Cyclic olefin copolymer, preparation method thereof, optical product and electronic device

Abstract

The present application discloses a cycloolefin copolymer and a preparation method thereof, an optical product and an electronic device; wherein the cycloolefin copolymer contains a halogenated heterocyclic structure portion, and the molecular structure of the cycloolefin copolymer is as follows: in formula (I), x, y and z are the polymerization degrees and satisfy: 20≥x≥1, y≥1, z≥1; m and o are the lengths of the monomer chains and satisfy: 1≤m≤10, 1≤o≤10; n is the length of the main chain and satisfies: 50≤n≤5000; at least one of R1, R2, R3, R4, R5, R6, R7 and R8 is a halogen atom.

Description

Technical Field

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

[0002] Cyclic olefin copolymer (COC) is a new class of thermoplastic optical plastics, primarily formed by the copolymerization of cycloolefin monomers with α-olefins. In the research and development and application of optical lens materials, COC has become a leader in the field due to its unique optical properties. In particular, when used as a lens material, the refractive index of COC is closely linked to the lens's thinness and optical performance. In theory, a higher refractive index allows for significantly reduced lens thickness and weight while maintaining the same optical performance. This is of great significance for optical devices that strive for lightweight, portable, and high-quality imaging.

[0003] The refractive index of current COC materials generally hovers around 1.54, significantly limiting their potential for application in high-end optics. In particular, cutting-edge technology fields such as aerospace satellites, drones, and integrated circuit chip inspection are experiencing a growing demand for ultra-high-definition microlenses. These applications require lens materials with even higher refractive indices to accurately capture minute details and achieve high-definition imaging. Consequently, existing COC materials struggle to meet these customized, high-performance requirements.

[0004] Furthermore, increasing a material's refractive index often comes with a significant challenge: increased dispersion. Dispersion is the phenomenon in which light is deflected to varying degrees by varying wavelengths as it passes through a medium. Its degree is measured by the Abbe number. The smaller the Abbe number, the more severe the dispersion, which can adversely affect the lens's imaging quality, such as color distortion and blurred edges. Therefore, while pursuing a high refractive index, effectively controlling and increasing the material's Abbe number to achieve a balance between refractive index and dispersion has become a key technical challenge urgently needed in the research and development of COC materials. Summary of the Invention

[0005] One purpose of the present application is to provide a cycloolefin copolymer that can solve the technical problems in the prior art of cycloolefin copolymers such as difficulty in achieving a high refractive index and a low Abbe number.

[0006] Another object of the present application is to provide a method for preparing a cycloolefin copolymer.

[0007] Another object of the present application is to provide an optical product prepared by the above-mentioned cycloolefin copolymer.

[0008] Yet another object of the present application is to provide an electronic device comprising the above optical product.

[0009] In order to achieve the above objectives, this application provides the following technical solutions.

[0010] According to the cyclic olefin copolymer of the first embodiment of the present application, the cyclic olefin copolymer contains a halogenated heterocyclic structure portion, and the molecular structure of the cyclic olefin copolymer is as follows:

[0011]

[0012] In formula (I), x, y and z are the degrees of polymerization and satisfy: 20≥x≥1, y≥1, z≥1;

[0013] m and o are the lengths of the monomer chain and satisfy: 1≤m≤10, 1≤o≤10;

[0014] n is the length of the main chain, and satisfies: 50≤n≤5000;

[0015] At least one of R1, R2, R3, R4, R5, R6, R7 and R8 is a halogen atom.

[0016] Optionally, in the formula (I), R1, R2, R3, R4, R5, R6, R7, and R8 are respectively selected from F, Cl, Br, I, a halogen atom or a hydrogen atom, but R1, R2, R3, R4, R5, R6, R7, and R8 cannot be H atoms at the same time, and at least one halogen atom is present.

[0017] Optionally, there are two or more halogen atoms in R1, R2, R3, R4, R5, R6, R7, and R8.

[0018] Optionally, the halogenated heterocyclic structure moiety includes a halogenated benzopyrrole, a halogenated benzodihydropyrrole or a halogenated carbazole.

[0019] Optionally, the cyclic olefin copolymer comprises the following halogenated heterocyclic polymer;

[0020]

[0021] Among them, 20≥x≥1, y≥1, z≥1, 1≤m≤10, 1≤o≤10, 50≤n≤5000.

[0022] Optionally, the cyclic olefin copolymer has a high refractive index of 1.60 to 1.72;

[0023] The glass transition temperature Tg of the cycloolefin copolymer is: 200°C <Tg<300℃。

[0024] According to the preparation method of the cycloolefin copolymer of the second embodiment of the present application, the preparation method comprises:

[0025] In a toluene solvent, a cycloolefin monomer, an α-olefin monomer and a halogenated heterocyclic olefin monomer are polymerized in the presence of a catalyst to obtain a cycloolefin copolymer. The molecular structure of the cycloolefin copolymer is as follows:

[0026]

[0027] In formula (I), x, y and z are the degrees of polymerization and satisfy: 20≥x≥1, y≥1, z≥1;

[0028] m and o are the lengths of the monomer chain and satisfy: 1≤m≤10, 1≤o≤10;

[0029] n is the length of the main chain, and satisfies: 50≤n≤5000;

[0030] At least one of R1, R2, R3, R4, R5, R6, R7 and R8 is a halogen atom.

[0031] Optionally, the structural formula of the cycloolefin monomer is as follows:

[0032]

[0033] The structural formula of the α-olefin monomer is as follows:

[0034]

[0035] The structural formula of the halogenated heterocyclic olefin monomer is as follows:

[0036]

[0037] Optionally, the halogenated heterocyclic olefin monomer is any one of the following structural formulas:

[0038]

[0039] Optionally, the catalyst is a metallocene catalyst.

[0040] Optionally, the chemical structural formula of the catalyst is any one of the following:

[0041]

[0042] Optionally, the molar ratio of the cycloolefin monomer, the α-olefin monomer and the halogenated heterocyclic olefin monomer is 1-50:1-50:5-100.

[0043] Optionally, the molar ratio of the catalyst to the cycloolefin monomer is 1:500 to 6000;

[0044] The molar ratio of the catalyst to the α-olefin monomer is 1:50 to 2000, and the α-olefin monomer is a polar or aromatic substituted olefin monomer.

[0045] Optionally, the polymerization reaction temperature is 25° C. to 150° C., and the polymerization reaction time is 0.5 h to 48 h.

[0046] According to the optical product of the third embodiment of the present application, the optical product is prepared from any of the above-mentioned cycloolefin copolymers.

[0047] The electronic device according to the fourth embodiment of the present application includes any of the above-mentioned optical products.

[0048] The beneficial effects of this application are:

[0049] The cycloolefin copolymer provided in the embodiments of the present application constructs an olefin monomer having a halogenated heterocyclic structure by introducing a halogen group with a high molar refractive index and a low molar volume into a heteroatom cyclic group. This design effectively combines two molecular structural features that enhance the refractive index, so that the prepared halogenated heterocyclic olefin monomer can significantly increase the refractive index of the cycloolefin copolymer to a level greater than 1.7 after copolymerization, meeting the high refractive index requirements of high-performance optical materials.

[0050] The cyclic olefin copolymers provided in the examples of this application are prepared by terpolymerizing a halogenated heterocyclic olefin monomer, an α-olefin, and a cycloolefin. The chain length and feed ratio of the α-olefin can be adjusted to control the polymer's glass transition temperature and elongation at break, enhancing its toughness. Furthermore, the cyclic olefin copolymers maintain excellent light transmittance, broadening their applications in optics and related fields.

[0051] Other features and advantages of the present application will become apparent from the following detailed description of exemplary embodiments of the present application. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] Figure 1 This is the H NMR spectrum of the halogenated heterocyclic monomer of Example 5 in this application;

[0053] Figure 2 This is the C NMR spectrum of the halogenated heterocyclic monomer of Example 5 in this application;

[0054] Figure 3 is the H NMR spectrum of the ternary copolymer of Example 48 in this application;

[0055] Figure 4This is a comparison chart of the refractive indices of the ternary copolymers of Examples 33-42, 50, and 51 of this application;

[0056] Figure 5 is the tensile fracture curve of Example 49 in this application;

[0057] Figure 6 This is a transmittance curve of the ternary copolymer of Example 48 in this application. DETAILED DESCRIPTION

[0058] 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.

[0059] 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.

[0060] Technologies, methods, and equipment known to ordinary technicians in the relevant art may not be discussed in detail, but where appropriate, the technologies, methods, and equipment should be considered part of the specification.

[0061] 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.

[0062] The cycloolefin copolymer (COC) and its preparation method, optical product and electronic device of the present application are described in detail below with reference to specific embodiments.

[0063] According to a cyclic olefin copolymer provided in one embodiment of the present application, the cyclic olefin copolymer comprises a halogenated heterocyclic structure portion, and the molecular structure of the cyclic olefin copolymer is as follows:

[0064]

[0065] In formula (I), x, y and z are the degrees of polymerization and satisfy: 20≥x≥1, y≥1, z≥1;

[0066] m and o are the lengths of the monomer chain and satisfy: 1≤m≤10, 1≤o≤10;

[0067] n is the length of the main chain, and satisfies: 50≤n≤5000;

[0068] At least one of R1, R2, R3, R4, R5, R6, R7 and R8 is a halogen atom.

[0069] The cycloolefin copolymer provided in the embodiments of the present application is a high-refractive-index cycloolefin copolymer having a halogenated heterocycle. The structure of the copolymer is shown in Formula (I), which involves multiple variables and substituents:

[0070] x, y, z: represent the degree of polymerization of different parts, specifically 20≥x≥1, y≥1, z≥1;

[0071] m, o: represent the number of specific substituents, ranging from 1≤m≤10, 1≤o≤10 respectively;

[0072] n: represents the total degree of polymerization of the polymer, ranging from 50≤n≤5000.

