Cyclic olefin copolymer and method for producing the same, optical article, and electronic device

Abstract

The embodiment of the present application provides a kind of cycloolefin copolymer and its preparation method, optical product and electronic equipment;Wherein, the preparation method of the cycloolefin copolymer includes: nitrogen-containing heterocyclic compound and alpha olefin containing bromine atom are mixed, and the copolymerization monomer of cycloolefin copolymer is prepared;Wherein, the nitrogen-containing heterocyclic compound includes indole or carbazole;The copolymerization monomer is mixed with the toluene solution of norbornene, and then added into catalyst system, to obtain reaction system;Wherein, the catalyst system is to mix metallocene catalyst as main catalyst with cocatalyst;The reaction system is added to extraction system, and cycloolefin copolymer is prepared.The preparation method of the cycloolefin copolymer provided in the embodiment of the present application can provide a kind of high refractive index cycloolefin copolymer.

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 preparation method of a cyclic olefin copolymer, a cyclic olefin copolymer, an optical product, and an electronic device. Background Art

[0002] Cyclic olefin copolymers (COC), a key class of thermoplastic optical plastics, are primarily copolymerized with cycloolefin monomers and α-olefins. They have become important engineering plastics in numerous fields, including optics, information technology, electrical appliances, and medical materials. However, existing COC materials, such as APEL and TOPAS, generally have a refractive index between 1.5 and 1.55, significantly lower than that of other optical materials, such as polycarbonate (PC).

[0003] Materials with high refractive index offer significant advantages in the design and performance of optical components. For example, high-refractive-index lenses and prisms enable thinner and lighter designs, reducing device weight and size while also improving image quality and clarity. Consequently, the development of high-refractive-index COC materials has become a current research hotspot. Summary of the Invention

[0004] The purpose of this application is to provide a method for preparing a cycloolefin copolymer, a cycloolefin copolymer, an optical product, and a new technical solution for electronic equipment.

[0005] In a first aspect, an embodiment of the present application provides a method for preparing a cycloolefin copolymer, the method for preparing the cycloolefin copolymer comprising:

[0006] Mixing a nitrogen-containing heterocyclic compound with an α-olefin containing a bromine atom to prepare a comonomer of a cycloolefin copolymer; wherein the nitrogen-containing heterocyclic compound comprises indole or carbazole;

[0007] The comonomer and norbornene toluene solution are mixed and then added to a catalyst system to obtain a reaction system; wherein the catalyst system is composed of a metallocene catalyst as a main catalyst and a cocatalyst;

[0008] The reaction system is added to the extraction system to prepare a cycloolefin copolymer.

[0009] Optionally, the preparation method comprises: sequentially adding the nitrogen-containing heterocyclic compound, the bromine-containing α-olefin and a catalyst into a predetermined solvent to prepare a comonomer of the cycloolefin copolymer.

[0010] Optionally, the bromine-containing α-olefin includes 4-bromo-1-butene or 5-bromo-1-pentene;

[0011] The set solvent includes at least one of n-hexane, acetonitrile, toluene, tetrahydrofuran, dichloromethane, diethyl ether and n-pentane.

[0012] The catalyst includes K2CO3.

[0013] Optionally, the mass ratio of the metallocene catalyst to the co-catalyst is 1:(10-2000).

[0014] Optionally, the metallocene catalyst includes any one of metallocene catalyst a, metallocene catalyst b and metallocene catalyst c.

[0015] The molecular formula of metallocene catalyst a is as follows:

[0016]

[0017] The molecular formula of metallocene catalyst b is as follows:

[0018]

[0019] The molecular formula of metallocene catalyst c is as follows:

[0020]

[0021] Optionally, the co-catalyst includes at least one of [Ph3C][B(C6F5)4], methylaluminoxane MAO and alkylaluminum.

[0022] The alkylaluminum includes any one of triethylaluminum, triisobutylaluminum and trioctylaluminum.

[0023] Optionally, the preparation of the comonomer of the cyclic olefin copolymer by adding the nitrogen-containing heterocyclic compound, the bromine atom-containing α-olefin and the catalyst in the set solvent includes the following steps:

[0024] The nitrogen-containing heterocyclic compound, the bromine atom-containing α-olefin and the catalyst are sequentially added in the set solvent, stirred and refluxed at a first set temperature for a first set time, and after the temperature is reduced to room temperature, the salt in the reaction is removed by filtration and the set solvent is removed by rotary evaporation to obtain the product; wherein the molar ratio of the nitrogen-containing heterocyclic compound to the bromine atom-containing α-olefin is 1:1-2.

[0025] The obtained product is washed with an organic solvent, and then the filtrate is collected and rotary evaporated to obtain a solid residue.

[0026] The solid residue is purified by silica gel column chromatography to obtain the comonomer of the cyclic olefin copolymer.

[0027] Optionally, the bromine-containing α-olefin includes 4-bromo-1-butene or 5-bromo-1-pentene, and the catalyst includes K2CO3;

[0028] Wherein, the salts removed by suction filtration in the reactants include K2CO3 and KBr;

[0029] The first set temperature is 70° C. to 80° C., and the first set time is 6 hours to 18 hours.

[0030] Optionally, the comonomer and norbornene toluene solution are mixed and then added to a catalyst system to obtain a reaction system, comprising:

[0031] Under anhydrous and oxygen-free conditions, the comonomer and a toluene solution of norbornene are mixed at a molar ratio of 1:1 to obtain a mixed monomer; wherein the toluene solution of norbornene is obtained by adding norbornene to a toluene solution;

[0032] Under anhydrous and oxygen-free conditions, the metallocene catalyst and the co-catalyst are mixed in a set amount ratio and activated to obtain a catalyst system;

[0033] The mixed monomers and the catalyst system are mixed, heated to a second set temperature, and reacted under a set pressure for a second set time to obtain a reaction system.

[0034] Optionally, the second set temperature is 50°C to 120°C;

[0035] The set pressure is 0.1Mpa to 1Mpa;

[0036] The second set time length is 4 hours to 12 hours.

[0037] Optionally, the reaction system is added to an extraction system to prepare a cycloolefin copolymer, comprising:

[0038] Concentrated hydrochloric acid added to ethanol forms an extraction system;

[0039] The reaction system was cooled to room temperature and then added to the extraction system and stirred;

[0040] The polymer is separated by suction filtration, washed with an organic solvent, and dried to obtain a cycloolefin copolymer.

[0041] In a second aspect, an embodiment of the present application provides a cycloolefin copolymer, characterized in that it is prepared using the preparation method described in the first aspect.

[0042] In a third aspect, the embodiments of the present application provide a cycloolefin copolymer, the general structural formula of the cycloolefin copolymer is as follows:

[0043]

[0044] Wherein, n=3 or 4, R represents a nitrogen-containing heterocyclic group, including an indole group or a carbazolyl group; x and y represent the number of repeating units.

[0045] Optionally, the first molecular formula of the cycloolefin copolymer is as follows:

[0046]

[0047] Optionally, the second molecular formula of the cycloolefin copolymer is as follows:

[0048]

[0049] Optionally, the third molecular formula of the cycloolefin copolymer is as follows:

[0050]

[0051] Optionally, the fourth molecular formula of the cycloolefin copolymer is as follows:

[0052]

[0053] Optionally, the molecular weight of the cycloolefin copolymer is 50,000 to 150,000, and the glass transition temperature thereof is 100° C. to 180° C.

[0054] In a fourth aspect, an embodiment of the present application provides an optical product, wherein the optical product is prepared from the cycloolefin copolymer according to the second aspect.

[0055] In a fifth aspect, an embodiment of the present application provides an electronic device, which includes the optical product described in the third aspect.

