Cyclic olefin copolymer and its preparation method and application

Abstract

The present application relates to the technical field of polymer synthesis, and provides a cycloolefin copolymer and its preparation method and application. The cycloolefin copolymer, the general structural formula of the cycloolefin copolymer is as shown in the following formula (1‑1) or formula (1‑2): In formula (1‑1) or formula (1‑2), the values ​​of x, y, and z satisfy: 0.57≤x / (x+y+z)≤0.67, 0.32≤y / (x+y+z)≤0.39, 0.01≤z / (x+y+z)≤0.04; A is an atom or an atomic group, B is an atom or an atomic group, and A and B are not hydrogen atoms at the same time. The present application introduces MDMON monomer in the cycloolefin copolymer, which can increase the glass transition temperature of the cycloolefin polymer, thereby improving the heat resistance of the cycloolefin copolymer.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer synthesis, and in particular to a cycloolefin copolymer and a preparation method and application thereof. Background Art

[0002] Cyclic olefin copolymer is a thermoplastic engineering plastic with high added value, which is polymerized from cyclic olefin and α-olefin. It is a very promising optical material. Cyclic olefin copolymer has high transparency, excellent heat resistance, chemical stability, melt fluidity and dimensional stability. It has been widely used in the manufacture of various optical lens prisms, car headlights, optical films for liquid crystal display screens, contact lenses, etc. Cyclic olefin copolymer is expected to replace polycarbonate and become the best material for the production of next generation high-density DVD. In addition, cyclic olefin copolymer resin also has a very low dielectric constant and can be used in the manufacture of electronic and electrical components. It has also become an emerging pharmaceutical and food packaging material due to its good moisture barrier properties.

[0003] There are two methods for synthesizing cycloolefin copolymers: one method is the chain polymerization of ethylene and norbornene monomers, and the other method is the ring-opening metathesis polymerization (ROMP) of norbornene monomers and hydrogenation. Currently, Mitsui Chemicals of Japan and Ticona of the United States have launched commercial COCs, with the trade names APEL and TOPAS respectively.

[0004] U.S. Patent US20200369812A1 discloses a method for preparing a cycloolefin copolymer, which is based on the copolymerization of ethylene and DMON as raw materials, and is ternary copolymerized by adding a second cycloolefin monomer (IndNB), in order to achieve the effect of increasing the glass transition temperature of the copolymer while maintaining the excellent properties of the cycloolefin copolymer. The technology is based on the basic composition of the molar ratio of ethylene to the total cycloolefin monomer unchanged, that is, the molar ratio of ethylene to the total cycloolefin monomer is about 64:36, and a high temperature resistant cycloolefin copolymer is prepared, and the reaction formula is shown in Formula 1 below:

[0005]

[0006] The patent provides performance test data of embodiments and comparative examples, such as Table 1 of the US20200369812A1 application document. It can be seen from the data provided in Table 1 that compared with the comparative example 2 (copolymer ethylene with DMON ratio 65:35), the glass transition temperature of the cycloolefin copolymer obtained by this technology is 143 to 152 ° C (the glass transition temperature of the comparative binary copolymer ethylene with DMON copolymer is 150 ° C), the refractive index is 1.55-1.56 (the refractive index of the comparative binary copolymer ethylene with DMON copolymer is 1.54), and the Abbe number is 43-49 (the Abbe number of the comparative binary copolymer ethylene with DMON copolymer is 56). It can be seen that under the premise of keeping the total cycloolefin monomer insertion rate basically unchanged, the effect of increasing the glass transition temperature of the cycloolefin copolymer by adding the second cycloolefin monomer is not obvious (basically below 150 ° C, up to 165 ° C), and the regulation trend is chaotic (with the increase of the third monomer, the glass transition temperature of the copolymer does not rise but decreases, such as P5 and P6), which is related to the selection of the second cycloolefin monomer. Moreover, compared with the cycloolefin copolymer without the introduction of the second cycloolefin monomer, the optical properties of the cycloolefin copolymer (the refractive index is not greatly improved, but the Abbe number is significantly reduced) deteriorate after the introduction of the second cycloolefin monomer. This is because the introduction of the benzene ring has a greater impact on the single existing norbornene ring, and this impact is inevitable. Summary of the invention

[0007] The purpose of the present application is to provide a cycloolefin copolymer and a preparation method and application thereof, aiming to solve the problem that the cycloolefin copolymer prepared by the existing method has a low glass transition temperature and poor optical properties.