[0073] Referring to formula (I), the halogenated heterocyclic structure of the cycloolefin copolymer includes eight independent substituents R1, R2, R3, R4, R5, R6, R7, and R8, and at least one of the eight independent substituents is a halogen atom.

[0074] The introduction of halogenated heterocyclic structures not only increases the refractive index of cycloolefin copolymers but also enhances their chemical and thermal stability. This is because the higher bond energy between halogen atoms and carbon atoms makes the material more durable in high-temperature or chemical environments.

[0075] By adjusting the molecular structure of the cyclic olefin copolymer (Formula (I)), the properties of the cyclic olefin copolymer can be precisely controlled by adjusting the values ​​of x, y, z, m, o, and n in Formula (I), as well as the specific substituents R1 to R8. This adjustability enables the cyclic olefin copolymer to meet the specific material performance requirements of different fields.

[0076] The cycloolefin copolymer provided in the embodiments of the present application constructs an olefin monomer having a halogenated heterocyclic structure by introducing a halogen group with a high molar refractive index and a low molar volume into a heteroatom cyclic group. This design effectively combines two molecular structural features that enhance the refractive index, so that the prepared halogenated heterocyclic olefin monomer can significantly increase the refractive index of the cycloolefin copolymer to a level greater than 1.7 after copolymerization, meeting the high refractive index requirements of high-performance optical materials.

[0077] The cyclic olefin copolymers provided in the embodiments of this application have a high refractive index and have broad application prospects in the fields of optics, electronics, and communications. For example, they can be used as high-refractive-index materials in optical devices to improve the optical performance of the devices; in electronic packaging materials, they can enhance the light transmittance and thermal stability of the packaging materials; and in the communications field, they can be used to manufacture high-performance optical fibers.

[0078] The cycloolefin copolymer of the embodiment of the present application is a high-refractive-index cycloolefin copolymer having a halogenated heterocycle. By introducing halogen atoms and halogenated heterocycle structures, the refractive index and stability of the cycloolefin copolymer are significantly improved, and the copolymer has excellent optical properties and broad application prospects.

[0079] In some examples of the present application, in the molecular formula of the cycloolefin copolymer, i.e., formula (I), R1, R2, R3, R4, R5, R6, R7, R8 are respectively selected from F, Cl, Br, I, a halogen atom or a H hydrogen atom, but R1, R2, R3, R4, R5, R6, R7, R8 cannot be H atoms at the same time, and there is at least one halogen atom therein.

[0080] According to the description in the examples of this application, in Formula (I), the eight substituents R1, R2, R3, R4, R5, R6, R7, and R8 are each selected from halogen atoms such as fluorine (F), chlorine (Cl), bromine (Br), and iodine (I), or hydrogen (H) atoms. However, it is stipulated that these eight substituents (i.e., R1 to R8) cannot all be hydrogen (H) atoms, and at least one halogen atom must be present. This design introduces specific chemical and physical properties to the cycloolefin copolymer.

[0081] About the role of halogen atoms:

[0082] The introduction of halogen atoms (particularly fluorine (F) and chlorine (Cl)) can significantly affect the optical, electrical, thermal, and chemical stability properties of cycloolefin copolymers. For example, the presence of halogen atoms helps increase the refractive index of cycloolefin copolymers, which is particularly important for optical materials.

[0083] Halogen atoms can also enhance the heat resistance and chemical corrosion resistance of cycloolefin copolymers, allowing them to remain stable under high temperatures or harsh chemical environments.

[0084] Regarding the restrictions on hydrogen atoms:

[0085] According to the description in the examples of this application, all substituents (ie, R1 to R8) are restricted from being hydrogen atoms at the same time. This is to ensure that the cycloolefin copolymer molecule contains at least one halogen atom, thereby giving it specific chemical and physical properties.

[0086] Due to the high polarizability of halogen atoms, their introduction can increase the refractive index of cycloolefin copolymers to greater than 1.7. Furthermore, the presence of halogen atoms can increase the glass transition temperature (Tg) of cycloolefin copolymers, allowing them to maintain their shape and performance at higher temperatures, which is crucial for materials that need to operate in high-temperature environments. Furthermore, the chemical inertness of halogen atoms helps improve the resistance of cycloolefin copolymers to chemical corrosion, allowing them to maintain stable performance in a variety of chemical environments.

[0087] Due to these excellent properties, cycloolefin copolymers containing halogenated heterocyclic structures may be widely used in many fields such as optics, electronics, aerospace, and medicine.

[0088] In some examples of the present application, two or more halogen atoms exist simultaneously in R1, R2, R3, R4, R5, R6, R7, and R8.

[0089] In this example of the present application, it is described that two or more halogen atoms (such as F, Cl, Br, I) are present in the eight substituents R1, R2, R3, R4, R5, R6, R7, and R8 in the molecular structure of the cycloolefin copolymer. This design can bring about multiple technical effects:

[0090] (1) Enhance the chemical stability of cycloolefin copolymers:

[0091] The introduction of halogen atoms, especially the presence of multiple halogen atoms, can significantly improve the chemical stability of cycloolefin copolymers. Due to their strong electronegativity, halogen atoms can attract electrons and form stable covalent bonds, thereby enhancing the rigidity and stability of the molecular chain.

[0092] (2) Optimizing the physical properties of cycloolefin copolymers:

[0093] The presence of multiple halogen atoms can also positively impact the physical properties of cycloolefin copolymers. For example, the introduction of halogen atoms can alter key physical parameters such as the glass transition temperature (Tg) of the cycloolefin copolymer. These changes can help optimize the mechanical properties and thermal stability of the cycloolefin copolymer, making it more suitable for specific applications.

[0094] (3) Improve and enhance the optical properties of cycloolefin copolymers:

[0095] The introduction of halogen atoms (F, Cl, Br, I) into cycloolefin copolymers significantly increases the material's refractive index due to their strong electronegativity and polarizability. High-refractive-index materials are widely used in optics, such as optical lenses, optical fibers, and light-guiding materials.

[0096] The unique electronic structure of halogen atoms can also impart unique optical properties to cycloolefin copolymers. For example, the introduction of certain halogen atoms (such as bromine or iodine) can cause cycloolefin copolymers to absorb or emit light within specific wavelength ranges, resulting in fluorescence, phosphorescence, or specific colors. This improved optical property has potential applications in optical materials, optoelectronic devices, and other fields.

[0097] In some examples of the present application, the halogenated heterocyclic structure includes a halogenated benzopyrrole, a halogenated benzodihydropyrrole, or a halogenated carbazole.

[0098] The cycloolefin copolymer contains a halogenated heterocyclic structure portion, which can be selected from halogenated benzopyrrole, halogenated benzodihydropyrrole or halogenated carbazole. These selections can bring at least the following effects:

[0099] The introduction of halogen atoms, particularly heavy halogens such as fluorine (F), chlorine (Cl), bromine (Br), and iodine (I), can significantly increase the refractive index of cycloolefin copolymers. High refractive indices are particularly important for optical materials because they can reduce light reflection losses at material interfaces and improve optical efficiency.

[0100] The introduction of halogenated heterocycles may increase the glass transition temperature (Tg) of cycloolefin copolymers by enhancing intermolecular interactions, such as dipole-dipole interactions between halogens and neighboring atoms. A higher glass transition temperature (Tg) means that the material can maintain its physical and mechanical properties at higher temperatures, broadening the material's application range, especially in high-temperature environments.

[0101] Halogenated heterocyclic structures generally have high chemical stability and can resist corrosion from chemical reactions such as oxidation and hydrolysis. This stability allows the material to maintain its performance under harsh environmental conditions, extending its service life.

[0102] Halogenated benzopyrroles, halogenated dihydrobenzopyrroles, and halogenated carbazoles possess specific electronic structures and spectral properties that influence the absorption and fluorescence properties of cycloolefin copolymers. These properties are particularly important in optoelectronic devices, enabling specific optical functions.

[0103] In some examples of the present application, the cyclic olefin copolymer includes the following halogenated heterocyclic polymer;

[0104]

[0105] Among them, 20≥x≥1, y≥1, z≥1, 1≤m≤10, 1≤o≤10, 50≤n≤5000.

[0106] According to the various halogenated heterocyclic polymers provided in the examples of this application, each halogenated heterocyclic polymer contains a halogenated heterocyclic structural portion, which can be a halogenated benzopyrrole, a halogenated benzodihydropyrrole, or a halogenated carbazole, etc. The introduction of these halogenated heterocycles has a significant effect on the optical, electrical, or thermal properties of the cycloolefin copolymer.

[0107] The cycloolefin copolymer, by introducing a halogenated heterocyclic structure and specific molecular structural parameters, forms a polymer material with unique physical and chemical properties. This material has broad application prospects in the fields of optics, electronics, and high-temperature resistance.

[0108] In some examples of the present application, the cyclic olefin copolymer has a high refractive index of 1.60 to 1.72. The glass transition temperature Tg of the cyclic olefin copolymer is: 200°C <Tg<300℃。

[0109] In the examples of this application, the cyclic olefin copolymers described exhibit two remarkable technical properties: a high refractive index and a specific glass transition temperature range.

[0110] The high refractive index (1.60-1.72) of the cycloolefin copolymer is one of its important physical properties. Refractive index is a measure of a material's ability to refract light. A high refractive index means the material can more effectively direct light in a specific direction, which is particularly important in optical applications. The use of high-refractive-index cycloolefin copolymers in optical components can significantly improve light transmittance and focusing efficiency, while reducing optical losses.