[0056] One beneficial effect of this application is:

[0057] According to the preparation method provided in the embodiment of the present application, a comonomer of a cycloolefin copolymer is prepared by copolymerizing a nitrogen-containing heterocyclic compound with an alpha-olefin containing a bromine atom; the comonomer is then mixed with a toluene solution of norbornene and then added to a catalyst system to obtain a reaction system; wherein the catalyst system is composed of a metallocene catalyst as a main catalyst and a co-catalyst to provide a suitable reaction activity; the reaction system is added to a mixed system consisting of ethanol and concentrated hydrochloric acid, and the reaction temperature and time are controlled to extract the cycloolefin copolymer. In the preparation method of the embodiment of the present application, the molecular structure and molecular weight distribution of the copolymer are regulated by optimizing the catalyst system and reaction conditions, thereby obtaining a COC material with a high refractive index.

[0058] Other features and advantages of the present specification will become apparent through the detailed description of exemplary embodiments of the present specification. DETAILED DESCRIPTION

[0059] Various exemplary embodiments of the present application will now be described in detail. It should be noted that unless otherwise specifically stated, the relative arrangements of components and steps, numerical expressions and numerical values ​​set forth in these embodiments do not limit the scope of the present application.

[0060] The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the present disclosure, its application, or uses.

[0061] 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.

[0062] 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.

[0063] The following describes in detail the preparation method of the cycloolefin copolymer, the cycloolefin copolymer, the optical product, and the electronic device provided in the embodiments of the present application with reference to specific examples.

[0064] The method for preparing a cyclic olefin copolymer provided in an embodiment of the present application includes the following steps S1 to S3:

[0065] Step S1, mixing a nitrogen-containing heterocyclic compound with an α-olefin containing a bromine atom to prepare a comonomer of a cycloolefin copolymer; wherein the nitrogen-containing heterocyclic compound comprises indole or carbazole;

[0066] Step S2, mixing the comonomer and norbornene toluene solution and adding the mixture to a catalyst system to obtain a reaction system; wherein the catalyst system is composed of a metallocene catalyst as a main catalyst and a co-catalyst;

[0067] Step S3: adding the reaction system to the extraction system to prepare a cycloolefin copolymer.

[0068] The preparation method of the cycloolefin copolymer provided in the embodiments of the present application, through a specially designed material matching step, 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, thinner and lighter designs can be achieved, thereby reducing the weight and volume of optical equipment and improving image quality and clarity.

[0069] In some examples of the present application, the preparation method includes: sequentially adding the nitrogen-containing heterocyclic compound, the bromine-containing α-olefin, and a catalyst into a predetermined solvent to prepare a comonomer of a cycloolefin copolymer.

[0070] According to step S1 provided in the embodiments of the present application, the main purpose is to prepare a comonomer for a cycloolefin copolymer. The specific process is to add a certain amount of a nitrogen-containing heterocyclic compound, a bromine-containing α-olefin, and a catalyst to a predetermined solvent, and to prepare the comonomer for the cycloolefin copolymer by controlling the reaction conditions.

[0071] In step S1, by selecting an appropriate solvent, sufficient contact and uniform mixing between the reactants can be ensured, thereby improving reaction efficiency. Specifically, in a copolymerization reaction, the solvent can effectively dissolve and disperse the reactants, such as nitrogen-containing heterocyclic compounds, bromine-containing α-olefins, and catalysts. By ensuring that the reactants are fully dissolved and uniformly dispersed in the solvent, the contact area between the reactants can be increased, reaction efficiency can be improved, and the polymerization reaction can be smoothly carried out.

[0072] In step S1, nitrogen-containing heterocyclic compounds play an important role in preparing the comonomers of cycloolefin copolymers. Nitrogen-containing heterocyclic compounds can act as reaction modifiers, controlling the composition and structure of the comonomers by influencing the reaction rate or reaction pathway. In other words, the addition of nitrogen-containing heterocyclic compounds can regulate the reaction process, improve copolymer properties, and control the copolymer structure.

[0073] On the other hand, the nitrogen-containing heterocyclic compound in the embodiments of the present application is, for example, indole or carbazole. During the preparation of the cycloolefin copolymer, the introduction of nitrogen-containing heterocyclic compounds such as carbazole or indole can increase the refractive index of the resulting cycloolefin copolymer. This is because nitrogen-containing heterocyclic compounds such as carbazole and indole can alter the electronic structure and steric configuration of the resulting cycloolefin copolymer during the copolymerization process, thereby affecting its optical properties.

[0074] Specifically: First, as nitrogen-containing heterocyclic compounds, carbazole and indole have unique molecular structures and electronic configurations. In copolymerization reactions, these compounds can chemically bond with cycloolefin monomers to form more complex copolymer structures. This structural change causes the electron distribution in the copolymer to change, which can improve the refractive index. Secondly, the introduction of nitrogen-containing heterocyclic compounds can also increase the polarity of the copolymer, which helps to improve the interaction between the copolymer and the surrounding environment, further affecting its optical properties. In addition, the introduction of carbazole and indole may also improve the crystallinity and orientation of the copolymer, all of which help to improve the refractive index. In short, in copolymerization reactions, the introduction of nitrogen-containing heterocyclic compounds such as carbazole and indole can help to increase the refractive index of cycloolefin copolymers, thereby expanding their application range in the optical field.

[0075] In step S1, the addition of bromine-containing α-olefins can increase the chain length of the copolymer and improve its physical properties. In other words, the bromine-containing α-olefins, as part of the comonomers of the cycloolefin copolymer, participate in the polymerization reaction, thereby affecting the chain structure and composition of the copolymer.

[0076] Specifically, by introducing the bromine-containing α-olefin, specific functional groups or side chain structures can be introduced into the resulting cycloolefin copolymer. These structures can modify the properties of the cycloolefin copolymer, such as refractive index and thermal stability. Secondly, bromine atoms are highly reactive functional groups. For example, substitution reactions of bromine atoms can be used to introduce other functional groups or polymer segments, thereby expanding the functionalization of the cycloolefin copolymer.

[0077] The bromine-containing α-olefin used in the embodiments of the present application has a specific structure and reaction characteristics, and can be copolymerized with other materials during the copolymerization reaction, thereby facilitating the subsequent acquisition of a cycloolefin copolymer with a specific structure and high refractive index performance.

[0078] In the step S1: a catalyst is introduced into the copolymerization reaction to promote the copolymerization reaction between the nitrogen-containing heterocyclic compound and the bromine-containing α-olefin.

[0079] According to step S2 provided in an embodiment of the present application: the comonomer of the cycloolefin copolymer prepared in step S1 is mixed with a toluene solution of norbornene, and then a catalyst system consisting of a metallocene catalyst as a main catalyst and a co-catalyst is added to the mixed system to form a reaction system.

[0080] In step S2, norbornene, a cyclic olefin, is mixed with the comonomer of the cyclic olefin copolymer obtained in step S1 and then copolymerized in the presence of a catalyst system. The introduction of norbornene can adjust the chain structure and properties of the copolymer and increase the cyclic structure of the copolymer, thereby improving the refractive index and other properties of the cyclic olefin copolymer.

[0081] It should be noted that, in step S2, the introduction of norbornene can increase the cyclic structure of the copolymer finally formed, which helps to improve the refractive index of the formed cycloolefin copolymer.

[0082] In step S2, a metallocene catalyst is used as a primary catalyst, which plays a key role in the copolymerization reaction. Metallocene catalysts have excellent catalytic activity and selectivity and can efficiently promote the polymerization of olefins. Through the synergistic effect with the added co-catalyst, the metallocene catalyst can control the copolymerization rate and selectivity, thereby obtaining a cycloolefin copolymer with a specific structure and high refractive index performance.