[0008] In order to achieve the above application purpose, the technical solution adopted in this application is as follows:

[0009] In a first aspect, the present application provides a cycloolefin copolymer, wherein the general structural formula of the cycloolefin copolymer is as shown in the following formula (1-1) or formula (1-2):

[0010]

[0011] In formula (1-1) or formula (1-2), 0.57≤x / (x+y+z)≤0.67, 0.32≤y / (x+y+z)≤0.39, 0.01≤z / (x+y+z)≤0.04; A is an atom or an atomic group, B is an atom or an atomic group, and A and B are not hydrogen atoms at the same time.

[0012] The cycloolefin copolymer provided in the present application is formed by polymerization of ethylene monomer (the first monomer from the left corresponding to the structure shown in formula (1-1) or (1-2)), DMON monomer (the second monomer from the left corresponding to the structure shown in formula (1-1) or (1-2)), and MDMON monomer (the third monomer from the left corresponding to the structure shown in formula (1-1) or (1-2)). Among them, the polymer formed by the ring-opening metathesis polymerization and hydrogenation of the MDMON monomer itself has a relatively high glass transition temperature, which can reach above 230°C. The present application introduces MDMON monomer into the cycloolefin copolymer to increase the glass transition temperature of the cycloolefin polymer, thereby improving the heat resistance of the cycloolefin copolymer. Since the glass transition temperature of the MDMON polymer is high, the cycloolefin copolymer formed by a small amount (accounting for 0.01 to 0.04 of the total molar amount of the polymer) of MDMON monomer can significantly increase the glass transition temperature of the cycloolefin polymer. At the same time, the cycloolefin copolymer provided by the present application can reduce the negative impact of the reaction on the optical properties of the cycloolefin copolymer, and maintain good optical properties of the cycloolefin copolymer, because the MDMON monomer may not contain a benzene ring substituent, or the benzene ring substituent is far away from the reaction site-norbornene ring. In addition, since the present application introduces a small amount of MDMON monomer to achieve the effect of significantly improving the glass transition temperature of the cycloolefin polymer, the content of the MDMON monomer can be reduced, which is conducive to improving the economic efficiency of preparing the cycloolefin polymer.

[0013] As a possible implementation of the cycloolefin copolymer of the present application, A and B are each independently selected from hydrogen atoms, halogen atoms, alkyl groups, substituted alkyl groups, heteroalkyl groups, aryl groups, substituted aryl groups, heterocyclic groups, alkoxy groups, hydroxyl groups, ester groups, cyano groups, amino groups, and thiol groups. The present application introduces MDMON containing the above A and B into the cycloolefin copolymer to increase the molecular volume of the polymer, and the volume effect of the MDMON monomer is conducive to increasing the glass transition temperature of the cycloolefin polymer.

[0014] As a possible implementation of the cycloolefin copolymer of the present application, the alkyl group is selected from an alkyl group having a carbon number less than or equal to 20. In this case, the alkyl group can increase the volume of the MDMON monomer, which is beneficial to increase the glass transition temperature of the cycloolefin polymer; at the same time, since the carbon number of the alkyl group is within a suitable range, the effect of steric hindrance on the reaction activity of the MDMON monomer can be reduced, thereby facilitating the acquisition of the cycloolefin copolymer represented by formula (1-1) or formula (1-2).

[0015] As a possible implementation of the cycloolefin copolymer of the present application, the carbon number of the substituted alkyl group is less than or equal to 20, and the substituent in the substituted alkyl group is at least one of a hydroxyl group, a carboxyl group, an ester group, a cyano group, an amino group, a thiol group, and a halogen atom. In this case, the above-mentioned substituted alkyl group can increase the volume of the MDMON monomer, prompting the MDMON monomer to produce a volume effect, which is conducive to improving the glass transition temperature of the cycloolefin polymer; at the same time, since the carbon number of the substituted alkyl group is within a suitable range, the effect of steric hindrance on the reactivity of the MDMON monomer can be reduced. Not only that, by introducing polar groups such as hydroxyl groups, carboxyl groups, ester groups, cyano groups, amino groups, and thiol groups into A and B, the polarity of the cycloolefin copolymer can be increased, thereby improving the compatibility between the cycloolefin copolymer and the polar material, so that the cycloolefin copolymer can be compatible with other polar materials or materials containing polar materials, thereby widening the scope of application of the cycloolefin copolymer.