[0111] The glass transition temperature (Tg) is the temperature at which a polymer transitions from a glassy state to a highly elastic state, and is an important indicator of the thermal properties of polymer materials. In this application, the glass transition temperature (Tg) of the cycloolefin copolymer is between 200°C and 300°C, which is a temperature range that is very advantageous for many practical application scenarios. A higher Tg means that the material can still maintain good shape stability and mechanical properties at high temperatures, which is especially important for optical devices that need to work at higher temperatures.

[0112] Although the Tg is relatively high, it is still within the processable range, allowing molding through appropriate process conditions (such as injection molding, extrusion, etc.), facilitating the manufacture of optical components with complex shapes.

[0113] When m ≥ 1, and as the value of m increases, Tg decreases significantly, while elongation at break and toughness increase. This provides the possibility of optimizing material properties by adjusting the molecular structure to meet the thermal stability and mechanical performance requirements of different application scenarios.

[0114] Changing the values ​​of m and o simultaneously can adjust the elongation at break of the cycloolefin polymer to a certain extent (≈12%), and achieve a certain degree of toughening effect.

[0115] Combining high refractive index with specific Tg range, the cycloolefin copolymer in the present application has demonstrated excellent optical properties and thermal stability. This material has a wide range of applications in the field of optics, particularly in optical components requiring high transmittance, high heat resistance and good processing properties. In addition, by adjusting the m value in the molecular structure, it is possible to balance the Tg and the toughness of the material to a certain extent, further expanding its range of application and optimizing material properties. These technical effects jointly make this cycloolefin copolymer become a kind of optical material with very high practical value.

[0116] According to another embodiment of the present application, a method for preparing a cycloolefin copolymer is provided, the method comprising:

[0117] In a toluene solvent, a cycloolefin monomer, an α-olefin monomer and a halogenated heterocyclic olefin monomer are polymerized in the presence of a catalyst to obtain a cycloolefin copolymer. The molecular structure of the cycloolefin copolymer is as follows:

[0118]

[0119] In formula (I), x, y and z are the degrees of polymerization and satisfy: 20≥x≥1, y≥1, z≥1;

[0120] m and o are the lengths of the monomer chain and satisfy: 1≤m≤10, 1≤o≤10;

[0121] n is the length of the main chain, and satisfies: 50≤n≤5000;

[0122] At least one of R1, R2, R3, R4, R5, R6, R7 and R8 is a halogen atom.

[0123] According to the preparation method of the cycloolefin copolymer provided in the embodiments of the present application, from the perspective of raw material selection, three monomers are included: cycloolefin monomer, α-olefin monomer and halogenated heterocyclic olefin monomer.

[0124] Cycloolefin monomer: As one of the main components of cycloolefin copolymers, cycloolefin monomer provides good optical properties and chemical stability. Its unique ring structure helps form polymers with high refractive index and good heat resistance.

[0125] α-Olefin Monomer: The introduction of α-olefins can adjust the physical and chemical properties of cycloolefin copolymers, such as flexibility and processability. The performance of cycloolefin copolymers can be further optimized by varying the type and ratio of α-olefins.

[0126] Halogenated heterocyclic olefin monomers: The addition of halogenated heterocyclic olefins introduces new functional groups into cyclic olefin copolymers, which may give the copolymers special reactivity, surface properties or optical properties.

[0127] The preparation methods provided in the examples of this application involve the use of solvents. Specifically, toluene is selected as the solvent based on its good solubility in the raw materials and its mildness in the polymerization reaction. Toluene has a moderate boiling point, which is beneficial for controlling the reaction temperature during the polymerization process and is easy to handle subsequently, such as recovering the solvent by distillation.

[0128] While toluene is somewhat volatile as a solvent, it is relatively easy to recycle and dispose of compared to other solvents. Furthermore, by optimizing the polymerization process and recycling procedures, environmental impact can be further reduced and production sustainability improved.

[0129] The preparation methods provided in the examples of this application involve the use of catalysts during the polymerization process. The choice of catalyst has a significant impact on the polymerization rate, molecular weight distribution, and structural properties of the product. A suitable catalyst can ensure efficient polymerization of monomers under mild conditions while maintaining product uniformity and stability.

[0130] In this application, by introducing different types of monomers, such as cycloolefins, α-olefins, and halogenated heterocyclic olefins, cycloolefin copolymers with complex structures and diverse properties can be prepared. This diversity provides the material with potential for application in different fields.

[0131] In some examples of the present application, the structural formula of the cycloolefin monomer is as follows:

[0132]

[0133] The structural formula of the α-olefin monomer is as follows:

[0134]

[0135] The structural formula of the halogenated heterocyclic olefin monomer is as follows:

[0136]

[0137] In some examples of the present application, the halogenated heterocyclic olefin monomer is any one of the following structural formulas:

[0138]

[0139] In some examples of the present application, the catalyst is a metallocene catalyst.

[0140] The catalyst is a metallocene catalyst, which has the following technical effects:

[0141] (1) Metallocene catalysts are known for their excellent catalytic activity. In the preparation of cycloolefin copolymers, metallocene catalysts can efficiently promote the copolymerization of cycloolefin monomers, α-olefin monomers, and halogenated heterocyclic olefin monomers. This high catalytic activity not only shortens the reaction time but also improves the yield and purity of the product, thereby reducing production costs and improving production efficiency.

[0142] (2) Metallocene catalysts have excellent copolymerization ability and can precisely control the way monomers are inserted into the polymer chain, thereby achieving fine-tuning of the polymer structure. In the preparation of cycloolefin copolymers, metallocene catalysts can ensure that cycloolefin monomers, α-olefin monomers, and halogenated heterocyclic olefin monomers are inserted into the polymer chain in a specific order and ratio, forming copolymers with specific structures and properties. This precise control is crucial for the preparation of cycloolefin copolymers with high performance and special functions.

[0143] (3) Metallocene catalysts have high thermal and chemical stability. During the polymerization process, they can maintain activity over a wide temperature range and are not prone to decomposition or deactivation. This stability allows metallocene catalysts to adapt to different polymerization conditions, including high temperature, high pressure, and reaction systems containing specific additives. Therefore, in the preparation of cycloolefin copolymers, metallocene catalysts can ensure the smooth progress of the reaction process and improve the quality and stability of the product.

[0144] (4) Metallocene catalysts have low toxicity and environmental pollution risks during preparation and use. They can be recycled and reused under mild conditions, thus reducing negative impacts on the environment.

[0145] In some examples of the present application, the chemical structural formula of the catalyst is any one of the following:

[0146]

[0147] In some examples of the present application, the molar ratio of the cycloolefin monomer, the α-olefin monomer, and the halogenated heterocyclic olefin monomer is 1-50:1-50:5-100.

[0148] In the examples of the present application, the molar ratio of the cycloolefin monomer, the α-olefin monomer, and the halogenated heterocyclic olefin monomer is set to 1-50:1-50:5-100. This ratio setting has significant technical effects in the preparation process of the cycloolefin polymer, which is mainly reflected in the following aspects:

[0149] First, the adjustability of the copolymer composition;

[0150] This molar ratio design provides flexibility in the composition of cycloolefin polymers. By adjusting the ratio of different monomers, the content of each monomer in the cycloolefin polymer can be precisely controlled, thereby regulating the physical and chemical properties of the cycloolefin polymer. For example, increasing the proportion of halogenated heterocyclic olefin monomers may improve the heat resistance, chemical resistance, or optical properties of the cycloolefin polymer.

[0151] Second, the stability of the polymerization reaction;

[0152] In copolymerization reactions, the ratio of monomers to each other influences the stability of the polymerization reaction. Within this molar ratio range, the various monomers can participate in the polymerization reaction relatively evenly, avoiding problems such as uneven reaction rates, local overheating, and monomer residue caused by large differences in monomer concentration. This helps improve polymerization efficiency and reduce the formation of by-products.

[0153] Third, optimization of copolymer properties;

[0154] By adjusting the monomer ratio, the properties of cycloolefin polymers can be optimized. For example, in the field of optical materials, appropriately increasing the proportion of halogenated heterocyclic olefin monomers can help increase the refractive index of the copolymer and reduce the Abbe number.

[0155] Fourth, control of process costs

[0156] A reasonable monomer ratio also helps control production costs. While maintaining the performance of cycloolefin polymers, optimizing the monomer ratio can reduce monomer usage and lower raw material costs. Furthermore, because cycloolefin polymers are more stable, they also reduce the additional costs associated with runaway reactions or excessive byproducts.

[0157] In some examples of the present application, the molar ratio of the catalyst to the cycloolefin monomer is 1:500-6000; the molar ratio of the catalyst to the α-olefin monomer is 1:50-2000, and the α-olefin monomer is a polar or aromatic substituted olefin monomer.

[0158] In the examples of this application, the molar ratio of catalyst to cycloolefin monomer and α-olefin monomer is a critical parameter in the preparation of cycloolefin copolymers. The molar ratio of catalyst to cycloolefin monomer is set at 1:500 to 1:6000, while the molar ratio to α-olefin monomer is set at 1:50 to 1:2000. This setting has a significant technical effect on achieving efficient and controllable copolymerization reactions and obtaining cycloolefin copolymers with excellent performance.

[0159] Specifically, the molar ratio of catalyst to monomer influences, among other things, the reaction rate. Under this setting, the catalyst dosage is moderate relative to the monomer, ensuring full catalytic activity while avoiding the potential side effects and increased costs associated with excess catalyst. Consequently, this ratio helps achieve high monomer conversion rates in a shorter timeframe, improving overall reaction efficiency. A suitable catalyst-to-monomer ratio helps control the progress of the copolymerization reaction.

[0160] The setting of the ratio of catalyst to monomer in the present application helps to obtain a cycloolefin copolymer with specific performance indicators such as refractive index and glass transition temperature (Tg).