[0083] The addition of a co-catalyst can further enhance the catalytic effect of the main catalyst. The combination of the co-catalyst and the main catalyst can optimize the copolymerization reaction environment, improve the stability and activity of the catalyst system, and thus ensure the efficient conduct of the copolymerization reaction.

[0084] In step S2, toluene is selected as the solvent to facilitate uniform mixing and dispersion of the reactants. Specifically, first, as an organic solvent, toluene can effectively dissolve norbornene, ensuring its uniform distribution in the reaction system. This increased solubility helps promote sufficient contact between norbornene and other reactants, thereby improving reaction efficiency and product quality. Second, the addition of toluene may affect the reactivity of norbornene through its solvent effect, for example, accelerating or optimizing the progress of the chemical reaction.

[0085] Toluene's relatively low volatility can reduce volatile organic compound (VOC) emissions during operation, benefiting the environment. Due to its relatively low price, using toluene as a solvent for norbornene can reduce production costs. Furthermore, toluene can be recycled and reused, further reducing costs and waste generation.

[0086] Through the above-mentioned step S2, a stable and efficient reaction system can be formed, providing a foundation for the smooth progress of the subsequent copolymerization reaction. The technical benefits of this step are mainly reflected in improving the efficiency of the copolymerization reaction, optimizing the structure and properties of the copolymer, and reducing production costs. At the same time, it also provides a prerequisite for the development of cycloolefin copolymers with excellent properties such as high refractive index.

[0087] According to the step S3 provided in the embodiments of the present application, the reaction system obtained in the step S2 is added into a mixed system mainly composed of ethanol and concentrated hydrochloric acid, and the cyclic olefin copolymer is prepared by controlling the reaction conditions and subsequent processing steps.

[0088] In the step S3, an extraction system is prepared, which is used as an extractant here to obtain the final product, i.e., the cyclic olefin copolymer. This step aims to realize the separation and purification of the cyclic olefin copolymer through an extraction process.

[0089] That is, the extraction system can selectively separate the copolymer from the reaction system, further improving the purity and refractive index of the copolymer.

[0090] According to the above steps S1 to S3 provided in the embodiments of the present application, the degree of polymerization of the cyclic olefin copolymer can be accurately controlled, so that the cyclic olefin copolymer with a high refractive index is obtained, which has a wide application prospect in the field of optics. For example, the refractive index of the cyclic olefin copolymer can be above 1.55, and even greater than 1.6.

[0091] In some examples of the present application, the α-olefin containing a bromine atom includes 4-bromo-1-butene or 5-bromo-1-pentene. The set solvent includes at least one of n-hexane, acetonitrile, toluene, tetrahydrofuran, dichloromethane, diethyl ether, and n-pentane. The catalyst includes K2CO3.

[0092] In the step S1 provided in the embodiments of the present application, the α-olefin containing a bromine atom includes 4-bromo-1-butene or 5-bromo-1-pentene. The introduction of the α-olefin containing a bromine atom such as 4-bromo-1-butene or 5-bromo-1-pentene plays a crucial role in the preparation of the comonomer of the cyclic olefin copolymer.

[0093] 4-bromo-1-butene is an α-olefin with a bromine atom located on the fourth carbon atom. 5-bromo-1-pentene is an α-olefin with a bromine atom located on the fifth carbon atom. Due to the presence of the bromine atom, these two compounds have high reactivity in the reaction and can participate in various organic synthesis reactions.

[0094] In the step S1 provided in the embodiments of the present application, the above-mentioned α-olefin containing a bromine atom, the nitrogen-containing heterocyclic compound, and the set solvent are subjected to a copolymerization reaction under the action of the catalyst. The introduction of the bromine atom not only changes the chemical properties of the olefin, making it more easily participate in the copolymerization reaction, but also can introduce specific functional groups in the copolymerization process. These functional groups may react with other monomers in the subsequent copolymerization reaction, thereby affecting the structure and performance of the final copolymer.

[0095] The presence of bromine atoms makes α-olefins more reactive with other monomers, such as nitrogen-containing heterocyclic compounds, thereby increasing the rate and efficiency of copolymerization. By introducing bromine-containing α-olefins, the molecular structure and segment distribution of the copolymer can be manipulated to a certain extent, thereby affecting its optical and mechanical properties. Furthermore, as a reactive functional group, bromine atoms can react with other groups in subsequent chemical reactions, thus endowing the copolymer with greater functionality and application potential.

[0096] According to the method for preparing a cyclic olefin copolymer provided in an embodiment of the present application, in the above-mentioned step S1, a solvent, i.e., a set solvent, is used. The set solvent can be at least one of n-hexane, acetonitrile, toluene, tetrahydrofuran, dichloromethane, ether, and n-pentane.

[0097] By selecting suitable solvent, can realize the regulation and control to reaction rate, thereby optimize the polymerization process of comonomer.Solvent also has an impact on the form and the molecular weight distribution of the cycloolefin copolymer that forms, and different solvents may cause the extension or contraction of polymer chain, thereby affect its physical and chemical properties.Desirable solvent should be easy to remove from polymkeric substance after reaction.In addition, the selection of solvent also should consider its safety, comprise inflammability, toxicity and volatility etc., to ensure safety in preparation process.The above-mentioned solvent that adopts in the application can meet above-mentioned requirements.

[0098] In particular, solvents such as n-hexane, toluene, tetrahydrofuran, and diethyl ether need to be dehydrated with sodium / benzophenone in advance. The dehydration step can further improve the purity of the solvent, ensuring the smooth progress of the reaction and the quality of the product.

[0099] n-Hexane is a non-polar solvent with a strong solubility for non-polar substances. It is chemically stable and is not prone to side reactions with reactants. By removing water, trace amounts of water can be further reduced, preventing moisture from affecting the reaction.

[0100] Acetonitrile is a polar solvent with good solubility for many organic compounds.

[0101] Toluene is an aromatic hydrocarbon solvent with good solubility for many organic substances. Its moderate boiling point makes it easily recyclable and reusable through distillation. Dehydration treatment can further reduce the impact of moisture on the reaction system.

[0102] Tetrahydrofuran is a polar solvent with a low boiling point and good solubility for many organic compounds. Dehydration of tetrahydrofuran can further reduce the occurrence of side reactions.

[0103] Dichloromethane is a halogenated hydrocarbon solvent with strong dissolving power. It is highly volatile and can be easily recovered by distillation.

[0104] Diethyl ether is an ether solvent with good solubility for many organic substances. It has a low boiling point and is easily recyclable. Diethyl ether, after dehydration, ensures the purity and smooth progress of the reaction.

[0105] As an alkane solvent, n-pentane has good solubility for non-polar substances. It is chemically stable and suitable for reaction systems that require non-polar solvents.

[0106] The advantages of using these solvents lie in their unique solubility and chemical properties, which can meet the needs of different chemical reactions and material preparations. Through water removal, the purity of the solvents can be further improved, the occurrence of side reactions can be reduced, and the smooth progress of the reaction and the quality of the product can be ensured.

[0107] In step S1 provided in the embodiment of the present application, the catalyst may be potassium carbonate K2CO3.

[0108] Potassium carbonate K2CO3, as a catalyst, plays an important role in the copolymerization of bromine-containing α-olefins and nitrogen-containing heterocyclic compounds. The details are as follows:

[0109] (1) Potassium carbonate (K2CO3) has a neutralizing effect, which can neutralize the acidic substances in the reaction system and stabilize the reaction environment. At the same time, it can also adjust the pH value of the reaction system to ensure that the reaction is carried out under appropriate pH conditions.

