016] The catalyst comprises a main catalyst and a co-catalyst;

[0017] The main catalyst includes a metallocene catalyst;

[0018] The co-catalyst includes at least one of [Ph3C][B(C6F5)4], methylaluminoxane (MAO) and alkylaluminum, wherein the alkylaluminum includes at least one of triethylaluminum, triisobutylaluminum and trioctylaluminum.

[0019] Optionally, the mass ratio of the main catalyst to the co-catalyst is 1:(100-2000).

[0020] Optionally, the cyclic olefin copolymer has a molecular weight of 50,000 to 180,000.

[0021] Optionally, the cycloolefin copolymer has a refractive index greater than 1.56 and a glass transition temperature greater than 145°C.

[0022] Optionally, when the first monomer is pyridine and the second monomer is 4-bromo-1-butene, the chemical formula of the cycloolefin copolymer is:

[0023]

[0024] Optionally, when the first monomer is quinoline and the second monomer is 4-bromo-1-butene, the chemical formula of the cycloolefin copolymer is:

[0025]

[0026] Optionally, when the first monomer is acridine and the second monomer is 4-bromo-1-pentene, the chemical formula of the cycloolefin copolymer is:

[0027]

[0028] Optionally, when the first monomer is pyridine and the second monomer is 5-bromo-1-butene, the chemical formula of the cycloolefin copolymer is:

[0029]

[0030] Optionally, when the first monomer is quinoline and the second monomer is 5-bromo-1-butene, the chemical formula of the cycloolefin copolymer is:

[0031]

[0032] Optionally, when the first monomer is acridine and the second monomer is 5-bromo-1-pentene, the chemical formula of the cycloolefin copolymer is:

[0033]

[0034] In a second aspect, an embodiment of the present application provides a method for preparing a cycloolefin copolymer, which is used to prepare the cycloolefin copolymer as described in the first aspect, and the preparation method comprises:

[0035] mixing a nitrogen-containing heterocyclic polymerizable monomer, norbornene, and a first solvent;

[0036] A catalyst is added, and a polymerization reaction is carried out at a set temperature and a set pressure; wherein the set temperature is 50° C. to 150° C., the set pressure is 0.1 MPa to 2 MPa, and the polymerization reaction time is 4 h to 24 h.

[0037] In a third aspect, an embodiment of the present application provides an optical product, wherein the optical product is prepared from the cycloolefin copolymer according to the first aspect.

[0038] In a fourth aspect, an embodiment of the present application provides an electronic device, wherein the electronic device includes the optical product described in the third aspect.

[0039] One beneficial effect of this application is:

[0040] According to a cyclic olefin copolymer provided in one embodiment of the present application, the chemical formula of the cyclic olefin copolymer is:

[0041]

[0042] Wherein, x is the number of nitrogen-containing heterocyclic polymerization monomers, y is the number of norbornene monomers, n is 3 or 4, and R is a nitrogen-containing heterocyclic group, including pyridine, quinoline and acridine. By introducing high molar refractive index groups such as pyridine, quinoline and acridine, high refractive index optical materials are prepared, which effectively expands the application range of the cycloolefin copolymer and provides new ideas for the development of high refractive index cycloolefin copolymers.

[0043] Other features and advantages of the present specification will become apparent from the following detailed description with reference to exemplary embodiments of the present specification. DETAILED DESCRIPTION

[0044] Various exemplary embodiments of the present application are now described in detail. It should be noted that the relative arrangement of components and steps, numerical expressions and numerical values ​​set forth in these embodiments do not limit the scope of the present application unless otherwise specifically stated.

[0045] The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the present application, its application, or uses.

[0046] Techniques and equipment known to ordinary technicians in the relevant art may not be discussed in detail, but where appropriate, the techniques and equipment should be considered part of the specification.

[0047] In all examples shown and discussed herein, any specific values ​​should be interpreted as merely exemplary and not limiting. Therefore, other examples of the exemplary embodiments may have different values.

[0048] The cyclic olefin copolymer and its preparation method, cyclic olefin copolymer, optical product and electronic device provided in the embodiments of the present application are described in detail below in conjunction with specific embodiments.

[0049] According to one embodiment of the present application, a cyclic olefin copolymer is provided, and the chemical formula of the cyclic olefin copolymer is:

[0050]

[0051] Wherein, x is the number of monomers of the nitrogen-containing heterocyclic polymerization monomer, y is the number of monomers of norbornene, n is 3 or 4, and R is a nitrogen-containing heterocyclic group, which includes at least one of a pyridyl group, a quinolyl group and an acridinyl group.

[0052] Specifically, in the chemical formula of the cycloolefin copolymer of the embodiment of the present application, x represents the number of nitrogen-containing heterocyclic polymerization monomers in the cycloolefin copolymer, y represents the number of norbornene monomers in the cycloolefin copolymer, n represents the number of carbon chains in the cycloolefin copolymer, R represents a nitrogen-containing heterocyclic group, and the nitrogen-containing heterocyclic group includes at least one of a pyridyl group, a quinolyl group and an acridinium group.

[0053] According to one embodiment of the application, the performance of the cycloolefin copolymer is significantly affected by the number of carbon chains (i.e. the value of n) in the monomer molecular structure. In order to optimize the performance of the cycloolefin copolymer and to be convenient to introduce the nitrogen-containing heterocyclic group, the number n of carbon chains set in the application is 3 or 4. The value of n can affect the volume of the monomer molecular structure and the crystallinity of the cycloolefin copolymer, and then affect its overall performance. The value of n in the application can promote the introduction of the nitrogen-containing heterocyclic group while maintaining the performance of the cycloolefin copolymer, thereby optimizing its overall structure and function.

[0054] In addition, R represents a nitrogen-containing heterocyclic group, which includes but is not limited to a pyridyl group, a quinolyl group and an acridinyl group, and their introduction can impart specific functions and properties to the cyclic olefin copolymer.

[0055] Furthermore, the cycloolefin copolymer of the embodiment of the present application introduces the nitrogen-containing heterocyclic group (including at least one of a pyridyl group, a quinolyl group and an acridinium group) into the chain segment of the cycloolefin copolymer, so that the refractive index of the cycloolefin copolymer can be better adapted to other optical materials, thereby effectively expanding the application scope of the cycloolefin copolymer.