[0161] The cycloolefin copolymer of the present application is widely used in the fields of optics, electronics, etc. due to its unique molecular structure and excellent performance.

[0162] In some examples of the present application, the polymerization reaction temperature is 25° C. to 150° C., and the polymerization reaction time is 0.5 h to 48 h.

[0163] In the examples of this application, the settings of polymerization temperature and time (temperature of 25°C to 150°C, time of 0.5h to 48h) have significant technical effects on the preparation process of cyclic olefin copolymers. The appropriate selection of these parameters affects the polymerization rate, the molecular weight of the product, and the properties of the final product.

[0164] The temperature of the polymerization reaction is one of the key factors affecting the reaction rate. Within the set temperature range (25°C to 150°C), as the temperature increases, molecular motion accelerates and the frequency of collisions between the monomer and the catalyst increases, thereby accelerating the polymerization reaction. However, excessively high temperatures may lead to catalyst deactivation and an increase in side reactions. Therefore, selecting this temperature range ensures the reaction rate while avoiding adverse factors.

[0165] At the same time, the polymerization reaction time (0.5h to 48h) also provides fine control over the reaction process. Appropriate polymerization temperature and time are crucial for obtaining cycloolefin copolymers with excellent properties. At the right temperature, the monomers can be inserted into the polymer chain in an orderly manner, forming a copolymer with a regular structure and uniform molecular weight distribution. In addition, by adjusting the polymerization time, the molecular weight, crystallinity and other parameters of the copolymer can be further optimized to meet the specific material performance requirements of different application fields.

[0166] A well-defined polymerization temperature and time range helps achieve process stability and reproducibility. In production, this means more precise control of reaction conditions, improving product consistency and quality stability.

[0167] 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 copolymers of the embodiments of the present application achieve properties such as high refractive index and low Abbe number, the optical product of the present application also has the same advantages, which will not be described in detail here.

[0168] 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.

[0169] The cycloolefin copolymer according to the present application is described in detail below with reference to specific examples.

[0170] In the present application, the halogenated heterocyclic olefin monomer of formula (IV) is preferably prepared according to the following reaction scheme. The halogenated heterocyclic olefin monomer is preferably norbornene. The α-olefin monomer of formula (III) is preferably an α-olefin monomer.

[0171] Example 1

[0172] The preparation process of monomer 1 having the structure of formula (IV) in this embodiment 1 is as follows:

[0173]

[0174] The specific process is as follows: 1-bromo-4-fluorobenzene (14.55 g, 0.1 mol), 2-chloro-4-fluoroaniline (17.85 g, 0.102 mol), anhydrous toluene (200 ml) and potassium tert-butoxide (13.4 g, 1.2 mol) were added to a round-bottom flask to form a mixture; the mixture was degassed and backfilled with nitrogen, and then palladium acetate (0.23 g, 0.001 mol) and tri-tert-butylphosphine tetrafluoroborate (0.435 g) were added. , 0.0015 mol), the reaction was carried out under nitrogen and stirred at 100° C. for 16 h; after cooling, the mixture was treated with 1 M aqueous hydrochloric acid to neutrality, and the mixture was separated with water and ethyl acetate. The organic phase was collected, dried over anhydrous magnesium sulfate, and then filtered. The filtrate was concentrated in vacuo, and the residue was purified by silica gel chromatography with 0-20% ethyl acetate / hexane to give 2-chloro-4-fluoro-N-(4-fluorophenyl)aniline (17.97 g, 75%) as a light yellow oil.

[0175] Potassium carbonate (13.82 g, 0.1 mol), 2-chloro-4-fluoro-N-(4-fluorophenyl)aniline (11.98 g, 0.05 mol), tri-tert-butylphosphine tetrafluoroborate (0.217 g, 0.0075 mol), palladium acetate (0.115 g, 0.005 mol) and anhydrous N, N-dimethylacetamide (200 mL) were stirred at 110 ° C. under nitrogen for 16 h; after cooling, the mixture was concentrated, the residue was treated with ethyl acetate, filtered, and the filter cake was washed with ethyl acetate; the filtrate was concentrated, and the residue was purified by silica gel chromatography with 20-50% dichloromethane / n-hexane to obtain a crude product, which was recrystallized from n-hexane-dichloromethane to obtain a pure white powder product 3,6-difluorocarbazole (15.24 g, 75%).

[0176] A round-bottom flask was charged with 3,6-difluorocarbazole (20.32 g, 0.1 mol), potassium hydroxide (16.83 g, 0.3 mol), 5-bromo-1-pentene (17.88 g, 0.12 mol), and acetonitrile (250 ml). The mixture was stirred and refluxed at 90°C for 12 h. After cooling, the mixture was concentrated, and the residue was treated with ethyl acetate, filtered, and the filter cake was washed with ethyl acetate. The filtrate was concentrated, and the residue was purified by silica gel chromatography with 20-50% ethyl acetate / n-hexane to obtain the desired product (monomer 1), 3',6'-difluoro-5-carbazole-1-pentene (24.42 g, 90%), as a pure yellow-white powder.

[0177] 1 HNMR (400MHz, Chloroform-d) δ7.79 (dd, J=8.1, 2.8Hz, 1H), 7.63 (dd, J=7.9, 2.5Hz, 1H), 7.38 (ddd, J=8.2, 5.0, 3.4Hz, 2H), 7.07 (td, J=8.1, 2. 7Hz, 1H), 6.98 (td, J=8.0, 2.5Hz, 1H), 5.76–5.63 (m, 1H), 4.15 (t, J=6.5Hz, 2H), 2.11 (tdt, J=7.3, 5.9, 1.1Hz, 2H), 1.86 (tt, J=7.7, 6.5Hz, 2H).

[0178] Example 2

[0179] The preparation process of monomer 2 having the structure of formula (III) in this embodiment 2 is as follows:

[0180]

[0181] The specific process is as follows: 4,4'-difluoro-2-nitro-1,1'-biphenyl (23.52 g, 0.1 mol), triphenylphosphine (65.57 g, 0.25 mol) and o-dichlorobenzene (300 ml) were added to a round-bottom flask, and the mixture was heated, stirred and refluxed at 175°C for 24 hours; the reaction mixture was cooled to ambient temperature and purified by column chromatography on silica gel with dichloromethane / n-hexane to obtain compound 2,7-difluorocarbazole (15.24 g, 75%) as a yellow-white solid.

[0182] 2,7-Difluorocarbazole (20.32 g, 0.1 mol), potassium hydroxide (16.83 g, 0.3 mol), 5-bromo-1-pentene (17.88 g, 0.12 mol) and acetonitrile (250 ml) were added to a round-bottom flask and stirred at 90°C for 12 h. After cooling, the mixture was concentrated, and the residue was treated with ethyl acetate and filtered, and the filter cake was washed with ethyl acetate; the filtrate was concentrated, and the residue was purified by silica gel chromatography with 20-50% ethyl acetate / n-hexane to obtain the target product (monomer 2) 2',7'-difluoro-5-carbazole-1-pentene (24.42 g, 90%) as a pure yellow-white powder.

[0183] 1 HNMR (400MHz, Chloroform-d) δ8.00 (dd, J=7.9, 4.9Hz, 1H), 7.95 (dd, J=7.8, 5.0Hz, 1H), 7.17-7.07 (m, 4H), 5.76-5.63 (m, 1H) , 5.16-5.08 (m, 1H), 5.01–4.93 (m, 1H), 4.21 (t, J=6.5Hz, 2H), 2.11 (tdt, J=7.3, 5.9, 1.1Hz, 2H), 1.86 (tt, J=7.8, 6.5Hz, 2H).

[0184] Example 3

[0185] The preparation process of monomer 3 having the structure of formula (III) in this embodiment 3 is as follows:

[0186]

[0187] The specific process is as follows: add carbazole (16.72 g, 0.1 mol), N-chloro-succinimide (29.37 g, 0.22 mol), N,N-dimethylformamide (150 mol) into a Shrek bottle, replace nitrogen several times, and stir at 60°C for 2 hours; extract with ethyl acetate / water, collect the organic phase and concentrate in vacuo, and purify 3,6-dichlorocarbazole (20.07 g, 85%) by silica gel chromatography with 20-50% ethyl acetate / n-hexane.

[0188] 3,6-Dichlorocarbazole (23.61 g, 0.1 mol), potassium hydroxide (16.83 g, 0.3 mol), 5-bromo-1-pentene (17.88 g, 0.12 mol) and acetonitrile (250 ml) were added to a round-bottom flask and stirred at 90°C for 12 h. After cooling, the mixture was concentrated, and the residue was treated with ethyl acetate and filtered, and the filter cake was washed with ethyl acetate; the filtrate was concentrated, and the residue was purified by silica gel chromatography with 20-50% ethyl acetate / n-hexane to obtain the target product (monomer 3) 3',6'-difluoro-5-carbazole-1-pentene (27.37 g, 90%) as a pure yellow-white powder.

[0189] 1 HNMR (400MHz, Chloroform-d) δ7.86 (d, J=1.8Hz, 1H), 7.82 (d, J=2.5Hz, 1H), 7.47 (d, J=8.1Hz, 1H); 7.38 (d, J=8.2Hz, 1H), 7.29–7.18 (m, 2H), 5.69 (tt, J=1 7.2, 6.0Hz, 1H), 5.12 (ddt, J=17.2, 2.2, 1.0Hz, 1H), 4.97 (ddt, J=17.2, 2.2, 1 .0Hz, 1H), 4.20–4.14 (m, 2H), 2.15–2.07 (m, 2H), 1.86 (tt, J=7.7, 6.5Hz, 2H).