[0110] (2) As a catalyst, potassium carbonate (K2CO3) can increase the reaction rate, thereby promoting the copolymerization of bromine-containing α-olefins and nitrogen-containing heterocyclic compounds. The catalytic effect of potassium carbonate (K2CO3) can also affect the molecular structure and segment distribution of the copolymer. By adjusting the amount of potassium carbonate and the reaction conditions, the structure and properties of the copolymer can be finely controlled.

[0111] (3) The catalytic effect of potassium carbonate facilitates the synthesis of cycloolefin copolymers with specific structures and properties. These copolymers may possess excellent optical properties, mechanical properties, and chemical stability, thus meeting the application requirements of different fields.

[0112] In some examples of the present application, the mass ratio of the metallocene catalyst to the co-catalyst is 1:(10-2000).

[0113] In the examples of this application, it is specifically mentioned that the mass ratio of the metallocene catalyst to the cocatalyst is set in the range of 1:(10-2000). This ratio range is based on the optimization requirements of the catalyst system activity and selectivity, aiming to achieve efficient and stable cycloolefin copolymerization.

[0114] Metallocene catalysts can exhibit high activity and selectivity in copolymerization reactions. However, they typically require the assistance of a cocatalyst to maximize their catalytic performance. Cocatalysts not only help activate the metal centers of the metallocene catalyst but also regulate the activity and selectivity of the resulting catalyst system, thereby affecting the copolymerization reaction rate and product structure.

[0115] In the examples of this application, the mass ratio of the metallocene catalyst (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 best 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 excessive side reactions, reducing the selectivity and purity of the product.

[0116] In the examples of this application, by adjusting this ratio range, fine control of the cycloolefin copolymerization reaction process can be achieved. In addition, a suitable ratio of the main catalyst to the co-catalyst can also help 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.

[0117] In some examples of the present application, the metallocene catalyst includes any one of metallocene catalyst a, metallocene catalyst b, and metallocene catalyst c;

[0118] Wherein, the molecular formula of metallocene catalyst a is as follows:

[0119]

[0120] Wherein, the molecular formula of metallocene catalyst b is as follows:

[0121]

[0122] Wherein, the molecular formula of metallocene catalyst c is as follows:

[0123]

[0124] In the methods for preparing cycloolefin copolymers provided in the examples of this application, the metallocene catalyst can be any of the three aforementioned catalysts. Metallocene catalysts have the characteristics of a single active center, a narrow molecular weight distribution, and high activity. They can catalyze the addition polymerization of cycloolefins and copolymerization with ethylene, propylene, and other materials, achieving a variety of organic reactions.

[0125] In some examples of the present application, the co-catalyst includes at least one of [Ph3C][B(C6F5)4], methylaluminoxane MAO and alkylaluminum; wherein the alkylaluminum includes any one of triethylaluminum, triisobutylaluminum and trioctylaluminum.

[0126] Cocatalysts play a crucial role in catalyst systems. They can combine with primary catalysts, such as metallocene catalysts, to modify certain properties of the primary catalyst, such as electronic structure, ionic valence, acidity and alkalinity, surface structure, and crystallite size. These changes help improve the primary catalyst's activity, selectivity, toxicity resistance, and stability, thereby optimizing the catalytic reaction.

[0127] In the examples of this application, the cocatalyst includes at least one of [Ph3C][B(C6F5)4], methylaluminoxane (MAO), and an aluminum alkyl. Each of these cocatalysts has its own unique characteristics, producing different technical effects when combined with a metallocene catalyst. When combined with a metallocene catalyst, these cocatalysts form a highly efficient catalyst system. Their synergistic effect optimizes catalytic reaction conditions, increases reaction speed, and reduces byproduct formation, thereby improving product purity and quality.

[0128] In general, co-catalysts play an indispensable role in catalytic reactions. By selecting appropriate co-catalysts and combining them with the main catalyst, the catalytic reaction process can be finely controlled to achieve better catalytic effects.

[0129] In some examples of the present application, the step of adding the nitrogen-containing heterocyclic compound, the bromine-containing α-olefin, and the catalyst to a predetermined solvent to prepare a comonomer of a cycloolefin copolymer may include the following steps 101 to 103:

[0130] Step 101: sequentially adding the nitrogen-containing heterocyclic compound, the bromine-containing α-olefin, and the catalyst to a predetermined solvent, stirring and refluxing the mixture at a first predetermined temperature for a first predetermined time, and after cooling to room temperature, removing salt from the reactants by suction filtration and removing the reaction solvent by rotary evaporation to obtain a product; wherein the molar ratio of the nitrogen-containing heterocyclic compound to the bromine-containing α-olefin is 1:1-2;

[0131] Step 102: washing the product obtained in step 101 with an organic solvent, collecting the filtrate, and then performing rotary evaporation to obtain a solid residue;

[0132] Step 103: purify the solid residue by silica gel column chromatography to obtain a comonomer of the cycloolefin copolymer.

[0133] According to the above steps 101 to 103 , this is a specific process for synthesizing the comonomer of the cycloolefin copolymer.

[0134] In step 101, a nitrogen-containing heterocyclic compound, a bromine-containing alpha-olefin, and a catalyst are sequentially added to a reaction solvent. The nitrogen-containing heterocyclic compound and the bromine-containing alpha-olefin are the primary components of the comonomer, while the catalyst promotes the reaction. The reaction solvent is introduced and the reaction conditions are controlled to allow these compounds to fully react during stirring and reflux. After cooling to room temperature, the salts and excess solvent produced during the reaction are removed by suction filtration and rotary evaporation, thereby obtaining a preliminary product.

[0135] In step 101, the reaction is stirred and refluxed at a first set temperature to ensure sufficient contact and reaction between the reactants. After the reaction proceeds for the first set time, the reaction mixture is cooled to room temperature. At this point, suction filtration can be used to remove salt byproducts produced during the reaction, while rotary evaporation can effectively remove excess solvent, thereby obtaining a preliminary product.

[0136] It should be noted that the molar ratio of the nitrogen-containing heterocyclic compound to the bromine-containing α-olefin is 1:1 to 2 as indicated in step 101. This ratio is selected to ensure that the two substances can react fully during the reaction while avoiding unnecessary side reactions caused by excess.

[0137] For example, in step 101, the set solvent is 100 ml, the nitrogen-containing heterocyclic compound is 40 mmol, the bromine-containing α-olefin is 48 mmol, and the catalyst is 100 mmol; wherein the set solvent includes at least one of n-hexane, acetonitrile, toluene, tetrahydrofuran, dichloromethane, ether and n-pentane; the nitrogen-containing heterocyclic compound includes indole or carbazole; the bromine-containing α-olefin is 4-bromo-1-butene or 5-bromo-1-pentene; and the catalyst is K2CO3.

[0138] In step 102, the product obtained in step 101 is further purified.

[0139] In step 102, the product of step 101 may be washed with an organic solvent. The organic solvent may be, for example, ethyl acetate. This step is intended to remove impurities that may be adsorbed on the surface of the product and unreacted raw materials, thereby improving the purity of the product. The washed solution is then filtrated and subjected to rotary evaporation to obtain a solid residue.

[0140] In step 103, the solid residue from step 102 is purified by silica gel column chromatography.

[0141] Silica gel column chromatography is a highly efficient separation technique that utilizes differences in the adsorption and desorption properties of substances on a silica gel column to separate the different components in a mixture. This step can further remove trace impurities from the solid residue, yielding a higher-purity comonomer for the cycloolefin copolymer. The silica gel column chromatography purification process requires n-hexane and ethyl acetate, with a mass ratio of n-hexane to ethyl acetate ranging from 30:1 to 10:1, for example.