[0056] In some examples of the present application, the raw materials for preparing the cycloolefin copolymer include at least a nitrogen-containing heterocyclic polymerization monomer and norbornene, and the nitrogen-containing heterocyclic polymerization monomer and the norbornene are polymerized in a first solvent.

[0057] In the examples of the present application, the raw materials for preparing the cycloolefin copolymer include at least a nitrogen-containing heterocyclic polymerization monomer and norbornene, and these raw materials are polymerized in a first solvent.

[0058] Nitrogen-containing heterocyclic polymer monomers in this example of the present application: These monomers can significantly increase the refractive index of cycloolefin copolymers by introducing nitrogen-containing heterocyclic groups, such as pyridyl, quinolyl, acridinium, etc. High refractive index materials have important applications in the fields of optical lenses, optical fibers, display technology, and sensors, as they can allow for more compact designs while maintaining good optical properties.

[0059] Norbornene in this example of the present application has a simple structure and a small molecular volume, which can effectively increase the insertion rate of norbornene in the cycloolefin copolymer. A high insertion rate helps to maintain the amorphous stability of the copolymer, which is crucial for the transparency and mechanical properties of optical materials.

[0060] In this example of the present application, the selection of the first solvent has an important influence on the efficiency of the polymerization reaction and the performance of the product. Specifically, the first solvent used in the present application may include, for example, acetonitrile, toluene, etc. These solvents can effectively dissolve the raw materials, promote the polymerization reaction, and help control the molecular weight and structure of the product.

[0061] Combined with the above raw material selection and polymerization conditions, the technical effects of this application are mainly reflected in the following aspects:

[0062] (1) Improve the refractive index: By introducing nitrogen-containing heterocyclic groups, the refractive index of cycloolefin copolymers is significantly improved, which can meet the special needs of high-end optical equipment for high-refractive index materials.

[0063] (2) Improved optical properties: The high insertion rate of norbornene helps maintain the amorphous stability of cycloolefin copolymers, thereby improving their transparency and optical properties. In addition, by adjusting the ratio of nitrogen-containing heterocyclic monomers and norbornene, the key optical indicators of cycloolefin copolymers, such as refractive index and Abbe number, can be further optimized.

[0064] (3) Enhanced thermal stability: The combination of nitrogen-containing heterocyclic groups and norbornene helps to improve the thermal stability of cycloolefin copolymers, enabling them to maintain good performance in high temperature environments.

[0065] (4) Broaden the scope of application: Since copolymers have excellent optical properties and thermal stability, they can be widely used in optical lenses, optical fibers, display technology, sensors and other fields, providing new material options for the development of these fields.

[0066] In the embodiments of the present application, norbornene is used as a key comonomer, and its sources are diversified. It can not only be used directly, but also be synthesized through a variety of norbornene derivatives.

[0067] For example, norbornene can be efficiently synthesized through the Alder reaction between cyclopentadiene and ethylene, which provides a wider range of raw material options for the preparation of cycloolefin copolymers.

[0068] In addition, in the polymerization process, the first solvent plays a crucial role. The first solvent in the present application should not only be able to effectively dissolve the nitrogen-containing heterocyclic polymerization monomer and norbornene, but also significantly promote the reactivity between the two. By optimizing the solvent system, the nitrogen-containing heterocyclic polymerization monomer and norbornene can better contact each other and polymerize, thereby greatly improving the preparation efficiency of cycloolefin copolymer. The selection of this solvent not only simplifies the preparation process, but also ensures the high quality and consistency of the product, laying the foundation for the large-scale production of cycloolefin copolymer.

[0069] In some examples of the present application, the first solvent includes at least one of acetonitrile, toluene, ethyl acetate, distilled water, hydrochloric acid, and ethanol.

[0070] Among the various first solvents provided in this example of the present application, organic solvents such as acetonitrile, toluene and ethyl acetate are used as reaction media in the polymerization reaction, which can effectively dissolve nitrogen-containing heterocyclic polymerization monomers and norbornene, and promote sufficient contact and reaction between monomers. Compared with the aqueous phase system, the organic solvent system can generally provide higher reaction efficiency and better product quality control.

[0071] The first solvent provided in this example of the present application may also be at least one of distilled water and hydrochloric acid. The addition of hydrochloric acid can be used to adjust the pH value of the reaction, affect the activity of the catalyst or the dissociation state of the monomer, and thus indirectly affect the progress of the polymerization reaction and the properties of the product.

[0072] The first solvent provided in this example of the present application may also be ethanol, which is a polar solvent with good solubility and volatility.

[0073] The present application is more diversified in solvent selection, covering organic solvents and aqueous phase systems. By carefully selecting solvent combinations, the present application aims to optimize polymerization reaction conditions and improve the preparation efficiency and product quality of cycloolefin copolymers.

[0074] In some examples of the present application, the raw materials for preparing the nitrogen-containing heterocyclic polymer monomer include a first monomer and a second monomer, and the first monomer and the second monomer are polymerized in a second solvent; the first monomer includes at least one of pyridine, quinoline and acridine; the second monomer includes at least one of 4-bromo-1-butene, 4-bromo-1-pentene, 5-bromo-1-butene and 5-bromo-1-pentene; the second solvent includes acetonitrile or ethyl acetate.

[0075] In this example of the present application, the raw materials for preparing the nitrogen-containing heterocyclic polymerization monomer include a first monomer and a second monomer, and the two monomers are to be polymerized in a second solvent. Wherein, the first monomer is selected from at least one of pyridine, quinoline and acridine, and these compounds all contain nitrogen heterocyclic structures and can provide the required nitrogen-containing heterocyclic groups. The second monomer is selected from at least one of 4-bromo-1-butene, 4-bromo-1-pentene, 5-bromo-1-butene and 5-bromo-1-pentene, which, as olefin compounds, can undergo polymerization reaction with the first monomer to form the required nitrogen-containing heterocyclic polymerization monomer.

[0076] In addition, it is worth noting that the second solvent mentioned in this example of the present application includes at least one of acetonitrile and ethyl acetate. Moreover, when the first monomer and the second monomer are polymerized in the second solvent, a catalyst needs to be added. The catalyst is, for example, potassium carbonate K2CO3, or sodium carbonate, sodium bicarbonate or potassium bicarbonate, etc., and its mechanism is to neutralize the generated HBr.