[0190] Example 4

[0191] The preparation process of monomer 4 having the structure of formula (III) in this embodiment 4 is as follows:

[0192]

[0193] The specific process is as follows: 4,4'-dichloro-2-nitrobiphenyl (26.81 g, 0.1 mol), triethyl phosphite (49.84 g, 0.3 mol) and o-dichlorobenzene (200 ml) are heated at 160 ° C for 5 hours under a nitrogen environment; after cooling, vacuum concentration is carried out, and the residual liquid is separated by column chromatography on silica gel with toluene / heptane to obtain 2,7-dichlorocarbazole (1.17 g, 75%).

[0194] 2,7-Dichlorocarbazole (23.60 g, 0.1 mol), potassium hydroxide (16.83 g, 0.3 mol), 5-bromo-1-pentene (17.88 g, 0.12 mol) and acetonitrile (250 ml) were added to a round-bottom flask and stirred at 90°C for 12 h. After cooling, the mixture was concentrated, and the residue was treated with ethyl acetate and filtered, and the filter cake was washed with ethyl acetate; the filtrate was concentrated, and the residue was purified by silica gel chromatography with 20-50% ethyl acetate / n-hexane to obtain the target product (monomer 2) 2',7'-dichloro-5-carbazole-1-pentene (27.37 g, 90%) as a pure yellow-white powder.

[0195] 1 HNMR (400MHz, Chloroform-d) δ7.99 (d, J=8.2Hz, 1H), 7.93 (d, J=7.9Hz, 1H), 7.33 (ddd, J=8.1, 6.2, 2.0Hz, 3H), 7.26 (d, J=1.8Hz, 1H), 7.20 (d, J=2.2H z, 1H), 5.69 (tt, J=17.2, 6.0Hz, 1H), 5.12 (ddt, J=17.2, 2.2, 1.0Hz, 1H), 4. 97 (ddt, J=17.2, 2.2, 1.0Hz, 1H), 2.10 (t, J=6.3Hz, 1H), 1.91–1.83 (m, 2H).

[0196] Example 5

[0197] The preparation process of the monomer 5 having the structure of formula (III) in this embodiment 5 is as follows:

[0198]

[0199] The specific process is as follows: add carbazole (16.72 g, 0.1 mol), N-bromo-succinimide (39.11 g, 0.22 mol), N,N-dimethylformamide (150 mol) into a Shrek bottle, replace nitrogen several times, and stir at 60°C for 2 h; extract with ethyl acetate / water, collect the organic phase and concentrate in vacuo, and purify 3,6-dibromocarbazole (27.62 g, 85%) by silica gel chromatography with 20-50% ethyl acetate / n-hexane.

[0200] 3,6-Dibromocarbazole (32.50 g, 0.1 mol), potassium hydroxide (16.83 g, 0.3 mol), 5-bromo-1-pentene (17.88 g, 0.12 mol), and acetonitrile (250 ml) were added to a round-bottom flask and stirred at 90°C for 12 hours. After cooling, the mixture was concentrated, and the residue was treated with ethyl acetate, filtered, and the filter cake washed with ethyl acetate. The filtrate was concentrated, and the residue was purified by silica gel chromatography with 20-50% ethyl acetate / n-hexane to obtain the desired product (monomer 5), 3',6'-dibromo-5-carbazole-1-pentene (35.37 g, 90%), as a pure yellow-white powder.

[0201] 1 HNMR (400MHz, Chloroform-d) δ8.06 (dd, J=2.0Hz, 1H), 7.52 (dd, J=8.7, 2.0Hz, 1H), 7.19 (d, J=8.7Hz, 1H) , 5.79 (tt, 0H), 5.05 (dd, 1H), 4.16 (t, J = 7.2Hz, 1H), 2.08 (td, J = 6.7, 6.2Hz, 1H), 1.90 (tt, J = 7.5Hz, 1H).

[0202] Example 6

[0203] The preparation process of monomer 6 having the structure of formula (III) in this embodiment 6 is as follows:

[0204]

[0205] The specific process is as follows: 4,4'-dibromo-2-nitrobiphenyl (5.70 g, 0.1 mol), triethyl phosphite (49.84 g, 0.3 mol) and o-dichlorobenzene (200 ml) are heated at 160 ° C for 5 h under a nitrogen environment; after cooling, the mixture is concentrated in vacuo, and the residual liquid is separated by column chromatography on silica gel with toluene / heptane to obtain 2,7-dibromocarbazole (243.75 g, 75%).

[0206] 2,7-Dichlorocarbazole (325.00 g, 0.1 mol), potassium hydroxide (16.83 g, 0.3 mol), 5-bromo-1-pentene (17.88 g, 0.12 mol) and acetonitrile (250 ml) were added to a round-bottom flask and stirred at 90°C for 12 h. After cooling, the mixture was concentrated, and the residue was treated with ethyl acetate and filtered, and the filter cake was washed with ethyl acetate; the filtrate was concentrated, and the residue was purified by silica gel chromatography with 20-50% ethyl acetate / n-hexane to obtain the target product (monomer 6) 2',7'-dibromo-5-carbazole-1-pentene (35.76 g, 91%) as a pure yellow powder.

[0207] 1HNMR (400MHz, Chloroform-d) δ8.01 (d, J=8.0Hz, 1H), 7.97 (d, J=8.0Hz, 1H), 7.69 (d, J=1.9Hz, 1H), 7.53 (ddd, J=8.1, 4.6, 2.0Hz, 1H), 5.69 (tt, J=17.2, 6.0Hz, 1H), 5.16–4.93 (m, 1H), 4.20 (t, J=6.5Hz, 1H), 2.15–2.07 (m, 1H), 1.91–1.83 (m, 1H).

[0208] Example 7

[0209] The preparation process of monomer 7 having the structure of formula (III) in this embodiment 7 is as follows:

[0210]

[0211] The specific process is as follows: 280 ml of acetic acid was added to a mixture of carbazole (16.72 g, 0.1 mol) and KI (21.58 g, 0.13 mol). After heating to reflux to dissolve all solids in the glacial acetic acid, the mixture was cooled and ground potassium iodate (32.1 g, 0.15 mol) was added. The reaction mixture was then heated to reflux again for 1 hour before cooling to room temperature. A large amount of compound precipitated during the reaction, which was isolated by filtration and washed with water to yield pure 3,6-diiodocarbazole (38.55 g, 92%) as a gray solid.

[0212] 3,6-Diiodocarbazole (41.90 g, 0.1 mol), potassium hydroxide (16.83 g, 0.3 mol), 5-bromo-1-pentene (17.88 g, 0.12 mol) and acetonitrile (250 ml) were added to a round-bottom flask and stirred at 90°C for 12 h. After cooling, the mixture was concentrated, and the residue was treated with ethyl acetate and filtered, and the filter cake was washed with ethyl acetate; the filtrate was concentrated, and the residue was purified by silica gel chromatography with 20-50% ethyl acetate / n-hexane to obtain the target product (monomer 5) 3',6'-diiodo-5-carbazole-1-pentene (43.84 g, 90%) as a pure yellow-white powder.

[0213] 1HNMR (400MHz, Chloroform-d) δ8.48 (d, J=2.0Hz, 1H), 7.63 (dd, J=7.7, 2.0Hz, 1H), 7.38 (d, J=7.7Hz, 0H), 7.30 (d, J=7.7Hz, 0H), 5.69 (tt, J=17.2, 6.0Hz , 1H), 5.12 (ddt, J=17.2, 2.2, 1.0Hz, 1H), 4.97 (ddt, J=17.2, 2.2, 1.0Hz, 1H ), 4.20–4.14 (m, 1H), 2.15–2.07 (m, 1H), 1.86 (ddd, J=14.1, 7.6, 6.5Hz, 1H).

[0214] Example 8

[0215] The preparation process of monomer 8 having the structure of formula (III) in this embodiment 8 is as follows:

[0216]

[0217] The specific process is as follows: 4,4'-diiodo-2-nitro-1,1'-biphenyl (45.10 g, 0.1 mol), triphenylphosphine (65.57 g, 0.25 mol) and o-dichlorobenzene (300 ml) were added to a round-bottom flask, and the mixture was heated, stirred and refluxed at 160°C under nitrogen protection for 16 h; cooled to ambient temperature, and purified by column chromatography on silica gel with dichloromethane / n-hexane to obtain compound 2,7-diiodocarbazole (29.33 g, 70%) as a yellow solid.

[0218] 2,7-Diiodocarbazole (41.90 g, 0.1 mol), potassium hydroxide (16.83 g, 0.3 mol), 5-bromo-1-pentene (17.88 g, 0.12 mol) and acetonitrile (250 ml) were added to a round-bottom flask and stirred at 90°C for 12 h. After cooling, the mixture was concentrated, and the residue was treated with ethyl acetate and filtered, and the filter cake was washed with ethyl acetate; the filtrate was concentrated, and the residue was purified by silica gel chromatography with 20-50% ethyl acetate / n-hexane to obtain the target product (monomer 8) 2',7'-diiodo-5-carbazole-1-pentene (44.81 g, 92%) as a pure yellow-white powder.

[0219] 1HNMR (400MHz, Chloroform-d) δ8.01 (d, J=7.5Hz, 0H), 7.97 (d, J=7.5Hz, 0H), 7.73 (d, J=1.9Hz, 1H), 7.67 (dd, J=7.5, 2.0 Hz, 1H), 5.69 (tt, J=17.2, 6.0Hz, 1H), 5.24–4.91 (m, 1H), 4.20 (t, J=6.5Hz, 1H)), 2.15–2.07 (m, 1H), 1.91–1.85 (m, 1H).