[0016] As a possible implementation of the cycloolefin copolymer of the present application, the number of carbon atoms in the heteroalkyl group is less than or equal to 20, and the heteroatoms in the heteroalkyl group are at least one of oxygen atoms, nitrogen atoms, sulfur atoms, and phosphorus atoms. In this case, the above-mentioned heteroalkyl group can increase the volume of the MDMON monomer, prompting the MDMON monomer to produce a volume effect, which is conducive to improving the glass transition temperature of the cycloolefin polymer; At the same time, the number of carbon atoms of the heteroalkyl group is within a suitable range, and the influence of steric hindrance on the reactivity of the MDMON monomer can be reduced. Not only that, the skeleton structure of the cycloolefin copolymer has excellent affinity, and after introducing oxygen atoms, nitrogen atoms, sulfur atoms, and phosphorus atoms in A and B, the polarity of the cycloolefin copolymer can be increased, thereby improving the compatibility between the cycloolefin copolymer and the polar material, so that the cycloolefin copolymer can be compatible with other polar materials or materials containing polar materials, thereby widening the scope of application of the cycloolefin copolymer.

[0017] As a possible implementation of the cycloolefin copolymer of the present application, the aromatic group is selected from phenyl, tolyl, naphthyl, benzyl or phenethyl. By introducing an aromatic group into the MDMON monomer structure of the cycloolefin polymer, the volume of the MDMON monomer can be increased, and the MDMON monomer is prompted to produce a volume effect, which is beneficial to increase the glass transition temperature of the cycloolefin polymer; moreover, the introduction of the benzene ring is beneficial to increase the refractive index of the cycloolefin polymer, thereby improving the optical properties of the cycloolefin polymer.

[0018] The aryl group in the substituted aryl group is selected from phenyl, tolyl, naphthyl, benzyl or phenethyl, and the substituent in the substituted aryl group is at least one of an alkyl group, a hydroxyl group, a carboxyl group, an ester group, a cyano group, an amino group, a thiol group, and a halogen atom. Among them, the aryl group in the substituted aryl group is conducive to improving the glass transition temperature and refractive index of the cycloolefin polymer; and the polar groups such as hydroxyl group, carboxyl group, ester group, cyano group, amino group, thiol group, etc. are conducive to adjusting the polarity of the cycloolefin polymer, thereby improving the compatibility between the cycloolefin polymer and other polar materials, so that it has a broader application prospect.

[0019] The heterocyclic group is selected from furan, pyran, pyridine or thiophene. The above groups have certain aromaticity, which is beneficial to improve the glass transition temperature and refractive index of the cycloolefin polymer; and the oxygen atoms, nitrogen atoms and sulfur atoms are beneficial to adjust the polarity of the cycloolefin polymer, thereby improving the compatibility between the cycloolefin polymer and other polar materials, so that it has a broader application prospect.

[0020] As a possible implementation of the cycloolefin copolymer of the present application, A and B are each independently selected from a hydrogen atom, a halogen atom, an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amino group, a thiol group, an -OC n H m 、-OCOC n H m , -C n H m 、-C6H5、-C6H4CH3、-C 10 H7, -CH2C6H5, -CH2CH2C6H5, -C n H m C6H5; wherein n is a positive integer less than or equal to 10, and m≤2n+1. Since A and B are not hydrogen atoms at the same time, the introduction of at least one of the above-mentioned substituted alkyl groups in formula (1-1) or formula (1-2) can increase the volume of the MDMON monomer, prompting the MDMON monomer to produce a volume effect, which is beneficial to increasing the glass transition temperature of the cycloolefin polymer; the introduction of the aromatic group is beneficial to increasing the glass transition temperature and refractive index of the cycloolefin polymer; and the introduction of the polar group or polar atom can increase the polarity of the cycloolefin copolymer, thereby improving the compatibility between the cycloolefin copolymer and the polar material, so that the cycloolefin copolymer can be compatible with other polar materials or materials containing polar materials, thereby broadening the application range of the cycloolefin copolymer.