[0077] Acetonitrile: It is an organic solvent with good solubility, which can dissolve the first monomer and the second monomer well, providing a uniform reaction environment for the polymerization reaction. In addition, acetonitrile has a moderate boiling point and is easy to remove by distillation and other methods, thereby simplifying the subsequent processing steps.

[0078] In addition to acetonitrile, ethyl acetate, as an organic solvent, also has good dissolving properties.

[0079] Potassium carbonate K2CO3 here not only serves as part of the solvent, but more importantly, it can play a catalytic role. Potassium carbonate K2CO3 can promote the polymerization reaction between the first monomer and the second monomer, and improve the reaction rate and yield. At the same time, K2CO3, as an alkaline compound, helps to neutralize the acidic byproducts that may be produced during the reaction, thereby stabilizing the reaction system.

[0080] Specifically, potassium carbonate K2CO3 reacts with HBr to generate H2CO3, which further decomposes into CO2.

[0081] In the present application, acetonitrile is used as the second solvent and K2CO3 is added as a catalyst, which can effectively control the process of the polymerization reaction so that the generated nitrogen-containing heterocyclic polymerization monomer has the expected structure and performance. In particular, the catalytic effect of K2CO3 helps to form a high molecular weight, high purity polymerization monomer, which lays a good foundation for the preparation of subsequent cycloolefin copolymers. In addition, due to the low volatility of acetonitrile and K2CO3, they are not easy to remain in the polymerization monomer, thereby avoiding the adverse effect on the performance of the subsequent cycloolefin copolymer.

[0082] It should be noted that acetonitrile and K2CO3 are both relatively environmentally friendly compounds. They are easy to decompose or recycle in the natural environment, which is in line with the development trend of green chemistry. Using these two compounds as solvents can help reduce environmental pollution in the production process and improve the sustainability of production.

[0083] In some examples of the present application, the nitrogen-containing heterocyclic polymerization monomer and the norbornene are polymerized under the catalytic action of a catalyst; the catalyst includes a main catalyst and a co-catalyst; the main catalyst includes a metallocene catalyst; the co-catalyst includes at least one of [Ph3C][B(C6F5)4], methylaluminoxane (MAO) and alkyl aluminum, wherein the alkyl aluminum includes at least one of triethyl aluminum, triisobutyl aluminum and trioctyl aluminum.

[0084] In the examples of the present application, the nitrogen-containing heterocyclic polymer monomer and the norbornene are polymerized under the catalytic action of a catalyst, wherein the catalyst system is mainly composed of a main catalyst and a co-catalyst, wherein the main catalyst is a metallocene catalyst, and the co-catalyst includes at least one of [Ph3C][B(C6F5)4], methylaluminoxane (MAO) and alkylaluminum. Furthermore, the alkylaluminum is further subdivided into triethylaluminum, triisobutylaluminum and trioctylaluminum, etc. The selection of this catalyst system has a significant impact on the efficiency of the polymerization reaction, the performance of the product, and the controllability of the entire preparation process.

[0085] The main catalyst in this application is a metallocene catalyst, including the following six types, namely (a) to (f):

[0086]

[0087] In the cycloolefin copolymer provided in the embodiments of the present application, the metallocene catalyst may be selected from at least one of the above six types.

[0088] The catalytic catalyst system in this application has a highly efficient catalytic effect, specifically:

[0089] Metallocene catalysts are used as main catalysts. Metallocene catalysts have high activity and good selectivity for monomer structures. In the preparation of cycloolefin copolymers, metallocene catalysts can effectively promote the copolymerization reaction between nitrogen-containing heterocyclic polymerization monomers and norbornene, and improve the reaction rate and yield.

[0090] The co-catalysts in this application, such as [Ph3C][B(C6F5)4], methylaluminoxane (MAO) and alkylaluminum, can further enhance the activity of the catalytic system by interacting with the main catalyst. They help stabilize the active center of the metallocene catalyst and prevent its deactivation, thereby extending the service life of the catalyst.

[0091] By selecting a suitable catalyst system, the present invention can accurately control the progress of the polymerization reaction, including key parameters such as monomer insertion rate, degree of polymerization, molecular weight distribution, etc. These parameters directly affect the properties of the final cycloolefin copolymer, such as refractive index, glass transition temperature, mechanical strength, etc.

[0092] In particular, the introduction of nitrogen-containing heterocyclic groups significantly improves the optical properties of the cycloolefin copolymer. The synergistic effect of the metallocene catalyst and the cocatalyst can ensure the uniform distribution of the nitrogen-containing heterocyclic groups in the cycloolefin copolymer segments, thereby optimizing the optical properties of the product.

[0093] Compared with traditional catalyst systems, the combination of metallocene catalysts and selected cocatalysts can generally carry out efficient polymerization reactions under milder reaction conditions. This helps to reduce energy consumption, reduce the formation of by-products, and improve product purity.

[0094] In general, the catalyst system in this example of the present application is more diverse in the selection of co-catalysts, for example, the present application covers compounds such as [Ph3C][B(C6F5)4], MAO and various alkyl aluminums. The innovation and pertinence of the present application in the selection of the catalyst system aims to improve the efficiency of the polymerization reaction and the performance of the product by optimizing the catalyst system.

[0095] In some examples of the present application, the mass ratio of the main catalyst to the co-catalyst is 1:(100-2000).

[0096] Among them, the mass ratio of the main catalyst to the co-catalyst is 1:(100-2000). The selection of this ratio range has important technical effects on the efficiency of the catalytic reaction, the performance of the product and the utilization rate of the catalyst.

[0097] When the ratio of the main catalyst to the co-catalyst is within the range of 1:(100-2000), the co-catalyst can effectively activate the main catalyst to achieve an optimal catalytic activity state, which helps to increase the rate of the polymerization reaction and shorten the reaction time.

[0098] Within this ratio range in this example of the present application, the entire catalyst can more effectively control the polymerization process, thereby obtaining a cycloolefin copolymer with specific performance requirements. For example, by adjusting the catalyst ratio, key performance parameters such as the refractive index, glass transition temperature, and molecular weight distribution of the product can be optimized.

[0099] A reasonable catalyst ratio helps to improve the utilization rate of the catalyst and reduce the waste of the catalyst. When the ratio of the main catalyst to the co-catalyst is too high or too low, it may cause the activity of the entire catalyst to decrease or become inactivated, thereby affecting the catalytic effect. Within the ratio range in the example of this application, it is possible to ensure that the activity of the catalyst is fully exerted while reducing unnecessary catalyst usage.