[0142] The step 101 provided in the example of the present application, step 103, describes in detail the synthetic method of the comonomer of cycloolefin copolymer.Wherein, by accurately controlling reaction conditions and material ratio, the efficient synthesis of the comonomer of cycloolefin copolymer is achieved, and production efficiency is improved.Wherein, organic solvent washing and silica gel column chromatography are utilized to purify, effectively removing the impurities in the product, ensuring the high purity of the comonomer, and providing high-quality raw materials for subsequent polymerization.Step 101 to step 103 is a fine and efficient synthesis process, which, by accurately controlling reaction conditions and purification steps, achieves the preparation of the comonomer of high-purity cycloolefin copolymer.

[0143] In some examples of the present application, the bromine-containing α-olefin includes 4-bromo-1-butene or 5-bromo-1-pentene, and the catalyst includes K2CO3; wherein the salt removed from the reactants includes K2CO3 and KBr; the first set temperature is 70°C to 80°C, and the first set time is 6h-18h.

[0144] In the examples of the present application, referring to step 101 above, the bromine-containing alpha-olefin is selected to be 4-bromo-1-butene or 5-bromo-1-pentene. Both compounds contain bromine atoms, which makes them particularly reactive and suitable for the preparation of comonomers. Furthermore, due to the different positions of the bromine atoms (on the fourth and fifth carbon atoms, respectively), they may result in different reaction characteristics and copolymer structures.

[0145] In this application's examples, K2CO3 was selected as the catalyst. K2CO3 promotes comonomer synthesis in the reaction by reducing the activation energy and increasing the reaction rate. Furthermore, as an inorganic salt, K2CO3 exhibits greater stability and environmental friendliness than some organic catalysts.

[0146] Referring to step 101 above, during the reaction, some salt byproducts, such as K2CO3 and KBr, are generated. These salts need to be removed after the reaction to ensure the purity of the final product.

[0147] In the examples of this application, reaction temperatures of 70°C to 80°C and reaction times of 6 to 18 hours are given. These conditions are specific to the materials used in the entire reaction, for example, the catalyst is K2CO3. Within this temperature and time range, the reaction in step 101 can proceed relatively completely while avoiding side reactions and product decomposition that may occur due to excessively long reaction times or high temperatures.

[0148] In some examples of the present application, the step of mixing the comonomer and the toluene solution of norbornene and then adding the mixture to the catalyst system to obtain a reaction system includes the following steps 201 to 203:

[0149] Step 201: Under anhydrous and oxygen-free conditions, the comonomer obtained in step 103 is mixed with a toluene solution of norbornene at a molar ratio of 1:1 to obtain a mixed monomer; wherein the toluene solution of norbornene is obtained by adding norbornene to a toluene solution;

[0150] Step 202: Under anhydrous and oxygen-free conditions, the metallocene catalyst and the co-catalyst are mixed in a set ratio and activated to obtain a catalyst system;

[0151] Step 203 , mixing the mixed monomers obtained in step 201 with the catalyst system obtained in step 202 , heating to a second set temperature and reacting at a set pressure for a second set time to obtain a reaction system.

[0152] According to an example of the present application, a process of mixing the comonomer of the cycloolefin copolymer obtained in step 1 with a toluene solution of norbornene and then adding the mixture to the catalyst system is described in detail, including steps 201 to 203.

[0153] In step 201, the reaction is first performed under anhydrous and oxygen-free conditions. Drying can be performed in advance to prevent the effects of moisture and oxygen on the reaction. Subsequently, the comonomer of the cycloolefin copolymer obtained in step 103 is mixed with a toluene solution of norbornene in a molar ratio of 1:1 to obtain a mixed monomer. The toluene solution of norbornene is prepared by adding norbornene to toluene. Toluene, as a solvent, facilitates uniform mixing of the norbornene and comonomer.

[0154] In step 202, the metallocene catalyst and co-catalyst are mixed in a predetermined ratio under anhydrous and oxygen-free conditions for activation. For example, the metallocene catalyst may be present in an amount of 3 mg to 5 mg, and the co-catalyst may be present in an amount of 3 ml to 4 ml. The purpose of this step is to activate the catalyst system, making it catalytically active and capable of initiating the subsequent polymerization reaction. The activation process involves temperature and time control to ensure sufficient reaction between the catalyst and co-catalyst to form an efficient catalytic system.

[0155] In step 203, the monomer mixture obtained in step 201 is mixed with the catalyst system obtained in step 202. The mixture is then heated to a second set temperature and reacted under a set pressure. This step is a critical stage in the polymerization reaction. By controlling the temperature and pressure conditions, the monomer mixture polymerizes under the action of the catalyst to form the target product. After the reaction proceeds for the second set time, a reaction system is obtained.

[0156] According to steps 201 to 203 provided in the example of this application, the technical effects are as follows:

[0157] By operating under anhydrous and oxygen-free conditions, the interference of moisture and oxygen on the reaction is avoided, thus ensuring the purity of the product.

[0158] The activation treatment of the metallocene catalyst and the co-catalyst can form a highly efficient catalytic system, thereby improving the rate and efficiency of the polymerization reaction.

[0159] By controlling reaction conditions such as reaction temperature, pressure and time, precise control of the polymerization reaction can be achieved to ensure that the structure and performance of the product meet the requirements.

[0160] Toluene is selected as the solvent due to its low toxicity and volatility, which meets environmental requirements. At the same time, by optimizing the reaction conditions, energy consumption and waste emissions can be reduced, achieving the goal of green chemistry.

[0161] In some examples of the present application, the second set temperature is 50° C. to 120° C.; the set pressure is 0.1 MPa to 1 MPa; and the second set time is 4 hours to 12 hours.

[0162] According to the above example, the ranges of the second set temperature, set pressure and second set time in step 203 are further described, which have a key technical effect on the smooth progress of the polymerization reaction and the regulation of product performance.

[0163] Setting the second set temperature within the range of 50°C to 120°C ensures that the polymerization reaction proceeds at an appropriate temperature. A temperature that is too low may result in a slow reaction rate, while a temperature that is too high may trigger side reactions or product decomposition. Within this temperature range, the polymerization reaction proceeds at an appropriate rate, improving reaction efficiency.

[0164] The coordinated control of temperature, pressure, and reaction time is crucial to the structure and properties of the resulting polymer. Within a set pressure range (e.g., 0.1 MPa to 1 MPa) and reaction time (e.g., 4 to 12 hours), the polymerization process can be regulated, enabling precise control of properties such as product molecular weight, molecular weight distribution, and degree of branching. This facilitates the preparation of cycloolefin copolymers with tailored properties to meet diverse application requirements.

[0165] Appropriate temperature and pressure conditions help maintain reaction stability and reduce the occurrence of side reactions. At the same time, by controlling the reaction time, problems such as product degradation or color change caused by excessive reaction time can be avoided, ensuring product quality and stability.

[0166] The set temperature, pressure, and reaction time ranges are easy to achieve and control in practice, facilitating industrial production. Furthermore, these conditions were chosen with safety and environmental considerations in mind, avoiding potential safety risks and environmental issues associated with excessively high temperatures or pressures.

[0167] In some examples of the present application, the step of adding the reaction system to the extraction system to prepare the cyclic olefin copolymer includes the following steps 301 to 303:

[0168] Step 301: Add concentrated hydrochloric acid to ethanol to form an extraction system;

[0169] Step 302: Cool the reaction system to room temperature and then add it to the extraction system and stir;

[0170] Step 303: Separate the polymer by suction filtration, wash it with an organic solvent, and dry it to obtain a cycloolefin copolymer.