[0021] As a possible implementation of the cycloolefin copolymer of the present application, A and B are connected to form a ring. When A and B are connected to form a ring, the volume of the MDMON monomer increases, and the volume effect increases, which is beneficial to increase the glass transition temperature of the cycloolefin polymer.

[0022] As a possible implementation of the application's cycloolefin copolymer, the ring is an aromatic ring, a cycloalkane or a ring structure containing an aromatic ring and a cycloalkane simultaneously. In this case, the cycloolefin polymer has a higher glass transition temperature. When the ring is an aromatic ring or a ring structure containing an aromatic ring and a cycloalkane simultaneously, the refractive index of the cycloolefin copolymer can be improved, and the Abbe number of the cycloolefin copolymer can not be reduced, and the optical property of the cycloolefin polymer is improved to a certain extent.

[0023] As a possible implementation of the cyclic olefin copolymer of the present application, the ring is one of the following ring structures:

[0024]

[0025] When A and B are connected to form the above ring structure, not only can the glass transition temperature of the cycloolefin polymer be increased, but also the refractive index of the cycloolefin copolymer can be increased without reducing the Abbe number, thereby improving the overall optical properties of the cycloolefin copolymer.

[0026] As a possible implementation of the cyclic olefin copolymer of the present application, the cyclic olefin copolymer is a copolymer shown in the following structure:

[0027]

[0028] The cycloolefin copolymer has a good glass transition temperature, thereby giving the glass transition temperature a good high temperature resistance. In addition, since the cycloolefin copolymer contains a benzene ring structure, the refractive index of the cycloolefin copolymer can be increased without reducing the Abbe number, thereby improving the overall optical properties of the cycloolefin copolymer.

[0029] As a possible implementation of the cycloolefin copolymer of the present application, the number average molecular weight of the cycloolefin copolymer is less than or equal to 80,000, and the weight average low molecular weight is less than or equal to 150,000. In this case, the cycloolefin copolymer has a lower viscosity and better fluidity at low temperatures, which is conducive to improving the processing performance of the polymer.

[0030] The second aspect of the present application provides a method for preparing a cycloolefin copolymer, comprising the following steps:

[0031] heating a solution system containing DMON, MDMON, ethylene, a catalyst and a co-catalyst to react to prepare the cycloolefin copolymer;

[0032] Wherein, the general structural formula of the cycloolefin copolymer is shown in the following formula (1-1) or formula (1-2):

[0033]

[0034] In formula (1-1) or formula (1-2), the values ​​of x, y, and z satisfy: 0.57≤x / (x+y+z)≤0.67, 0.32≤y / (x+y+z)≤0.39, 0.01≤z / (x+y+z)≤0.04; R1 is an atom or an atomic group, R2 is an atom or an atomic group, and R1 and R2 are not hydrogen atoms at the same time;

[0035] The catalyst is a metallocene catalyst.

[0036] The preparation method of the cycloolefin copolymer provided by the present application selects DMON and the four-membered ring-shaped cycloolefin monomer MDMON as the cycloolefin monomer, wherein the polymer formed by the ring-opening metathesis polymerization and hydrogenation of the MDMON monomer itself has a high glass transition temperature, which can reach above 230°C. Therefore, the present application uses ethylene, DMON and MDMON monomers as raw materials for polymerization reaction, which can increase the glass transition temperature of the ternary cycloolefin polymer, thereby improving the heat resistance of the cycloolefin copolymer. Since the glass transition temperature of the MDMON polymer is high, adding a small amount (0.01 to 0.04 of the total molar amount of the sticky polymer) of MDMON monomer in the combination reaction can significantly increase the glass transition temperature of the cycloolefin polymer. At the same time, the preparation method of the cycloolefin copolymer provided by the present application, since the MDMON monomer does not contain a benzene ring substituent or the benzene ring substituent is far away from the reaction site-norbornene ring, can reduce the negative impact of the reaction on the optical properties of the cycloolefin copolymer, so that the cycloolefin copolymer maintains good optical properties. In addition, the present application introduces a small amount of MDMON monomer to achieve the effect of significantly increasing the glass transition temperature of the cycloolefin polymer. Therefore, the addition amount of MDMON monomer can be reduced, which is beneficial to improving the economic efficiency of preparing the cycloolefin polymer.