[0100] By adjusting the ratio of the main catalyst to the co-catalyst in the catalyst, more precise control of the polymerization process can be achieved. This helps to deal with the effects of different monomer combinations, changes in reaction conditions and other factors on the reaction process, ensure that the reaction proceeds as expected, and improve the stability and consistency of the product.

[0101] The catalyst in this example of the present application can shorten the reaction time and improve the performance of the product, thereby helping to improve production efficiency and product quality and further reduce costs.

[0102] By optimizing the catalyst ratio, the catalytic system in the example of the present application can further improve the performance of the product and the utilization rate of the catalyst while ensuring efficient catalysis.

[0103] In this example of the present application, the mass ratio of the main catalyst to the co-catalyst is set within the range of 1:(10-2000) in order to find a balance point so that the activity and selectivity of the formed catalyst system reach the optimal state. For example, when the amount of the co-catalyst is too small, the metallocene catalyst may not be fully activated, resulting in a slower reaction rate. When the amount of the co-catalyst is too much, although the reaction rate can be increased, it may induce too many side reactions, reducing the selectivity and purity of the product.

[0104] In the examples of the present application, by adjusting the ratio range between the main catalyst and the co-catalyst, fine control of the cycloolefin copolymerization process can be achieved. In addition, a suitable ratio of the main catalyst to the co-catalyst also helps to improve the stability of the catalyst system, reduce its deactivation and decomposition during the reaction, thereby extending the life of the catalyst system and reducing production costs.

[0105] In some examples of the present application, the molecular weight of the cyclic olefin copolymer is 50,000 to 180,000.

[0106] In this example of the present application, it is mentioned that the molecular weight of the cycloolefin copolymer ranges from 50,000 to 180,000, which has a significant technical effect on the performance, processability and application areas of the material.

[0107] Within the molecular weight range of this example of the present application, the cycloolefin copolymer can maintain sufficient mechanical strength to meet the needs of various application scenarios.

[0108] Too low a molecular weight may result in increased brittleness, while too high a molecular weight may make the material too soft and unsuitable for certain applications.

[0109] Within the molecular weight range of this example of the present application, the cycloolefin copolymer has an appropriate molecular weight, which helps to improve the thermal stability of the material so that it can still maintain good performance in a high temperature environment. This is particularly important for applications such as optical devices and electronic components that need to work at high temperatures.

[0110] Within the molecular weight range of this example of the present application, the cycloolefin copolymer can exhibit a higher refractive index, which is crucial for the manufacture of optical devices. High refractive index materials can make optical devices thinner and lighter while maintaining excellent optical properties. In addition, the appropriate molecular weight helps to maintain the high transparency of the material, reduce scattering and absorption, and improve the imaging quality of optical devices.

[0111] Within the molecular weight range of this example of the present application, the cycloolefin copolymer has good melt fluidity, which is beneficial to the material's processing processes such as injection molding and extrusion. This can not only improve production efficiency, but also reduce processing costs. In addition, this molecular weight range makes it difficult for the material to produce defects such as bubbles and cracks during the molding process, thereby improving the yield and quality of the product.

[0112] The molecular weight range in the examples of this application is relatively large, with the upper limit reaching 180,000, which makes the cycloolefin copolymers of the examples of this application likely to exhibit superior performance in certain specific application fields, such as higher mechanical strength, better processability, etc.

[0113] In some examples of the present application, the refractive index of the cyclic olefin copolymer is greater than 1.56, and the glass transition temperature thereof is greater than 145°C.

[0114] Specifically, under the condition that the wavelength of the incident light is 589nm, the refractive index of the cycloolefin copolymer is greater than 1.56, which can make the optical device prepared from the cycloolefin copolymer thinner, and thus better meet the needs of miniaturization, micro-micronization and ultra-thinness of optical devices.

[0115] In the examples of the present application, the refractive index of the cycloolefin copolymer is greater than 1.56, and its glass transition temperature (Tg) is greater than 145°C. The improvement of these two performance indicators brings significant technical effects, which are mainly reflected in the following aspects:

[0116] (1) Improvement of optical performance:

[0117] The refractive index is greater than 1.56, which means that the cyclic olefin copolymer has a higher optical density, which enables more refraction of light inside the material. This property is particularly important when manufacturing optical devices, because it allows better optical effects to be achieved while keeping the device thin.

[0118] For example, when manufacturing optical components such as lenses and prisms, high refractive index materials can reduce the thickness of the components, thereby reducing weight, reducing costs, and improving imaging quality.

[0119] (2) Enhanced thermal stability:

[0120] The glass transition temperature is greater than 145°C, which indicates that the cyclic olefin copolymer has excellent thermal stability. This means that at higher temperatures, the material can still maintain its glassy physical properties and is not prone to deformation or flow. This property is particularly important for optical devices or electronic components that need to work in high temperature environments, as it can ensure the stability and reliability of the device at high temperatures.

[0121] For example, in applications such as LED lighting and lasers, high Tg materials can withstand higher operating temperatures and extend the service life of the device.

[0122] Due to the high refractive index and high thermal stability, the cycloolefin copolymer of the present application has significantly improved its application potential in multiple fields. In addition to traditional optical device manufacturing, it can also be used to manufacture high-performance electronic components, sensors, medical devices, etc.

[0123] The high refractive index and high thermal stability of the cycloolefin copolymer provided in the present application bring about significant technical effects, which not only improve the optical properties and thermal stability of the material, but also broaden its application fields.

[0124] It should be noted that, in the embodiment of the present application, by setting the glass transition temperature of the cycloolefin copolymer to be greater than 145° C., the optical device can maintain a glassy state within a wider temperature range, thereby significantly improving the applicability of the cycloolefin copolymer.

[0125] Optionally, the cyclic olefin copolymer has a haze of less than or equal to 0.12.

[0126] Specifically, the haze is the percentage of the transmitted light intensity that deviates from the incident light by more than 2.5° to the total transmitted light intensity. The greater the haze, the lower the transparency of the optical module and the lower the imaging degree. Therefore, when the haze of the cycloolefin copolymer is less than or equal to 0.12, the optical device prepared by the cycloolefin copolymer can have higher transparency and better imaging effect.

[0127] Optionally, the cyclic olefin copolymer has an Abbe number of 31 to 45.