[0220] The preparation process of monomer 9-12 having the structure of formula (III) is as follows:

[0221]

[0222] A round-bottom flask was added with 5-halogenated indole (5-fluoroindole 13.51 g, 5-chloroindole 15.16 g, 5-bromoindole 19.60 g or 5-iodoindole 23.41 g, 0.1 mol), potassium hydroxide (16.83 g, 0.3 mol), 5-bromo-1-pentene (17.88 g, 0.12 mol) and acetonitrile (250 ml), stirred and refluxed at 60 ° C for 8 h. After cooling, the mixture was concentrated, the residue was treated with ethyl acetate, filtered, and the filter cake was washed with ethyl acetate; The liquid was concentrated, and the residue was purified by silica gel chromatography with 20-50% ethyl acetate / n-hexane to obtain pure yellow oily liquid products (monomer 9) 5'-fluoro-5-indole-1-pentene (17.22 g, 86%), (monomer 10) 5'-chloro-5-indole-1-pentene (19.71 g, 93%), (monomer 11) 5'-bromo-5-indole-1-pentene (24.29 g, 92%), and (monomer 12) 5'-iodo-5-indole-1-pentene (28.02 g, 90%).

[0223] (Monomer 9) 5'-fluoro-5-indole-1-pentene (17.22 g, 86%), 1 HNMR (400MHz, Chloroform-d) δ7.80–7.74 (m, 1H), 7.29 (d, J=4.9Hz, 1H), 7.12 (td, J=7.9, 2.0Hz, 1H), 7.06 (d, J=7.9Hz, 0H), 6. 45–6.40 (m, 1H), 5.69 (tt, J=17.2, 6.0Hz, 1H), 5.21–4.91 (m, 2H), 4.10 (t, J=6.5Hz, 2H), 2.13–2.05 (m, 1H), 1.92–1.83 (m, 2H).

[0224] (Monomer 10) 5'-chloro-5-indole-1-pentene (19.71 g, 93%) 1 HNMR (400MHz, Chloroform-d) δ7.70–7.64 (m, 1H), 7.31–7.24 (m, 2H), 6.98 (d, J=2.2Hz, 1H), 6.45–6.40 (m, 1H), 5.69 (tt, J=17.2, 6.0Hz, 1H), 5.17–4.93 (m, 1H), 4.10 (t, J=6.5Hz, 2H), 2.24–2.02 (m, 1H), 1.98–1.75 (m, 12H).

[0225] (Monomer 11) 5'-bromo-5-indole-1-pentene (24.29 g, 92%), 1 HNMR (400MHz, Chloroform-d) δ7.91 (d, J=2.2Hz, 1H), 7.73 (s, 1H), 7.49 (s, 1H), 7.30 (s, 1H), 6.54–6.33 (m, 1H), 5.69 (tt, J=17 .2, 6.0Hz, 1H), 5.06 (dd, J=73.1, 2.4Hz, 2H), 4.10 (t, J=6.5Hz, 2H), 2.09 (dddd, J=7.4, 6.6, 5.9, 1.0Hz, 2H), 1.92–1.84 (m, 2H).

[0226] (Monomer 12) 5'-iodo-5-indole-1-pentene (28.02 g, 90%), 1 HNMR (400MHz, Chloroform-d) δ7.82–7.49 (m, 3H), 7.31 (d, J=5.1Hz, 1H), 6.44 (dd, J=5.1, 0.7Hz, 1H), 5.69 (tt, J=17 .2, 6.0Hz, 1H), 5.17–4.90 (m, 2H), 4.10 (t, J=6.5Hz, 2H), 2.09 (dddd, J=7.8, 7.0, 6.0, 1.2Hz, 2H), 1.92–1.84 (m, 2H).

[0227] Examples 13-16 The preparation process of monomers 13-16 having the structure of formula (III) is as follows:

[0228]

[0229] The specific process is as follows: 6-halogenated indole (6-fluoroindole 13.51 g, 6-chloroindole 15.16 g, 6-bromoindole 19.60 g or 6-iodoindole 23.41 g, 0.1 mol), potassium hydroxide (16.83 g, 0.3 mol), 5-bromo-1-pentene (17.88 g, 0.12 mol) and acetonitrile (250 ml) are added to a round-bottom flask, and stirred and refluxed at 60°C for 8 hours. After cooling, the mixture is concentrated, and the residue is treated with ethyl acetate, filtered, and the filter cake is washed with ethyl acetate. The filtrate was concentrated and the residue was purified by silica gel chromatography with 20-50% ethyl acetate / n-hexane to obtain pure yellow oily liquid products (monomer 13) 6'-fluoro-5-indole-1-pentene (17.22 g, 86%), (monomer 14) 6'-chloro-5-indole-1-pentene (19.71 g, 93%), (monomer 15) 6'-bromo-5-indole-1-pentene (24.29 g, 92%), and (monomer 16) 6'-iodo-5-indole-1-pentene (28.02 g, 90%). (Monomer 13) 6'-Fluoro-5-indole-1-pentene (17.22 g, 86%) 1H NMR (500 MHz, Chloroform-d) δ 7.40 (dd, J = 8.0, 4.9 Hz, 1H), 7.29 (d, J = 5.0 Hz, 1H), 7.22 (dt, J = 7.8, 2.5 Hz, 1H), 6.97 (td, J = 8.1, 2.7 Hz, 1H), 6.61 (dd, J = 5.1, 2.3 Hz, 1H), 5.69 (tt, J = 17.2, 6.0 Hz, 1H), 5.22–4.83 (m, 1H), 4.08 (t, J = 6.5 Hz, 2H), 2.26–2.00 (m, 1H), 1.92–1.84 (m, 2H).

[0230] (Monomer 14) 6'-chloro-5-indole-1-pentene (19.71 g, 93%) 1 HNMR (500MHz, Chloroform-d) δ7.49 (d, J=8.3Hz, 1H), 7.47 (t, J=2.2Hz, 1H), 7.29 (d, J=5.1Hz, 1H), 7.19 (dd, J=8.2, 2.2Hz, 1H), 6.56 (dd, J=5.1, 2.3Hz, 1H), 5.69 (tt, J=17.2, 6.0Hz, 1H), 5.04 (dddt, J=73.1, 17.2, 2.2, 1.0Hz, 2H), 4.08 (t, J=6.5Hz, 2H), 2.13–2.05 (m, 2H), 1.92–1.84 (m, 2H).

[0231] (Monomer 15) 6'-bromo-5-indole-1-pentene (24.29 g, 92%) 1H NMR (500 MHz, Chloroform-d) δ 7.70 (t, J = 2.2 Hz, 1H), 7.48 (d, J = 8.3 Hz, 1H), 7.42 (dd, J = 8.4, 2.2 Hz, 1H), 7.30 (d, J = 5.1 Hz, 1H), 6.56 (dd, J = 5.1, 2.3 Hz, 1H), 5.69 (tt, J = 17.2, 6.0 Hz, 1H), 5.21–4.92 (m, 2H), 4.08 (t, J = 6.5 Hz, 2H), 2.13–2.05 (m, 2H), 1.92–1.84 (m, 2H).

[0232] (Monomer 16) 6'-iodo-5-indole-1-pentene (28.02 g, 90%) 1H NMR (500 MHz, Chloroform-d) δ 7.82 (t, J = 2.3 Hz, 1H), 7.54 (dd, J = 7.7, 2.2 Hz, 1H), 7.40 (d, J = 7.7 Hz, 1H), 7.31 (d, J = 4.9 Hz, 1H) H), 6.58 (dd, J=5.0, 2.3Hz, 1H), 5.69 (tt, J=17.2, 6.0Hz, 1H), 5.27–4.86 (m, 2H), 4.08 (t, J=6.5Hz, 2H), 2.09 (dddd, J=7.5, 6.6, 5.9, 1.0Hz, 2H), 1.92–1.84 (m, 2H).

[0233] The preparation process of monomers 17-20 having the structure of formula (III) is as follows:

[0234]

[0235] The specific process is as follows: 6-halogenated indoline (6-fluoroindoline 13.71 g, 6-chloroindole 15.36 g, 6-bromoindole 19.80 g or 6-iodoindole 23.61 g, 0.1 mol), triethylamine (30.36 g, 0.3 mol), 5-bromo-1-pentene (17.88 g, 0.12 mol) and DMF (150 ml) are added to a round-bottom flask, and stirred under reflux at 40 ° C for 8 h under nitrogen protection. After cooling, the mixture is extracted with ethyl acetate / water, the organic phase is enriched, and vacuum concentrated. The residue was purified by silica gel chromatography with 20-50% ethyl acetate / n-hexane to give pure yellow oily liquid products (monomer 17) 6'-fluoro-5-indoline-1-pentene (17.86 g, 87%), (monomer 18) 6'-chloro-5-indoline-1-pentene (17.73 g, 89%), (monomer 19) 6'-bromo-5-indoline-1-pentene (22.71 g, 89%), and (monomer 20) 6'-iodo-5-indoline-1-pentene (26.62 g, 85%).

[0236] (Monomer 17) 6'-Fluoro-5-indoline-1-pentene (17.86 g, 87%) 1 HNMR (400MHz, Chloroform-d) δ7.09 (dd, J=8.3, 5.0Hz, 1H), 6.77 (td, J=8.2, 1.9Hz, 1H), 6.52 (dd, J=8.0, 1.9Hz, 1H), 5.72 (tt, J=17.2, 7.1Hz, 1H), 5.05 (dddt, J=76.2, 1 7.0, 2.0, 1.0Hz, 1H), 3.54 (ddd, J=18.7, 5.1, 3.3Hz, 2H), 3.26 (d, J=6.8Hz, 2H), 3.0 0 (ddt, J=5.1, 3.1, 1.0Hz, 2H), 2.12–2.05 (m, 2H), 1.76 (ddd, J=8.1, 6.8, 1.3Hz, 2H).