[0037] The general structural formula of the catalyst is shown in the following formula (2):

[0038]

[0039] In formula (2), M 1 is selected from scandium, titanium, vanadium, zirconium, hafnium, niobium or tantalum, M 2 、M 3 Each independently selected from carbon, silicon, germanium or tin;

[0040] X represents carbon or silicon;

[0041] R1 and R2 are each independently selected from a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an aryloxy group, an aralkyl group, an alkaryl group or an aralkenyl group;

[0042] R3 and R4 are each independently selected from a hydrogen atom or a hydrocarbon group;

[0043] R5, R6, R7, and R8 are each independently selected from a hydrogen atom, a hydrocarbon group, or a silicon-containing group, wherein the silicon-containing group is connected to the carbon atom at the corresponding substitution position through a silicon atom;

[0044] R 10 , R 11 , R 12 , R 15 , R 16 , R 17 are each independently selected from alkyl, alkoxy, alkenyl, aryl, aryloxy, aralkyl, alkaryl or aralkenyl;

[0045] R9, R 13 , R 14 , R 18 are each independently selected from a hydrogen atom, a hydrocarbon group or a hydrocarbonoxy group;

[0046] Wherein, at least one of R5, R6, R7, and R8 is a silicon-containing group, and / or the M 2 、M 3 At least one of them is silicon.

[0047] The catalyst represented by formula (2) is beneficial to promoting the polymerization of three polymerization monomers to form a cycloolefin polymer represented by formula (1-1) or formula (1-2).

[0048] As a possible implementation of the method for preparing the cycloolefin copolymer of the present application, at least one of the R6 and R7 is the silicon-containing group, or the M 2 、M 3 At least one of them is silicon.

[0049] In this case, the catalyst shown in formula (2) is beneficial to promoting the polymerization activity of the three polymerization monomers, and the substituent in the substituted alkyl containing heteroatoms contains a silicon group, which is beneficial to controlling the selectivity of the reaction monomers, and then controlling the ratio of the three reaction monomers, and finally obtaining a cycloolefin polymer having the ratio of each monomer in the structure of formula (1-1) or formula (1-2).

[0050] As a possible implementation of the preparation method of the cycloolefin copolymer of the present application, R5, R6, R7, and R8 are independently selected from hydrocarbon groups or silicon-containing groups having carbon atoms less than or equal to 6. In this case, the silicon-containing group can control the selectivity of the reaction monomers through steric effect, thereby controlling the ratio of the three reaction monomers; moreover, when R5, R6, R7, and R8 are the catalysts shown in formula (2) with silicon-containing groups, when catalyzing the polymerization reaction of the three reaction monomers, a cycloolefin copolymer with a low molecular weight (such as a number average molecular weight less than or equal to 80,000 and a weight average low molecular weight less than or equal to 150,000) can be obtained without adding additives such as chain transfer agents.

[0051] As a possible implementation method of the preparation method of the cycloolefin copolymer of the present application, R 10 , R 11 , R 12 , R 15 , R 16 , R 17 The number of carbon atoms is less than or equal to 10. In this case, the catalyst has a suitable spatial size, which is beneficial to improving its catalytic activity.

[0052] As a possible implementation of the preparation method of the cycloolefin copolymer of the present application, the co-catalyst is at least one of methylaluminoxane, modified methylaluminoxane, and an organic boron compound. Methylaluminoxane, modified methylaluminoxane, and an organic boron compound can activate the catalyst of the structure shown in formula (2) to improve the catalyst activity. When R5, R6, R7, and R8 in the catalyst are silicon-containing groups, the selectivity of the catalyst to the reaction monomer can also be improved, thereby controlling the reaction monomer ratio of the polymerization reaction.

[0053] As a possible implementation of the method for preparing the cycloolefin copolymer of the present application, the temperature of the heating reaction is 50-90° C. and the time is 2-60 min. In this case, the catalyst has good catalytic activity, which is conducive to improving the polymerization reaction efficiency.