[0128] Specifically, the Abbe number is an index used to represent the dispersion ability of a transparent medium. The greater the refractive index of the medium, the more severe the dispersion and the smaller the Abbe number; conversely, the smaller the refractive index of the medium, the milder the dispersion and the larger the Abbe number. Therefore, when the Abbe number of the cyclic olefin copolymer is 31 to 45, the optical device prepared by the cyclic olefin copolymer can have very small dispersion.

[0129] Optionally, the visible light transmittance of the cycloolefin copolymer is greater than or equal to 84.2%.

[0130] Specifically, the visible light transmittance at an angle of 0° refers to the percentage of the energy of light passing through the cyclic olefin copolymer to the energy of the incident light when the visible light is incident perpendicular to the surface of the cyclic olefin copolymer. The greater the visible light transmittance, the better the imaging effect of the optical module; conversely, the smaller the visible light transmittance, the worse the imaging effect of the optical module. Therefore, when the visible light transmittance of the cyclic olefin copolymer is greater than or equal to 84.2%, more visible light can be received by the optical device made of the cyclic olefin copolymer, so that the imaging effect of the optical device is better.

[0131] The raw materials for preparing the nitrogen-containing heterocyclic polymerization monomer in the present application include a first monomer and a second monomer, and the first monomer and the second monomer are polymerized in a second solvent; wherein the first monomer includes at least one of pyridine, quinoline and acridine; and the second monomer includes at least one of 4-bromo-1-butene, 4-bromo-1-pentene, 5-bromo-1-butene and 5-bromo-1-pentene.

[0132] Specifically, when the first monomer is pyridine and the second monomer is 4-bromo-1-butene, the chemical formula of the cycloolefin copolymer is:

[0133]

[0134] When the first monomer is quinoline and the second monomer is 4-bromo-1-butene, the chemical formula of the cycloolefin copolymer is:

[0135]

[0136] When the first monomer is acridine and the second monomer is 4-bromo-1-pentene, the chemical formula of the cycloolefin copolymer is:

[0137]

[0138] When the first monomer is pyridine and the second monomer is 5-bromo-1-butene, the chemical formula of the cycloolefin copolymer is:

[0139]

[0140] When the first monomer is quinoline and the second monomer is 5-bromo-1-butene, the chemical formula of the cycloolefin copolymer is:

[0141]

[0142] When the first monomer is acridine and the second monomer is 5-bromo-1-pentene, the chemical formula of the cycloolefin copolymer is:

[0143]

[0144] Among them, since the first monomer and the second monomer have a simple structure and a small molecular volume, the insertion rate of the first monomer and the second monomer in the nitrogen-containing heterocyclic polymerization monomer can be effectively improved, thereby effectively ensuring the compatibility of the refractive index of the cycloolefin copolymer with other optical materials, and expanding the application range of the cycloolefin copolymer.

[0145] Of course, under the condition that the preparation requirements of the cycloolefin copolymer are met, the first monomer and the second monomer may also be selected from other chemical substances, and those skilled in the art may make the selection according to actual needs, and this application does not make any specific limitation here.

[0146] In addition, the second solvent in the embodiment of the present application can also make the first monomer react better with the second monomer, thereby significantly improving the preparation efficiency of the nitrogen-containing heterocyclic polymerization monomer.

[0147] According to another embodiment of the present application, a method for preparing a cyclic olefin copolymer is provided, which is used to prepare the cyclic olefin copolymer as described above, and the preparation method comprises the following steps S1 and S2:

[0148] Step S1, mixing a nitrogen-containing heterocyclic polymerization monomer, norbornene and a first solvent;

[0149] Step S2, adding a catalyst, and performing a polymerization reaction at a set temperature and a set pressure; wherein the set temperature is 50° C. to 150° C., the set pressure is 0.1 MPa to 2 MPa, and the polymerization reaction time is 4 h to 24 h.

[0150] Specifically, in the preparation method provided in the embodiment of the present application, the prepared nitrogen-containing heterocyclic polymerization monomer is first dissolved in the first solvent; then norbornene is added and mixed; finally, a catalyst is added, and a polymerization reaction is carried out at a set temperature and a set pressure, and the reaction product is the cycloolefin copolymer; in the polymerization reaction stage, the set temperature is 50°C to 150°C, the set pressure is 0.1Mpa to 2Mpa, and the polymerization reaction time is 4h to 24h.

[0151] In the preparation method provided in the embodiment of the present application, the lower limit temperature of the polymerization reaction is 50°C to ensure that the reaction system can maintain a liquid state and allow the monomer and catalyst to be fully mixed and reacted. Lower temperatures may result in a too slow reaction rate or even failure of the reaction.

[0152] In the preparation method provided in the embodiment of the present application, the upper limit temperature of the polymerization reaction is 150° C. This can prevent the monomer or catalyst from decomposing due to excessively high temperature, producing by-products, and affecting the purity and performance of the product. At the same time, high temperature may also increase energy consumption and safety hazards.

[0153] The temperature range in the present application, i.e., 50° C. to 150° C., can ensure a relatively high reaction rate while avoiding the adverse effects of high temperature.

[0154] In the preparation method provided in the embodiment of the present application, the lower limit of the pressure in the polymerization reaction is 0.1Mpa and the upper limit of the pressure is 2Mpa. Within this pressure range, the gas in the reaction system can be discharged smoothly to avoid gas accumulation affecting the reaction. At the same time, the lower pressure condition is also conducive to energy saving.

[0155] However, excessive pressure will increase equipment requirements and safety risks, and may also increase energy consumption.

[0156] This pressure range in the present application can meet the reaction requirements while maintaining low energy consumption and safety risks.

[0157] In the preparation method provided in the embodiment of the present application, the lower limit of the polymerization reaction time is 4h, which ensures that the reaction is fully carried out, the monomer conversion rate is high, and the product molecular weight distribution is uniform. Too short a reaction time may cause incomplete monomer conversion and poor product performance. In the preparation method provided in the embodiment of the present application, the upper limit of the polymerization reaction time is 24h, which avoids the reaction time being too long to cause by-product generation or product degradation, while saving production time and cost.

[0158] The reaction time range in the present application is 4 h to 24 h, which can not only ensure a high monomer conversion rate, but also avoid unnecessary energy consumption and time waste.