[0171] According to steps 301 to 303 provided in the example of this application, a key step in the process of preparing cycloolefin copolymer is described, namely, using a mixed system of ethanol and concentrated hydrochloric acid to extract and purify the polymer in the obtained reaction system.

[0172] In step 301, first, concentrated hydrochloric acid is added to ethanol to form an extraction system. For example, the ethanol is 300 ml and the concentrated hydrochloric acid is 4 ml. The purpose of this step is to prepare an extraction agent so as to isolate the cycloolefin copolymer from the reaction system. The mixing of ethanol and concentrated hydrochloric acid can form a solution with specific properties that can interact with the target polymer, thereby achieving a separation effect.

[0173] Specifically, the extraction system composed of ethanol and concentrated hydrochloric acid can achieve selective extraction of the copolymer based on the solubility difference between the copolymer and other reaction components, thereby improving the purity of the final copolymer.

[0174] The addition of concentrated hydrochloric acid lowers the pH of the system, which helps change the solubility of the copolymer in the solvent and promotes its precipitation from the reaction system. Furthermore, ethanol, as a good solvent, interacts with the copolymer, further promoting its precipitation and separation.

[0175] Extraction using an ethanol and concentrated hydrochloric acid extraction system simplifies subsequent separation and purification steps. The copolymer can be directly isolated from the mixed system, avoiding the use of other complex separation techniques and improving production efficiency.

[0176] Among them, concentrated hydrochloric acid is a strong acid with extremely high reactivity. In the copolymerization reaction, if concentrated hydrochloric acid is introduced, it may chemically react with certain components in the reaction system, thereby changing the kinetics or thermodynamic conditions of the reaction, resulting in the copolymerization reaction being unable to continue. The strong acidity of concentrated hydrochloric acid may destroy the equilibrium conditions required for the copolymerization reaction. Copolymerization reactions usually require a specific pH value and ionic strength to maintain the reaction. The addition of concentrated hydrochloric acid may significantly change these conditions, making it impossible for the reaction system to maintain the stable state required for the copolymerization reaction, thereby causing the reaction to be interrupted. In addition, concentrated hydrochloric acid may also interact with the catalyst or initiator in the reaction system. These interactions may cause the catalyst to be deactivated or the initiator to be consumed too quickly, making it impossible to effectively maintain the progress of the copolymerization reaction.

[0177] In step 302, the reaction system is cooled to room temperature and then added to the extraction system prepared above with stirring. Cooling to room temperature ensures that the reaction system is stable when added to the extraction system, preventing temperature fluctuations from adversely affecting the extraction effect. Stirring facilitates full contact between the polymer and the extractant, improving extraction efficiency.

[0178] In step 303, the cycloolefin copolymer can be separated from the extraction system by suction filtration. Suction filtration is an effective solid-liquid separation method that can quickly remove impurities and solvents in the solution. The isolated cycloolefin copolymer is then washed with an organic solvent, such as ethyl acetate, to remove residual extraction agent and other impurities. Finally, the purified cycloolefin copolymer can be obtained by, for example, vacuum drying.

[0179] Efficient separation and purification: Using a mixture of ethanol and concentrated hydrochloric acid as the extraction agent effectively separates the polymer from the reaction system, achieving efficient purification. This extraction method offers excellent selectivity and ease of operation, making it suitable for large-scale production.

[0180] According to steps 301 to 303 provided in the example of this application, the technical effect is as follows: through a series of steps of filtration, washing, and drying, impurities and residual solvents in the cyclic olefin copolymer can be removed, significantly improving the purity of the product. The pure cyclic olefin copolymer has better performance and stability, which can meet the requirements of high-end applications.

[0181] According to another embodiment of the present application, a cycloolefin copolymer is provided. The cycloolefin copolymer is prepared using the preparation method described above.

[0182] According to the cycloolefin copolymer provided in the embodiments of the present application, the copolymer is obtained by adopting the above-mentioned carefully designed preparation method, and in particular, has a significant improvement in refractive index.

[0183] During the preparation process, nitrogen-containing heterocyclic compounds and bromine-containing α-olefins were selected as the primary comonomers. These monomers can form specific segment structures during polymerization, which can influence the propagation path of light in the polymer, thereby achieving regulation of the refractive index. Furthermore, through the precise selection of catalyst type and dosage, as well as meticulous control of reaction conditions such as temperature, pressure, and time, the molecular structure and segment arrangement of the copolymer can be precisely controlled, further enhancing its refractive index.

[0184] In addition, in the subsequent extraction, washing and drying processes, an efficient and environmentally friendly ethanol and concentrated hydrochloric acid mixed system was used to ensure that while impurities and residual solvents were removed, the refractive index of the copolymer was not negatively affected.

[0185] A carefully designed preparation method has yielded a cyclic olefin copolymer with a high refractive index. This cyclic olefin copolymer has broad application prospects in the field of optical materials, including the manufacture of high-refractive-index lenses, optical components, and high-performance optical coatings, providing strong support for the development of optical technology.

[0186] According to another embodiment of the present application, a cyclic olefin copolymer is further provided, and the general structural formula of the cyclic olefin copolymer is as follows:

[0187]

[0188] Wherein, n=3 or 4, R represents a nitrogen-containing heterocyclic group, including an indole group or a carbazolyl group; x and y represent the number of repeating units.

[0189] It should be noted that the cyclic olefin copolymers provided in the examples of this application utilize indole or carbazole as the raw material for the comonomer. Therefore, the R group in the above general structural formula can be an indole group or a carbazole group. Combined with n=3 or 4, the cyclic olefin copolymers have four structures. Among these, the indole group or the carbazole group plays an important role in the high refractive index.

[0190] In some examples of the present application, the first molecular formula of the cyclic olefin copolymer is as follows:

[0191]

[0192] In some examples of the present application, the second molecular formula of the cyclic olefin copolymer is as follows:

[0193]

[0194] In some examples of the present application, the third molecular formula of the cyclic olefin copolymer is as follows:

[0195]

[0196] In some examples of the present application, the fourth molecular formula of the cyclic olefin copolymer is as follows:

[0197]

[0198] In some examples of the present application, the molecular weight of the cyclic olefin copolymer is 50,000 to 150,000, and the glass transition temperature thereof is 100° C. to 180° C.

[0199] According to the examples of this application, the key physical properties of the cycloolefin copolymer provided in this application are further refined. Specifically, it points out the molecular weight range and the glass transition temperature range of the copolymer.

[0200] About molecular weight, it is the average length of polymer chains or the measurement of quality. The size of molecular weight directly affects the physical and chemical properties of polymer. In the present application, the molecular weight of cycloolefin copolymer is between 50000 and 150000. This specific scope means that this copolymer has a molecular chain of moderate length, thereby can show good processing properties, mechanical strength and thermal stability. Molecular weight is too low and may cause the material to be too soft, while molecular weight is too high and may make the material too brittle or difficult to process.

[0201] Glass transition temperature is an important thermal property of polymers. It indicates the transition temperature of the polymer from the glassy state to the rubbery state, that is, the temperature at which the polymer chain segments begin to move freely. The high or low glass transition temperature determines the performance of the polymer at different temperatures. In this application, the glass transition temperature of the cycloolefin copolymer is set at 100°C to 180°C. This temperature range means that the copolymer can still maintain a certain shape and performance at high temperatures, and will not be too brittle at low temperatures. Such a glass transition temperature range enables the copolymer to exhibit good performance in a variety of application scenarios, such as the insulating layer of electronic equipment, optical lenses, etc.

[0202] The present application also provides an optical product, which can be prepared using the cycloolefin copolymer of any of the above embodiments. Since the cycloolefin copolymer of the present application also 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.