[0054] A third aspect of the present application provides an application of a cyclic olefin copolymer as a camera lens material, wherein the cyclic olefin copolymer is the cyclic olefin copolymer described in the first aspect or a cyclic olefin copolymer prepared by the method described in the second aspect.

[0055] The cyclic olefin copolymer provided in the present application has a high glass transition temperature, and therefore has good high temperature resistance and maintains good optical properties. It can be used as a camera lens material, giving the camera lens good high temperature resistance and optical properties.

[0056] As a possible implementation of the application of the cyclic olefin copolymer of the present application, the camera lens material is a vehicle-mounted camera lens material or a security camera lens material. Compared with the currently commercially available cyclic olefin copolymer material, the cyclic olefin copolymer provided by the present application is used as a vehicle-mounted camera lens material or a security camera lens material, which has better heat resistance without affecting the optical performance of the camera lens. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] Figure 1 The cycloolefin monomer MDMON prepared in Example 1 of the present application 1 H-NMR spectrum;

[0058] Figure 2 The novel cycloolefin monomer MDMON prepared in Example 1 of the present application13 C-NMR spectrum;

[0059] Figure 3 is a DSC curve diagram of the cyclic olefin copolymer P1 obtained in Example 2 of the present application;

[0060] Figure 4 The cycloolefin copolymer P1 obtained in Example 2 of the present application 13 C-NMR spectrum;

[0061] Figure 5 is a DSC curve diagram of the cyclic olefin copolymer P2 obtained in Example 3 of the present application;

[0062] Figure 6 The cycloolefin copolymer P2 obtained in Example 3 of the present application 13 C-NMR spectrum;

[0063] Figure 7 This is a DSC curve diagram of the cyclic olefin copolymer P3 obtained in Example 4 of the present application;

[0064] Figure 8 The cycloolefin copolymer P3 obtained in Example 4 of the present application 13 C-NMR spectrum;

[0065] Fig. 9 This is a DSC curve diagram of the cyclic olefin copolymer P4 obtained in Example 5 of the present application;

[0066] Fig.10 The cycloolefin copolymer P5 obtained in Comparative Example 1 13 C-NMR spectrum;

[0067] Fig.11 This is the DSC curve of the cycloolefin copolymer P5 obtained in Comparative Example 1.

[0068] In the DSC curve diagram, the horizontal axis "Temperature" represents temperature, and the vertical axis "Heat Flow" represents heat flow. DETAILED DESCRIPTION

[0069] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clearly understood, the present application is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.

[0070] In this application, the term "and / or" describes the association relationship of associated objects, indicating that there may be three relationships. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone. A and B can be singular or plural. The character " / " generally indicates that the associated objects are in an "or" relationship.

[0071] In this application, "at least one" means one or more, and "plurality" means two or more. "At least one of the following" or similar expressions refers to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, c can be single or multiple, respectively.

[0072] It should be understood that in the various embodiments of the present application, the size of the serial numbers of the above-mentioned processes does not mean the order of execution, some or all of the steps can be executed in parallel or sequentially, and the execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.

[0073] The terms used in the embodiments of the present application are only for the purpose of describing specific embodiments, and are not intended to limit the present application. The singular forms "a", "said" and "the" used in the embodiments of the present application and the appended claims are also intended to include plural forms, unless the context clearly indicates other meanings.

[0074] The weight of the relevant components mentioned in the embodiment description of the present application can not only refer to the specific content of each component, but also represent the proportional relationship between the weights of the components. Therefore, as long as the content of the relevant components is proportionally enlarged or reduced according to the embodiment description of the present application, it is within the scope disclosed in the embodiment description of the present application. Specifically, the mass described in the embodiment description of the present application can be a mass unit known in the chemical industry such as μg, mg, g, kg, etc.

[0075] The terms "first" and "second" are used only for descriptive purposes to distinguish objects such as substances from each other, and should not be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features. For example, without departing from the scope of the embodiments of the present application, the first XX may also be referred to as the second XX, and similarly, the second XX may also be referred to as the first XX. Thus, the features defined as "first" and "second" may explicitly or implicitly include one or more of the features.