[0159] In the embodiment of the present application, the preparation efficiency and preparation quality of the cycloolefin copolymer are significantly improved by selecting the set temperature range to be 50° C. to 150° C., the set pressure range to be 0.1 MPa to 2 MPa, and the polymerization reaction time range to be 4 h to 24 h.

[0160] The preparation method of the cycloolefin copolymer provided in the embodiment of the present application is intended to synthesize a cycloolefin copolymer with specific properties, particularly a cycloolefin copolymer with high refractive index characteristics. High refractive index materials can improve the design and performance of optical components. If the refractive index of optical components such as lenses and prisms is high, a thinner and lighter design can be achieved, thereby reducing the weight and volume of optical equipment, and improving imaging quality and clarity.

[0161] The present application also provides an optical product, which can be prepared by the above-mentioned cycloolefin copolymer. Since the cycloolefin copolymer of the present application has the optical property of high refractive index, the optical product of the present application also has the same advantages, which will not be described in detail here.

[0162] An embodiment of the present application further provides an electronic device, which includes the above-mentioned optical product. Since the optical product has good optical properties, the electronic device also has the same advantages, which will not be elaborated here.

[0163] The present invention is further described below in conjunction with specific embodiments.

[0164] Example 1

[0165] Preparation process of nitrogen-containing heterocyclic polymerization monomers:

[0166] To 200 ml of acetonitrile, 50 mmol of pyridine, 60 mmol of 4-bromo-1-butene and 100 mmol of K2CO3 were added in sequence, and the mixture was stirred and refluxed at 100°C for 24 h. After cooling to room temperature, the salts (K2CO3, KBr) in the reaction system were removed by suction filtration, and the acetonitrile was removed by rotary evaporation. The mixture was then washed with ethyl acetate, and the filtrate was collected and rotary evaporated. The solid residue was recrystallized with water and filtered to obtain nitrogen-containing heterocyclic polymerization monomer 1.

[0167] Preparation process of cycloolefin copolymer:

[0168] Under anhydrous and oxygen-free conditions, a 250 ml reaction container (such as a Schlenk bottle) is replaced with nitrogen to exhaust air, and 100 ml of toluene is added to the reaction container, followed by 30 mmol of nitrogen-containing heterocyclic polymerizable monomer 1 and 30 mmol of a toluene solution of norbornene;

[0169] Take another dry reaction container, add a catalyst in anhydrous and oxygen-free environment, the catalyst includes a main catalyst and a co-catalyst; wherein the main catalyst is:

[0170] And the main catalyst is 4mg;

[0171] The cocatalyst is 3 ml of MAO solution, which is pre-activated for 5 minutes; the formed polymerized monomer is transferred into a reaction container, heated to 70°C and reacted for 6 hours; 200 ml of ethanol is taken, and 2 ml of concentrated hydrochloric acid is added to the ethanol, the reaction system is cooled to room temperature, poured in and stirred, and the polymer is separated by suction filtration; then washed with ethyl acetate for 3 times, and vacuum dried to obtain a cycloolefin copolymer. The chemical formula of the obtained cycloolefin copolymer is as follows:

[0172]

[0173] Example 2

[0174] Preparation process of nitrogen-containing heterocyclic polymerization monomers:

[0175] To 100 ml of acetonitrile, 50 mmol of quinoline, 60 mmol of 4-bromo-1-butene and 100 mmol of K2CO3 were added in sequence, and the mixture was stirred and refluxed at 100°C for 24 h. After cooling to room temperature, the salts (K2CO3, KBr) in the reaction system were removed by suction filtration, and the acetonitrile was removed by rotary evaporation. The mixture was then washed with ethyl acetate, and the filtrate was collected and rotary evaporated. The solid residue was recrystallized with water and filtered to obtain nitrogen-containing heterocyclic polymerization monomer 2;

[0176] Preparation process of cycloolefin copolymer:

[0177] Under anhydrous and oxygen-free conditions, a 250 ml reaction container (such as a Schlenk bottle) is replaced with nitrogen to exhaust air, and 100 ml of toluene is added to the reaction container, followed by 30 mmol of nitrogen-containing heterocyclic polymerizable monomer 2 and 30 mmol of a toluene solution of norbornene;

[0178] Take another dry reaction container, add a catalyst in anhydrous and oxygen-free environment, the catalyst includes a main catalyst and a co-catalyst; wherein the main catalyst is:

[0179] And the main catalyst is 4mg;

[0180] The cocatalyst is 3 ml of MAO solution, which is pre-activated for 5 minutes; the formed polymerized monomer is transferred into a reaction container, heated to 70°C and reacted for 8 hours; 200 ml of ethanol is taken, and 2 ml of concentrated hydrochloric acid is added to the ethanol, the reaction system is cooled to room temperature, poured in and stirred, and the polymer is separated by suction filtration; then washed with ethyl acetate for 3 times, and vacuum dried to obtain a cycloolefin copolymer. The chemical formula of the obtained cycloolefin copolymer is as follows:

[0181]

[0182] Example 3

[0183] Preparation process of nitrogen-containing heterocyclic polymerization monomers:

[0184] To 100 ml of acetonitrile, 50 mmol of acridine, 60 mmol of 4-bromo-1-pentene and 100 mmol of K2CO3 were added in sequence, and the mixture was stirred and refluxed at 100°C for 24 h. After cooling to room temperature, the salts (K2CO3, KBr) in the reaction system were removed by suction filtration, and the acetonitrile was removed by rotary evaporation. The mixture was then washed with ethyl acetate, and the filtrate was collected and rotary evaporated. The solid residue was recrystallized with water and filtered to obtain nitrogen-containing heterocyclic polymerization monomer 3;

[0185] Preparation process of cycloolefin copolymer:

[0186] Under anhydrous and oxygen-free conditions, a 250 ml reaction container (such as a Schlenk bottle) is replaced with nitrogen to exhaust air, and 100 ml of toluene is added to the reaction container, followed by 30 mmol of nitrogen-containing heterocyclic polymer monomer 3 and 30 mmol of a toluene solution of norbornene;

[0187] Take another dry reaction container, add a catalyst in anhydrous and oxygen-free environment, the catalyst includes a main catalyst and a co-catalyst; wherein the main catalyst is:

[0188] And the main catalyst is 5mg;