[0203] An embodiment of the present application also provides an electronic device, which includes the optical product of any of the above embodiments. Since the optical product has good optical properties, the electronic device also has the same advantages, which will not be described in detail here.

[0204] The cycloolefin polymer and the preparation method thereof according to the present application are described in detail below with reference to specific examples.

[0205] Example 1

[0206] This embodiment 1 provides a cycloolefin copolymer, the molecular formula of which is as follows:

[0207]

[0208] This embodiment 1 provides a method for preparing a cycloolefin copolymer, and the reaction formula is as follows:

[0209]

[0210] This embodiment 1 provides a method for preparing a cycloolefin copolymer, and the specific method is as follows:

[0211] 100 ml of acetonitrile (presumed solvent) was placed in a 250 ml flask, and 40 mmol of indole, 48 mmol of 4-bromo-1-butene, and 100 mmol of K2CO3 were added in sequence. The mixture was stirred and refluxed at 80°C for 12 h. After cooling to room temperature, the salts (including K2CO3 and 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 purified by column chromatography on a silica gel column using a dry method to obtain the pure comonomer 1.

[0212] Under anhydrous and oxygen-free conditions, a 250 ml Schlenk flask was replaced with nitrogen, and 100 ml of toluene was added, followed by the addition of 30 mmol of comonomer 1 and a 30 mmol toluene solution of norbornene to form a mixed monomer; in another dry reaction tube, 4 mg of metallocene catalyst c and 3 ml of MAO solution (a type of co-catalyst) were added under anhydrous and oxygen-free conditions, and pre-activated for 5 minutes to form a catalyst system; thereafter, the mixed monomer was transferred into the above dry reaction tube through a double needle to mix with the catalyst system, and the temperature was raised to 70°C and reacted for 12 hours to form a reaction system;

[0213] 300 ml of ethanol was placed in a beaker, and 3 ml of concentrated hydrochloric acid was added to form an extraction system. The reaction system was cooled to room temperature and then poured into the extraction system and stirred for a period of time. The cycloolefin copolymer was separated by filtration, and then washed with ethyl acetate three times and dried under vacuum to obtain the following cycloolefin copolymer, whose molecular formula is:

[0214]

[0215] Example 2

[0216] This embodiment 2 provides a cycloolefin copolymer, the molecular formula of which is as follows:

[0217]

[0218] This embodiment 2 provides a method for preparing a cycloolefin copolymer, and the reaction formula is as follows:

[0219]

[0220] This embodiment 2 provides a method for preparing a cycloolefin copolymer, and the specific method is as follows:

[0221] 100 ml of acetonitrile (presumed solvent) was placed in a 250 ml flask, and 40 mmol of carbazole, 48 mmol of 4-bromo-1-butene, and 100 mmol of K2CO3 were added in sequence. The mixture was stirred and refluxed at 80°C for 12 h. After cooling to room temperature, the salts (including K2CO3 and 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 purified by column chromatography on a silica gel column using a dry method to obtain the pure comonomer 2.

[0222] Under anhydrous and oxygen-free conditions, a 250 ml Schlenk flask was replaced with nitrogen, and 100 ml of toluene was added, followed by the addition of 30 mmol of comonomer 2 and 30 mmol of a toluene solution of norbornene to form a mixed monomer; in another dry reaction tube, 3 mg of metallocene catalyst c and 3 ml of MAO solution (a type of co-catalyst) were added under anhydrous and oxygen-free conditions, and pre-activated for 5 minutes to form a catalyst system; thereafter, the mixed monomer was transferred into the above dry reaction tube through a double needle to mix with the catalyst system, and the temperature was raised to 70°C and reacted for 12 hours to form a reaction system;

[0223] 300 ml of ethanol was placed in a beaker, and 4 ml of concentrated hydrochloric acid was added to form an extraction system. The reaction system was cooled to room temperature and then poured into the extraction system and stirred for a period of time. The cycloolefin copolymer was separated by filtration, and then washed with ethyl acetate three times and vacuum dried to obtain the following cycloolefin copolymer, whose molecular formula is:

[0224]

[0225] Example 3

[0226] This embodiment 2 provides a cycloolefin copolymer, the molecular formula of which is as follows:

[0227]

[0228] This embodiment 3 provides a method for preparing a cycloolefin copolymer, and the reaction formula is as follows:

[0229]

[0230] This embodiment 3 provides a method for preparing a cycloolefin copolymer, and the specific method is as follows:

[0231] 100 ml of acetonitrile (presumed solvent) was placed in a 250 ml flask, and 40 mmol of indole, 48 mmol of 5-bromo-1-pentene, and 100 mmol of K2CO3 were added in sequence. The mixture was stirred and refluxed at 80°C for 12 h. After cooling to room temperature, the salts (including K2CO3 and KBr) in the reaction system were removed by suction, 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 purified by column chromatography on a silica gel column using a dry method to obtain the pure comonomer 3.

[0232] Under anhydrous and oxygen-free conditions, a 250 ml Schlenk flask was replaced with nitrogen, and 100 ml of toluene was added, followed by the addition of 30 mmol of comonomer 3 and 30 mmol of a toluene solution of norbornene to form a mixed monomer; in another dry reaction tube, 5 mg of metallocene catalyst c and 4 ml of MAO solution (a type of co-catalyst) were added under anhydrous and oxygen-free conditions, and pre-activated for 5 minutes to form a catalyst system; thereafter, the mixed monomer was transferred into the above dry reaction tube through a double needle to be mixed with the catalyst system, and the temperature was raised to 70°C and reacted for 12 hours to form a reaction system;

[0233] 300 ml of ethanol was placed in a beaker, and 4 ml of concentrated hydrochloric acid was added to form an extraction system. The reaction system was cooled to room temperature and then poured into the extraction system and stirred for a period of time. The cycloolefin copolymer was separated by filtration, and then washed with ethyl acetate three times and vacuum dried to obtain the following cycloolefin copolymer, whose molecular formula is:

[0234]

[0235] Example 4

[0236] This embodiment 4 provides a cycloolefin copolymer, the molecular formula of which is as follows:

[0237]

[0238] This embodiment 4 provides a method for preparing a cycloolefin copolymer, and the reaction formula is as follows:

[0239]

[0240] This embodiment 4 provides a method for preparing a cycloolefin copolymer, and the specific method is as follows:

[0241] 100 ml of acetonitrile (set solvent) was placed in a 250 ml flask, and 40 mmol of carbazole, 48 mmol of 5-bromo-1-pentene, and 100 mmol of K2CO3 were added in sequence. The mixture was stirred and refluxed at 80°C for 12 h. After cooling to room temperature, the salts (including K2CO3 and 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 purified by column chromatography on a silica gel column using a dry method to obtain the pure comonomer 4.

[0242] Under anhydrous and oxygen-free conditions, a 250 ml Schlenk flask was replaced with nitrogen, and 100 ml of toluene was added, followed by the addition of 30 mmol of comonomer 4 and 30 mmol of a toluene solution of norbornene to form a mixed monomer; in another dry reaction tube, 3 mg of metallocene catalyst c and 3 ml of MAO solution (a type of co-catalyst) were added under anhydrous and oxygen-free conditions, and pre-activated for 5 minutes to form a catalyst system; thereafter, the mixed monomer was transferred into the above dry reaction tube through a double needle to be mixed with the catalyst system, and the temperature was raised to 70°C and reacted for 12 hours to form a reaction system;

[0243] 300 ml of ethanol was placed in a beaker, and 4 ml of concentrated hydrochloric acid was added to form an extraction system. The reaction system was cooled to room temperature and then poured into the extraction system and stirred for a period of time. The cycloolefin copolymer was separated by filtration, and then washed with ethyl acetate three times and vacuum dried to obtain the following cycloolefin copolymer, whose molecular formula is:

[0244]

[0245] Comparative Example 1

[0246] Under anhydrous and oxygen-free conditions, a 250ml Schlenk flask was purged with nitrogen and charged with 100ml of toluene, 5mg of metallocene catalyst a, 5ml of MAO solution (a co-catalyst), and 1ml of triethylaluminum. Ethylene was then introduced to a pressure of 0.8MPa. The mixture was stirred and heated to 70°C for 30 minutes. The polymerization was terminated by adding 200ml of a 10wt% HCl solution in ethanol. The resulting copolymer was filtered, rinsed with ethanol, and then dried in vacuo.