[0237] (Monomer 18) 6'-chloro-5-indoline-1-pentene (17.73 g, 89%) 1HNMR (500MHz, Chloroform-d) δ7.13 (dt, J=8.4, 1.0Hz, 1H), 7.01 (dd, J=8.5, 1.9Hz, 1H), 6.86 (d, J=2.0Hz, 1H), 5.79–5.66 (m, 1H), 5.31–4. 83 (m, 2H), 3.54 (ddd, J=18.7, 5.1, 3.3Hz, 2H), 3.40–3.06 (m, 2H), 2.99 (ddt, J=5.3, 1.9, 0.9Hz, 2H), 2.28–1.97 (m, 2H), 1.81–1.72 (m, 2H).

[0238] (Monomer 19) 6'-bromo-5-indoline-1-pentene (22.71 g, 89%) 1 HNMR (400MHz, Chloroform-d) δ7.20 (dd, J=8.5, 1.9Hz, 1H), 7.07 (dt, J=8.5, 1.0Hz, 1H), 6.90 (d, J=2.0Hz, 1H), 5.79–5.66 (m, 1H), 5.27–4.87 (m, 2H), 3.54 (ddd, J=18.7, 5.1, 3.3Hz, 2H), 3.28–3.22 (m, 2H), 2.12–2.05 (m, 2H), 1.76 (tt, J=8.2, 6.8Hz, 2H).

[0239] (Monomer 20) 6'-iodo-5-indoline-1-pentene (26.62 g, 85%) 1 HNMR (500MHz, Chloroform-d) δ7.35 (dd, J=8.0, 1.9Hz, 1H), 7.25 (d, J=1.9Hz, 1H), 6.94 (dt, J=7.9, 1.1Hz, 1H), 5.79–5.66 (m, 1H), 5.28– 4.67 (m, 2H), 3.56 (dd, J=5.1, 3.3Hz, 2H), 3.26 (t, J=6.8Hz, 2H), 2.99 (ddd, J=4.3, 1.8, 1.1Hz, 2H), 2.12–2.05 (m, 2H), 1.81–1.72 (m, 2H).

[0240] The preparation process of monomers 21-24 having the structure of formula (III) is as follows:

[0241]

[0242] 5-halogenated indoline (5-fluoroindoline 13.71 g, 5-chloroindole 15.36 g, 5-bromoindole 19.80 g or 5-iodoindole 23.61 g, 0.1 mol), triethylamine (30.36 g, 0.3 mol), 5-bromo-1-pentene (17.88 g, 0.12 mol) and DMF (150 ml) were added to a round-bottom flask and stirred under reflux at 40 ° C for 8 h under nitrogen protection. After cooling, the mixture was extracted with ethyl acetate / water, the organic phase was concentrated in vacuo, and the residue was The product was purified by silica gel chromatography with 20-50% ethyl acetate / n-hexane to obtain pure yellow oily liquid products (monomer 21) 5'-fluoro-5-indoline-1-pentene (17.86 g, 87%), (monomer 22) 5'-chloro-5-indoline-1-pentene (17.73 g, 89%), (monomer 23) 5'-bromo-5-indoline-1-pentene (22.71 g, 89%), and (monomer 24) 5'-iodo-5-indoline-1-pentene (26.62 g, 85%).

[0243] (Monomer 21) 5'-Fluoro-5-indoline-1-pentene (17.86 g, 87%) 1 HNMR (500MHz, Chloroform-d) δ6.87–6.86 (m, 1H), 6.86–6.84 (m, 1H), 6.78 (ddd, J=8.1, 1.8, 0.9Hz, 1H), 5.79–5.66 (m, 1H), 5.19–4.88 (m, 2H), 3.24 (t, J=6.8Hz, 2H), 2.95 (ddt, J=5.1, 3.3, 0.9Hz, 2H), 2.13–2.05 (m, 2H), 1.81–1.72 (m, 2H).

[0244] (Monomer 22) 5'-chloro-5-indoline-1-pentene (17.73 g, 89%) 1 HNMR (500MHz, Chloroform-d) δ7.04 (dd, J=8.9, 2.3Hz, 1H), 6.99 (dt, J=2.1, 1.0Hz, 1H), 6.75 (d, J=9.0Hz, 1H), 5.72 (tt, J=17.2, 7.1H z, 1H), 5.05 (dddt, J=76.2, 17.0, 2.0, 1.0Hz, 2H), 3.54 (ddd, J=18.7, 5.1, 3.3Hz, 2H), 2.09 (td, J=8.3, 7.1Hz, 2H), 1.81–1.72 (m, 2H).

[0245] (Monomer 23) 5'-bromo-5-indoline-1-pentene (22.71 g, 89%) 1HNMR (500MHz, Chloroform-d) δ7.28 (dd, J=9.0, 2.2Hz, 1H), 7.14 (dt, J=2.2, 0.9Hz, 1H), 6.71 (d, J=9.0Hz, 1H), 5.79–5.66 (m, 1H), 5.05 (dddt, J=76.2, 17.0, 2.0, 1.0Hz, 2H), 3.24 (t, J=6.8Hz, 2H), 3.01 (dddd, J=5.2, 3.1, 2.0, 1.0Hz, 2H), 2.12–2.05 (m, 2H), 1.76 (tt, J=8.2, 6.8Hz, 2H).

[0246] (Monomer 24) 5'-iodo-5-indoline-1-pentene (26.62 g, 85%) 1 HNMR (500MHz, Chloroform-d) δ7.50 (dd, J=8.5, 2.3Hz, 1H), 7.28 (dt, J=2.2, 1.0Hz, 1H), 6.62 (d, J=8.4Hz, 1H), 5.72 (tt, J=17.2, 7.1Hz, 1H), 5 .23–4.90(m, 2H), 3.54(ddd, J=18.7, 5.1, 3.3Hz, 2H), 3.24(t, J=6.8Hz, 2H), 3.00–2.98 (m, 2H), 2.19–2.00 (m, 2H), 1.76 (tt, J=8.2, 6.8Hz, 2H).

[0247] Example 25 The preparation process of monomer 25 having the structure of formula (III) is as follows:

[0248]

[0249] The specific process is: 4,4'-dibromo-2-nitrobiphenyl (35.70g, 0.1mol), triethyl phosphite (49.84g, 0.3mol) and o-dichlorobenzene (200ml) are heated at 160°C under a nitrogen environment for 5h; after cooling, vacuum concentration is carried out, and the residual liquid is separated by column chromatography on silica gel with toluene / heptane to obtain 2,7-dibromocarbazole (243.75g, 75%).

[0250] 2,7-Dibromocarbazole (32.50 g, 0.1 mol), N-bromo-succinimide (39.11 g, 0.22 mol), and N,N-dimethylformamide (150 mol) were added to a Shrek flask, the nitrogen atmosphere was replaced several times, and the mixture was stirred at 60°C for 2 h. The mixture was extracted with ethyl acetate / water, and the organic phase was collected and concentrated in vacuo. The residue was purified by silica gel chromatography with 20-50% ethyl acetate / n-hexane to obtain 2,3,6,7-tetrabromocarbazole (36.20 g, 75%).

[0251] A round-bottom flask was charged with 2,3,6,7-tetrabromocarbazole (48.28 g, 0.1 mol), potassium hydroxide (16.83 g, 0.3 mol), 5-bromo-1-pentene (17.88 g, 0.12 mol), and acetonitrile (250 ml). The mixture was stirred and refluxed at 90°C for 12 h. After cooling, the mixture was concentrated, and the residue was treated with ethyl acetate, filtered, and the filter cake washed with ethyl acetate. The filtrate was concentrated, and the residue was purified by silica gel chromatography with 20-50% ethyl acetate / n-hexane to obtain the desired product (monomer 25), 2',3'6',7'-tetrabromo-5-carbazole-1-pentene (49.58 g, 90%), as a pure off-white powder. NMR (400MHz, Chloroform-d) δ8.08 (s, 1H), 7.97 (s, 1H), 7.41 (d, J=5.5Hz, 2H), 5.69 (tt, J=17.2, 6.0H z, 1H), 5.17–4.91 (m, 2H), 4.23–4.17 (m, 2H), 2.11 (dd, J=7.3, 1.3Hz, 2H), 1.86 (tt, J=7.7, 6.5Hz, 2H).

[0252] Example 26 The preparation process of monomer 26 having the structure of formula (III) is as follows:

[0253]

[0254] The specific process is as follows: 4,4'-diiodo-2-nitro-1,1'-biphenyl (45.10 g, 0.1 mol), triphenylphosphine (65.57 g, 0.25 mol), and o-dichlorobenzene (300 ml) were added to a round-bottom flask and heated with stirring at reflux under nitrogen at 160°C for 16 hours. The mixture was cooled to ambient temperature and purified by column chromatography on silica gel using dichloromethane / n-hexane to obtain 2,7-diiodocarbazole (29.33 g, 70%) as a yellow solid.

[0255] To a mixture of 2,7-diiodocarbazole (53.19 g, 0.1 mol) and KI (21.58 g, 0.13 mol) was added 280 ml of acetic acid. After heating to reflux to dissolve all solids in the glacial acetic acid, the mixture was cooled and ground potassium iodate (32.1 g, 0.15 mol) was added. The reaction mixture was then heated to reflux again for 1 hour before being cooled to room temperature. A large amount of compound precipitated during the reaction, which was isolated by filtration and washed with water to yield pure 2,3,6,7-tetraiodocarbazole (70.533 g, 90%) as a gray solid.