[0189] The cocatalyst is 3 ml of MAO solution, which is pre-activated for 5 minutes; the formed polymerized monomer is transferred into a reaction container, heated to 80°C and reacted for 12 hours; 200 ml of ethanol is taken, and 2 ml of concentrated hydrochloric acid is added to the ethanol, the reaction system is cooled to room temperature, poured in and stirred, and the polymer is separated by suction filtration; then washed with ethyl acetate for 3 times, and vacuum dried to obtain a cycloolefin copolymer. The chemical formula of the obtained cycloolefin copolymer is as follows:

[0190]

[0191] Example 4

[0192] Preparation process of nitrogen-containing heterocyclic polymerization monomers:

[0193] To 200 ml of acetonitrile, 50 mmol of pyridine, 60 mmol of 5-bromo-1-butene and 100 mmol of K2CO3 were added in sequence, and the mixture was stirred and refluxed at 100°C for 24 h. After cooling to room temperature, the salts (K2CO3, KBr) in the reaction system were removed by suction filtration, and the acetonitrile was removed by rotary evaporation. The mixture was then washed with ethyl acetate, and the filtrate was collected and rotary evaporated. The solid residue was recrystallized with water and filtered to obtain nitrogen-containing heterocyclic polymerization monomer 4.

[0194] Preparation process of cycloolefin copolymer:

[0195] Under anhydrous and oxygen-free conditions, a 250 ml reaction container (such as a Schlenk bottle) is replaced with nitrogen to exhaust air, and 100 ml of toluene is added to the reaction container, followed by 30 mmol of nitrogen-containing heterocyclic polymerization monomer 4 and 30 mmol of a toluene solution of norbornene;

[0196] Take another dry reaction container, add a catalyst in anhydrous and oxygen-free environment, the catalyst includes a main catalyst and a co-catalyst; wherein the main catalyst is:

[0197] And the main catalyst is 5mg;

[0198] The cocatalyst is 3 ml of MAO solution, which is pre-activated for 5 minutes; the formed polymerized monomer is transferred into a reaction container, heated to 70°C and reacted for 6 hours; 200 ml of ethanol is taken, and 2 ml of concentrated hydrochloric acid is added to the ethanol, the reaction system is cooled to room temperature, poured in and stirred, and the polymer is separated by suction filtration; then washed with ethyl acetate for 3 times, and vacuum dried to obtain a cycloolefin copolymer. The chemical formula of the obtained cycloolefin copolymer is as follows:

[0199]

[0200] Example 5

[0201] Preparation process of nitrogen-containing heterocyclic polymerization monomers:

[0202] To 100 ml of acetonitrile, 50 mmol of quinoline, 60 mmol of 5-bromo-1-butene and 100 mmol of K2CO3 were added in sequence, and the mixture was stirred and refluxed at 100°C for 24 h. After cooling to room temperature, the salts (K2CO3, KBr) in the reaction system were removed by suction filtration, and the acetonitrile was removed by rotary evaporation. The mixture was then washed with ethyl acetate, and the filtrate was collected and rotary evaporated. The solid residue was recrystallized with water and filtered to obtain nitrogen-containing heterocyclic polymerization monomer 5.

[0203] Preparation process of cycloolefin copolymer:

[0204] Under anhydrous and oxygen-free conditions, a 250 ml reaction container (such as a Schlenk bottle) is replaced with nitrogen to exhaust air, and 100 ml of toluene is added to the reaction container, followed by 30 mmol of nitrogen-containing heterocyclic polymerizable monomer 5 and 30 mmol of a toluene solution of norbornene;

[0205] Take another dry reaction container, add a catalyst in anhydrous and oxygen-free environment, the catalyst includes a main catalyst and a co-catalyst; wherein the main catalyst is:

[0206] And the main catalyst is 5mg;

[0207] The cocatalyst is 3 ml of MAO solution, which is pre-activated for 5 minutes; the formed polymerized monomer is transferred into a reaction container, heated to 70°C and reacted for 8 hours; 200 ml of ethanol is taken, and 2 ml of concentrated hydrochloric acid is added to the ethanol, the reaction system is cooled to room temperature, poured in and stirred, and the polymer is separated by suction filtration; then washed with ethyl acetate for 3 times, and vacuum dried to obtain a cycloolefin copolymer. The chemical formula of the obtained cycloolefin copolymer is as follows:

[0208]

[0209] Example 6

[0210] Preparation process of nitrogen-containing heterocyclic polymerization monomers:

[0211] To 100 ml of acetonitrile, 50 mmol of acridine, 60 mmol of 5-bromo-1-pentene and 100 mmol of K2CO3 were added in sequence, and the mixture was stirred and refluxed at 100°C for 24 h. After cooling to room temperature, the salts (K2CO3, KBr) in the reaction system were removed by suction filtration, and the acetonitrile was removed by rotary evaporation. The mixture was then washed with ethyl acetate, and the filtrate was collected and rotary evaporated. The solid residue was recrystallized with water and filtered to obtain nitrogen-containing heterocyclic polymerization monomer 6;

[0212] Preparation process of cycloolefin copolymer:

[0213] Under anhydrous and oxygen-free conditions, a 250 ml reaction container (such as a Schlenk bottle) is replaced with nitrogen to exhaust air, and 100 ml of toluene is added to the reaction container, followed by 30 mmol of nitrogen-containing heterocyclic polymer monomer 6 and 30 mmol of a toluene solution of norbornene;

[0214] Take another dry reaction container, add a catalyst in anhydrous and oxygen-free environment, the catalyst includes a main catalyst and a co-catalyst; wherein the main catalyst is:

[0215] And the main catalyst is 5mg;

[0216] The cocatalyst is 3 ml of MAO solution, which is pre-activated for 5 minutes; the formed polymerized monomer is transferred into a reaction container, heated to 80°C and reacted for 12 hours; 200 ml of ethanol is taken, and 2 ml of concentrated hydrochloric acid is added to the ethanol, the reaction system is cooled to room temperature, poured in and stirred, and the polymer is separated by suction filtration; then washed with ethyl acetate for 3 times, and vacuum dried to obtain a cycloolefin copolymer. The chemical formula of the obtained cycloolefin copolymer is as follows:

[0217]

[0218] According to the above-mentioned Examples 1 to 6, the preparation method of the cycloolefin copolymer can be seen in the following reaction formula:

[0219]

[0220] Comparative Example 1

[0221] Under anhydrous and oxygen-free conditions, a 250 ml reaction container (such as a Schlenk bottle) is replaced with nitrogen to expel air, and 100 ml of toluene, 5 mg of the main catalyst (f), 5 ml of MAO solution, 1 ml of triethylaluminum are added, and ethylene is charged to 0.7 MPa; stirred, the temperature is raised to 70°C and reacted for 30 minutes, 200 ml of 10 wt% HCl ethanol solution is added to terminate the polymerization, the polymer is filtered, washed with ethanol and vacuum dried.