[0247] Comparative Example 2

[0248] Under anhydrous and oxygen-free conditions, a 250ml Schlenk flask was purged with nitrogen and charged with 100ml of toluene, 5mg of metallocene catalyst B, 5ml of MAO solution (a co-catalyst), and 1ml of triethylaluminum. Ethylene was then introduced to a pressure of 0.8MPa. The mixture was stirred and heated to 80°C for 30 minutes. The polymerization was terminated by adding 100ml of a 10wt% HCl solution in ethanol. The resulting copolymer was filtered, rinsed with ethanol, and then dried in vacuo.

[0249] 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 in Examples 1 to 4 and Comparative Examples 1 and 2 can be referred to as shown in Table 1.

[0250] Table 1

[0251]

[0252] It can be seen from Table 1 above that compared with Comparative Examples 1 and 22, Examples 1 to 4 have higher refractive indices (>1.6), higher NB monomer insertion rates (>30%), and higher glass transition temperatures (>145).

[0253] 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.

[0254] 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 for illustration only and are not intended to limit the scope of the present application. It should be understood by those skilled in the art that the above examples 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 method for preparing a cycloolefin copolymer, characterized in that: include: Mixing a nitrogen-containing heterocyclic compound with an α-olefin containing a bromine atom to prepare a comonomer of a cycloolefin copolymer; wherein the nitrogen-containing heterocyclic compound comprises indole or carbazole; The comonomer and norbornene toluene solution are mixed and then added to a catalyst system to obtain a reaction system; wherein the catalyst system is composed of a metallocene catalyst as a main catalyst and a cocatalyst; The reaction system is added to the extraction system to prepare a cycloolefin copolymer.

2. The preparation method according to claim 1, characterized in that The preparation method comprises: sequentially adding the nitrogen-containing heterocyclic compound, the bromine-containing α-olefin and a catalyst into a predetermined solvent to prepare a comonomer of the cycloolefin copolymer.

3. The preparation method according to claim 2, characterized in that The bromine-containing α-olefin includes 4-bromo-1-butene or 5-bromo-1-pentene; The set solvent includes at least one of n-hexane, acetonitrile, toluene, tetrahydrofuran, dichloromethane, diethyl ether and n-pentane; The catalyst includes K2CO3.

4. The preparation method according to claim 1, characterized in that The mass ratio of the metallocene catalyst to the co-catalyst is 1:(10-2000).

5. The preparation method according to claim 1, characterized in that The metallocene catalyst includes any one of metallocene catalyst a, metallocene catalyst b and metallocene catalyst c; The molecular formula of metallocene catalyst a is as follows: The molecular formula of metallocene catalyst b is as follows: The molecular formula of metallocene catalyst c is as follows:

6. The preparation method according to claim 1, characterized in that The co-catalyst includes at least one of [Ph3C][B(C6F5)4], methylaluminoxane MAO and alkyl aluminum; The alkyl aluminum includes any one of triethyl aluminum, triisobutyl aluminum and trioctylaluminum.

7. The preparation method according to claim 2, characterized in that The method of sequentially adding the nitrogen-containing heterocyclic compound, the bromine-containing α-olefin and the catalyst into a predetermined solvent to prepare a comonomer of a cycloolefin copolymer comprises the following steps: A nitrogen-containing heterocyclic compound, a bromine-containing α-olefin, and a catalyst are sequentially added to a set solvent, stirred and refluxed at a first set temperature for a first set time, and after cooling to room temperature, salts in the reactants are removed by suction filtration, and the set solvent is removed by rotary evaporation to obtain a product; wherein the molar ratio of the nitrogen-containing heterocyclic compound to the bromine-containing α-olefin is 1:1-2; The obtained product is washed with an organic solvent, and the filtrate is collected and then subjected to rotary evaporation to obtain a solid residue; The solid residue is purified by silica gel column chromatography to obtain the comonomer of the cycloolefin copolymer.

8. The preparation method according to claim 7, characterized in that The bromine-containing α-olefin includes 4-bromo-1-butene or 5-bromo-1-pentene, and the catalyst includes K2CO3; Wherein, the salts removed by suction filtration in the reactants include K2CO3 and KBr; The first set temperature is 70° C. to 80° C., and the first set time is 6 hours to 18 hours.

9. The preparation method according to claim 4, characterized in that The comonomer and norbornene toluene solution are mixed and then added to a catalyst system to obtain a reaction system, comprising: Under anhydrous and oxygen-free conditions, the comonomer and a toluene solution of norbornene are mixed at a molar ratio of 1:1 to obtain a mixed monomer; wherein the toluene solution of norbornene is obtained by adding norbornene to a toluene solution; Under anhydrous and oxygen-free conditions, the metallocene catalyst and the co-catalyst are mixed in a set amount ratio and activated to obtain a catalyst system; The mixed monomers and the catalyst system are mixed, heated to a second set temperature, and reacted under a set pressure for a second set time to obtain a reaction system.

10. The preparation method according to claim 9, characterized in that The second set temperature is 50°C to 120°C; The set pressure is 0.1MPa to 1MPa; The second set time length is 4 hours to 12 hours.

11. The preparation method according to claim 10, characterized in that: The step of adding the reaction system to the extraction system to prepare a cycloolefin copolymer comprises: Concentrated hydrochloric acid added to ethanol forms an extraction system; The reaction system was cooled to room temperature and then added to the extraction system and stirred; The polymer is separated by suction filtration, washed with an organic solvent, and dried to obtain a cycloolefin copolymer.

12. A cycloolefin copolymer, characterized in that The method is described in any one of claims 1 to 11.

13. A cycloolefin copolymer, characterized in that The general structural formula of the cycloolefin copolymer is as follows: Wherein, n=3 or 4, R represents a nitrogen-containing heterocyclic group, including an indole group or a carbazolyl group; x and y represent the number of repeating units.

14. The cyclic olefin copolymer according to claim 13, characterized in that The molecular formula of the cycloolefin copolymer is as follows: Wherein, x and y represent the number of repeating units.

15. The cyclic olefin copolymer according to claim 13, characterized in that The molecular formula of the cycloolefin copolymer is as follows: Wherein, x and y represent the number of repeating units.

16. The cyclic olefin copolymer according to claim 13, wherein The molecular formula of the cycloolefin copolymer is as follows: Wherein, x and y represent the number of repeating units.

17. The cyclic olefin copolymer according to claim 13, wherein The molecular formula of the cycloolefin copolymer is as follows: Wherein, x and y represent the number of repeating units.

18. The cyclic olefin copolymer according to any one of claims 13 to 17, characterized in that The molecular weight of the cycloolefin copolymer is 50,000 to 150,000, and the glass transition temperature is 100° C. to 180° C.

19. An optical product, characterized in that: The optical product is prepared from the cyclic olefin copolymer according to any one of claims 13 to 18.

20. An electronic device, characterized in that: The optical article according to claim 19 is included.

Images