[0076] The term "COC" is an abbreviation for "Cyclic Olefin Copolymer", which means cyclic olefin copolymer;

[0077] The term "DVD" is an abbreviation for "Digital Video Disc", which means High-density Digital Video Disc;

[0078] The term “ROMP” is an abbreviation for “Ring-Opening Metathesis Polymerization”, which means ring-opening metathesis polymerization;

[0079] The term "DMON" is an abbreviation for "1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalener", which means dimethyl-bridged octahydronaphthalene;

[0080] The term "MDMON" is an abbreviation of "Modified DMON", which means dimethyl octahydronaphthalene containing a substituent, and is the third monomer introduced in the examples of the present application;

[0081] The term "IndNB" is an abbreviation for "1,4,4a,9a-tetrahydro-1,4-methano-fluorene r", which means indenonorbornene;

[0082] The term "IndDMON" is an abbreviation for "5,5a,6,9,9a,10,10a,11-octahydro-4bH-5,10,6,9-dimethano-benzo[b]fluorener", which means indenodimethano-octahydronaphthalene;

[0083] The term "MAO" is an abbreviation for "Methylaluminoxane", which means methylaluminoxane.

[0084] COC is widely used due to its excellent properties such as high transparency, excellent heat resistance, chemical stability, melt fluidity and dimensional stability. A large amount of COC materials are consumed in China every year for the manufacture of various products. However, the current Tg of COC materials is lower than 140°C, which does not meet the needs of application scenarios with high long-term use temperatures. Therefore, it is particularly important to develop optical resin materials with better heat resistance.

[0085] In view of this, an embodiment of the present application provides a cycloolefin copolymer, which is a random copolymer formed by an ethylene monomer and two cycloolefin monomers, and its general structural formula is shown in the following formula (1-1) or formula (1-2):

[0086]

[0087] The structure of formula (1-1) or formula (1-2) shows the molar content of the three monomers in the cycloolefin copolymer, but does not represent the arrangement order of the three monomers in the cycloolefin copolymer. In the structure of formula (1-1) or formula (1-2) in the embodiment of the present application, the three monomers are randomly arranged in the molecular chain to form a random copolymer.

[0088] In the embodiment of the present application, the two olefin monomers are DMON monomer and MDMON monomer, and the structures of the ethylene monomer (corresponding to the first monomer from the left of the structure shown in formula (1-1) or formula (1-2)) and the DMON monomer (corresponding to the second monomer from the left of the structure shown in formula (1-1) or formula (1-2)) are shown in the following formula (1-1) and formula (1-2), respectively:

[0089]

[0090] The MDMON monomer includes two cases according to the structural difference of formula (1-1) or formula (1-2), and its structure corresponds to the third monomer from the left of the structure shown in formula (1-1) and formula (1-2), and the monomer structures of the two cases are shown in the following formula (1-3-1) and formula (1-3-2), respectively:

[0091]

[0092] Among them, the structures (MDMON monomers) shown in formula (1-3-1) and formula (1-3-2) form polymers after self-ring-opening metathesis polymerization and hydrogenation, which have a relatively high glass transition temperature, which can reach above 230° C. Therefore, the embodiment of the present application introduces MDMON monomers into the cycloolefin copolymer to increase the glass transition temperature of the cycloolefin polymer, thereby improving the heat resistance of the cycloolefin copolymer.

[0093] Moreover, the reaction site-norbornene ring in the structure of formula (1-3-1) and formula (1-3-2) may not be connected to the benzene ring. Even if a benzene ring structure or a substituent containing a benzene ring structure is introduced into the structure of formula (1-3-1) and formula (1-3-2), the distance between the benzene ring and the norbornene ring is relatively far. Therefore, the structure of formula (1-3) can reduce the negative impact of the polymerization reaction on the optical properties of the cycloolefin copolymer, so that the cycloolefin copolymer provided in the embodiment of the present application maintains good optical properties. The good optical properties at least include that the Abbe number of the cycloolefin copolymer does not decrease.

[0094] In the embodiment of the present application, since the glass transition temperature of the MDMON polymer is high, in formula (1-1) or formula (1-2), the values ​​of x, y, and z satisfy: 0.57≤x / (x+y+z)≤0.67, 0.32≤y / (x+y+z)≤0.39, 0.01≤z / (x+y+z)≤0.04. The cycloolefin copolymer formed by a small amount of MDMON monomer can significantly increase the glass transition temperature of the cycloolefin polymer. In addition, the embodiment of the present application introduces a small amount of MDMON monomer can achieve the effect of significantly increasing the glass transition temperature of the cycloolefin polymer, so the content of the MDMON monomer can be reduced, which is conducive to improving the economic efficiency of preparing the cycloolefin polymer.