[0222] Comparative Example 2

[0223] Under anhydrous and oxygen-free conditions, a 250 ml reaction container (such as a schlenk bottle) is replaced with nitrogen to expel air, and 100 ml of toluene, 5 mg of the main catalyst (f), 5 ml of MAO solution, 1 ml of triethylaluminum are added, and ethylene is charged to 0.7 MPa; stirred, the temperature is raised to 80°C and reacted for 30 minutes, 100 ml of 10 wt% HCl ethanol solution is added to terminate the polymerization, the polymer is filtered, and washed with ethanol and vacuum dried.

[0224] The main catalyst (f) in Comparative Examples 1 and 2 is:

[0225]

[0226] The comonomer insertion rate, glass transition temperature (Tg), weight average molecular weight (Mw), transmittance, haze, refractive index (nD), and Abbe number of the cycloolefin copolymers prepared by Examples 1 to 6, and Comparative Examples 1 and 2 can be referred to as shown in Table 1.

[0227] Table 1

[0228]

[0229] It can be seen from Table 1 above that compared with Comparative Examples 1 and 2, Examples 1-6 have a higher refractive index (>1.56) and a higher glass transition temperature (>145°C).

[0230] The above embodiments focus on the differences between the various embodiments. As long as the different optimization features between the various embodiments are not contradictory, they can be combined to form a better embodiment. Considering the simplicity of the text, they will not be repeated here.

[0231] Although some specific embodiments of the present application have been described in detail by way of example, it should be understood by those skilled in the art that the above examples are only for illustration, not for limiting the scope of the present application. It should be understood by those skilled in the art that the above embodiments may be modified without departing from the scope and spirit of the present application. The scope of the present application is defined by the appended claims.

Claims

1. A cycloolefin copolymer, characterized in that The chemical formula of the cycloolefin copolymer is: Wherein, x is the number of monomers of the nitrogen-containing heterocyclic polymerization monomer, y is the number of monomers of norbornene, n is 3 or 4, and R is a nitrogen-containing heterocyclic group, which includes at least one of a pyridyl group, a quinolyl group and an acridinyl group.

2. The cycloolefin copolymer according to claim 1, characterized in that The raw materials for preparing the cycloolefin copolymer at least include a nitrogen-containing heterocyclic polymerization monomer and norbornene, and the nitrogen-containing heterocyclic polymerization monomer and the norbornene are polymerized in a first solvent.

3. The cycloolefin copolymer according to claim 2, characterized in that The first solvent includes at least one of acetonitrile, toluene, ethyl acetate, distilled water, hydrochloric acid and ethanol.

4. The cycloolefin copolymer according to claim 3, characterized in that The raw materials for preparing the nitrogen-containing heterocyclic polymerizable monomer include a first monomer and a second monomer, and the first monomer and the second monomer are polymerized in a second solvent; The first monomer includes at least one of pyridine, quinoline and acridine; The second monomer includes at least one of 4-bromo-1-butene, 4-bromo-1-pentene, 5-bromo-1-butene and 5-bromo-1-pentene; The second solvent includes acetonitrile or ethyl acetate.

5. The cycloolefin copolymer according to claim 2, characterized in that The nitrogen-containing heterocyclic polymer monomer and the norbornene are polymerized under the catalytic action of a catalyst; The catalyst comprises a main catalyst and a co-catalyst; The main catalyst includes a metallocene catalyst; The co-catalyst includes at least one of [Ph3C][B(C6F5)4], methylaluminoxane (MAO) and alkylaluminum, wherein the alkylaluminum includes at least one of triethylaluminum, triisobutylaluminum and trioctylaluminum.

6. The cycloolefin copolymer according to claim 5, characterized in that The mass ratio of the main catalyst to the co-catalyst is 1:(100-2000).

7. The cycloolefin copolymer according to claim 1, characterized in that The molecular weight of the cyclic olefin copolymer is 50,000 to 180,000.

8. The cycloolefin copolymer according to claim 1, characterized in that The refractive index of the cycloolefin copolymer is greater than 1.56, and the glass transition temperature thereof is greater than 145°C.

9. The cycloolefin copolymer according to claim 4, characterized in that When the first monomer is pyridine and the second monomer is 4-bromo-1-butene, the chemical formula of the cycloolefin copolymer is:

10. The cycloolefin copolymer according to claim 4, characterized in that When the first monomer is quinoline and the second monomer is 4-bromo-1-butene, the chemical formula of the cycloolefin copolymer is:

11. The cycloolefin copolymer according to claim 4, characterized in that When the first monomer is acridine and the second monomer is 4-bromo-1-pentene, the chemical formula of the cycloolefin copolymer is:

12. The cycloolefin copolymer according to claim 4, characterized in that When the first monomer is pyridine and the second monomer is 5-bromo-1-butene, the chemical formula of the cycloolefin copolymer is:

13. The cycloolefin copolymer according to claim 4, characterized in that When the first monomer is quinoline and the second monomer is 5-bromo-1-butene, the chemical formula of the cycloolefin copolymer is:

14. The cycloolefin copolymer according to claim 4, characterized in that When the first monomer is acridine and the second monomer is 5-bromo-1-pentene, the chemical formula of the cycloolefin copolymer is:

15. A method for preparing a cycloolefin copolymer, characterized in that: For preparing the cycloolefin copolymer according to any one of claims 1 to 14, the preparation method comprises: mixing a nitrogen-containing heterocyclic polymerizable monomer, norbornene, and a first solvent; A catalyst is added, and a polymerization reaction is carried out at a set temperature and a set pressure; wherein the set temperature is 50° C. to 150° C., the set pressure is 0.1 MPa to 2 MPa, and the polymerization reaction time is 4 h to 24 h.

16. An optical product, characterized in that: The optical product is prepared from the cyclic olefin copolymer according to any one of claims 1 to 14.

17. An electronic device, characterized in that: The optical product comprising claim 16.

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