[0256] 2,3,6,7-Tetraiodocarbazole (78.37 g, 0.1 mol), potassium hydroxide (16.83 g, 0.3 mol), 5-bromo-1-pentene (17.88 g, 0.12 mol), and acetonitrile (250 ml) were added to a round-bottom flask and stirred at 90°C for 12 hours. After cooling, the mixture was concentrated, and the residue was treated with ethyl acetate and filtered, and the filter cake was washed with ethyl acetate. The filtrate was concentrated, and the residue was purified by silica gel chromatography with 20-50% ethyl acetate / n-hexane to obtain the target product (monomer 8), 2',3',6',7'-tetraiodo-5-carbazole-1-pentene (43.84 g, 90%), as a pure yellow-white powder. NMR (500MHz, Chloroform-d) δ8.63 (s, 2H), 7.55 (s, 2H), 5.87–5.52 (m, 1H), 5.26–4.88 (m , 2H), 4.47–3.96 (m, 2H), 2.11 (tdt, J=7.3, 5.9, 1.1Hz, 2H), 1.86 (tt, J=7.7, 6.5Hz, 2H).

[0257] Examples 27-32 show the effects of different catalysts on the terpolymerization of heterocyclic halogenated monomers, α-olefins and cycloolefins.

[0258] First, Shrek flasks ① and ② were dried in a forced-air drying oven at 120°C for 1 hour. Then, under a nitrogen atmosphere, 30 mL of toluene, 30 mmol of norbornene, 15 mmol of 1-octene, and 30 mmol of heterocyclic halogenated monomer 5 were added to Shrek flask ①. Subsequently, 10 μmol of different metallocene catalysts (Cat. 1-6) and 10 mmol of dry methylaluminoxane were dissolved in 1 mL of toluene and added to Shrek flask ② under a nitrogen atmosphere. The monomers from Shrek flask ① were then added to flask ②, and the mixture was reacted at 70°C with rapid stirring (800 rpm) for 12 hours. After the reaction, the reaction mixture was poured into 300 mL of ethanolic hydrochloric acid solution, and the polymer was filtered and repeatedly washed with an acetone-ethyl acetate mixture before drying in a vacuum oven to constant weight. The specific reaction conditions and results are shown in Table 1.

[0259] Table 1

[0260]

[0261] It should be noted that all data are based on the results of at least two parallel experiments (unless otherwise stated). Activity: 103 gmol-1h-1 is the unit. Mw is the weight-average molecular weight, determined by GPC in chloroform.

[0262] As shown in Table 1, the insertion rate of catalyst Cat.1 is relatively high relative to the heterocyclic halogenated monomer.

[0263] Examples 33-40 show the effects of different heterocyclic halogenated monomers on the ternary copolymerization of α-olefin and cycloolefin under the preferred Cat.1 catalyst.

[0264] First, Shrek flasks ① and ② were dried in a forced-air drying oven at 120°C for 1 hour. Then, under a nitrogen atmosphere, 30 mL of toluene, 30 mmol of norbornene, 15 mmol of 1-octene, and 30 mmol of different heterocyclic halogenated monomers (monomers 2, 5, 7, 10, 11, 12, 18, 23, 25, and 27) were added to Shrek flask ①. Then, under a nitrogen atmosphere, 10 μmol of metallocene catalyst Cat. 1 and 10 mmol of dry methylaluminoxane were dissolved in 1 mL of toluene and added to Shrek flask ②. The monomers from Shrek flask ① were then added to flask ②, and the mixture was reacted at 70°C with rapid stirring (800 rpm) for 12 hours. After the reaction, the reaction mixture was poured into 300 mL of ethanolic hydrochloric acid solution, and the polymer was filtered and repeatedly washed with an acetone-ethyl acetate mixture before drying in a vacuum oven to constant weight. The specific reaction conditions and results are shown in Table 2.

[0265] Table 2

[0266]

[0267] It should be noted that all data are based on the results of at least two parallel experiments (unless otherwise specified). Activity: 103 gmol-1h-1 is the unit. Mw is the weight-average molecular weight, measured by GPC in chloroform.

[0268] As shown in Table 2, when the halogenated heterocycle is a carbazole ring system, the refractive index is significantly higher than that of the indole ring system or the indoline ring system. When the number of halogen atoms on the halogenated heterocycle gradually increases, the refractive index also increases significantly.

[0269] Examples 43-51 show the effects of different monomer ratios on the ternary copolymerization of heterocyclic halogenated monomers, α-olefins and cycloolefins in the presence of a preferred Cat. 1 catalyst.

[0270] First, Shrek flasks ① and ② were dried in a forced-air drying oven at 120°C for 1 hour. Then, under a nitrogen atmosphere, 30 mL of toluene and varying ratios of norbornene, 1-octene, and heterocyclic halogenated monomer 5 were added to Shrek flask ①. Then, under a nitrogen atmosphere, 10 μmol of Cat.1 metallocene catalyst and 10 mmol of dry methylaluminoxane dissolved in 1 mL of toluene were added to Shrek flask ②. The monomers from Shrek flask ① were then added to flask ②. The mixture was then stirred rapidly (800 rpm) at 70°C for 12 hours. After the reaction, the reaction mixture was poured into 300 mL of ethanolic hydrochloric acid solution, and the polymer was filtered. The resulting polymer was repeatedly washed with an acetone-ethyl acetate mixture and finally dried in a vacuum oven to constant weight. The specific reaction conditions and results are shown in Table 3.

[0271] Table 3

[0272]

[0273]

[0274] It should be noted that all data are based on the results of at least two parallel experiments (unless otherwise stated). Activity: 103 gmol-1h-1 is the unit. Mw is the weight-average molecular weight, determined by GPC in chloroform.

[0275] The data in Table 3 demonstrate that, maintaining the cycloolefin monomer concentration constant and increasing the halogenated heterocyclic olefin monomer concentration gradually increases the insertion rate. Increasing the amount of 1-octene significantly increases the polymer's elongation at break and decreases its glass transition temperature. Compared to Mitsui 5014, this product exhibits significant performance advantages in refractive index and elongation at break.

[0276] Although some specific embodiments of the present application have been described in detail by way of examples, 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 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 cycloolefin copolymer comprises a halogenated heterocyclic structure portion, and the molecular structure of the cycloolefin copolymer is as follows: In formula (I), x, y and z are the degrees of polymerization and satisfy: 20≥x≥1, y≥1, z≥1; m and o are the lengths of the monomer chain and satisfy: 1≤m≤10, 1≤o≤10; n is the length of the main chain, and satisfies: 50≤n≤5000; At least one of R1, R2, R3, R4, R5, R6, R7 and R8 is a halogen atom.

2. The cyclic olefin copolymer according to claim 1, characterized in that In the formula (I), R1, R2, R3, R4, R5, R6, R7, and R8 are independently selected from halogen atoms or H atoms, but R1, R2, R3, R4, R5, R6, R7, and R8 cannot be H atoms at the same time, and at least one halogen atom is present.

3. The cyclic olefin copolymer according to claim 2, characterized in that There are two or more halogen atoms in R1, R2, R3, R4, R5, R6, R7 and R8.

4. The cyclic olefin copolymer according to claim 1, wherein The halogenated heterocyclic structure moiety includes halogenated benzopyrrole, halogenated benzodihydropyrrole or halogenated carbazole.

5. The cyclic olefin copolymer according to claim 1, wherein The cyclic olefin copolymer includes the following halogenated heterocyclic polymers; Among them, 20≥x≥1, y≥1, z≥1, 50≤n≤5000.

6. The cyclic olefin copolymer according to claim 1, wherein The cyclic olefin copolymer has a high refractive index of 1.60 to 1.72; The glass transition temperature Tg of the cycloolefin copolymer is: 200°C <Tg<300℃。 7. A method for preparing a cycloolefin copolymer, characterized in that: The preparation method comprises: In a toluene solvent, a cycloolefin monomer, an α-olefin monomer and a halogenated heterocyclic olefin monomer are polymerized in the presence of a catalyst to obtain a cycloolefin copolymer. The molecular structure of the cycloolefin copolymer is as follows: In formula (I), x, y and z are the degrees of polymerization and satisfy: 20≥x≥1, y≥1, z≥1; m and o are the lengths of the monomer chain and satisfy: 1≤m≤10, 1≤o≤10; n is the length of the main chain, and satisfies: 50≤n≤5000; At least one of R1, R2, R3, R4, R5, R6, R7 and R8 is a halogen atom.

8. The method for preparing a cycloolefin copolymer according to claim 7, wherein The structural formula of the cycloolefin monomer is as follows: The structural formula of the α-olefin monomer is as follows: The structural formula of the halogenated heterocyclic olefin monomer is as follows: Among them, 1≤m≤10, 1≤o≤10.

9. The method for preparing a cycloolefin copolymer according to claim 7, wherein: The halogenated heterocyclic olefin monomer is any one of the following structural formulas:

10. The method for preparing a cyclic olefin copolymer according to claim 7, wherein: The catalyst is a metallocene catalyst.

11. The method for preparing a cycloolefin copolymer according to claim 10, wherein: The chemical structural formula of the catalyst is any one of the following:

12. The method for preparing a cyclic olefin copolymer according to claim 7, wherein: The molar ratio of the cycloolefin monomer, the α-olefin monomer and the halogenated heterocyclic olefin monomer is 1-50:1-50:5-100.

13. The method for preparing a cyclic olefin copolymer according to claim 7, wherein: The molar ratio of the catalyst to the cycloolefin monomer is 1:500-6000; The molar ratio of the catalyst to the α-olefin monomer is 1:50 to 2000.

14. The method for preparing a cyclic olefin copolymer according to claim 7, wherein: The polymerization reaction temperature is 25° C. to 150° C., and the polymerization reaction time is 0.5 h to 48 h.

15. An optical product, characterized in that: The optical product is prepared from the cyclic olefin copolymer according to any one of claims 1 to 6.

16. An electronic device, characterized in that: The optical product according to claim 15 is included.

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