[0095] Formula (1-3-1), formula (1-3-2) structure, i.e. A, B in MDMON monomer, are A, B in cycloolefin shown in formula (1-1) or formula (1-2). Wherein, A is an atom or an atomic group, B is an atom or an atomic group, and A and B are not hydrogen atoms at the same time. In formula (1-3-1) and formula (1-3-2), atoms or atomic groups that are not hydrogen at the same time are introduced, and non-hydrogen atoms or atomic groups can increase the volume of MDMON monomer, prompting MDMON monomer to produce a volume effect, which is conducive to improving the glass transition temperature of cycloolefin copolymer. In addition, the skeleton structure of the cycloolefin copolymer provided in the embodiment of the present application itself has excellent affinity and has good compatibility with non-polar or weakly polar materials. The embodiment of the present application can also adjust the polarity of the cycloolefin copolymer by introducing polar groups or polar atoms in A and B, so that it can be more suitable for the polarity requirements of the cycloolefin copolymer in different application scenarios.

[0096] As a possible implementation, A and B are each independently selected from hydrogen atoms, halogen atoms, alkyl groups, substituted alkyl groups, heteroalkyl groups, aryl groups, substituted aryl groups, heteroaryl groups, alkoxy groups, hydroxyl groups, ester groups, cyano groups, amino groups, and thiol groups. When A and B are not hydrogen atoms at the same time, the introduction of MDMON containing the above A and B into the cycloolefin copolymer increases the molecular volume of the polymer, and the volume effect of MDMON increases the glass transition temperature of the cycloolefin polymer.

[0097] As a possible implementation, the alkyl group is selected from an alkyl group having a carbon number less than or equal to 20. In this case, the alkyl group can increase the volume effect of the MDMON monomer, which is beneficial to increase the glass transition temperature of the cycloolefin polymer; at the same time, since the carbon number of the alkyl group is within a suitable range, the effect of steric hindrance on the reaction activity of the MDMON monomer can be reduced, thereby facilitating the acquisition of the cycloolefin copolymer represented by formula (1-1) or formula (1-2). In some embodiments, the carbon number of the alkyl group is less than or equal to 10. Exemplarily, the alkyl group can be the following groups having isomeric structures: -CH3, -C2H5, -C3H7, -C4H9, -C5H 11、-C6H 13 、-C7H 15 、-C8H 17 、-C9H 19 , -C 10 H 21 .

[0098] As a possible implementation method, the number of carbon atoms of the substituted alkyl group is less than or equal to 20, and the substituent in the substituted alkyl group is at least one of a hydroxyl group, a carboxyl group, an ester group, a cyano group, an amino group, a thiol group, and a halogen atom. In this case, the above-mentioned substituted alkyl group can increase the volume of the MDMON monomer, prompting the MDMON monomer to produce a volume effect, which is beneficial to increase the glass transition temperature of the cycloolefin polymer; at the same time, since the number of carbon atoms of the substituted alkyl group is within a suitable range, the effect of steric hindrance on the reactivity of the MDMON monomer can be reduced. In addition, by introducing polar groups such as hydroxyl groups, carboxyl groups, ester groups, cyano groups, amino groups, and thiol groups into A and B, the polarity of the cycloolefin copolymer can be increased, thereby improving the compatibility between the cycloolefin copolymer and the polar material, so that the cycloolefin copolymer can be compatible with other polar materials or materials containing polar materials, thereby broadening the application range of the cycloolefin copolymer. In some embodiments, the number of carbon atoms of the substituted alkyl group is less than or equal to 10. Exemplarily, the substituted alkyl group can be -CH2OH, -C2H4OH, -C3H6OH, -C4H8OH, -C5H 10 OH, -C6H 12 OH, -C7H 14 OH, -C8H 16 OH, -C9H 18 OH, -C 10 H 20 OH, -CH2COOH, -C2H4COOH, -C3H6COOH, -C4H8COOH, -C5H 10 COOH, -C6H 12 COOH, -C7H 14 COOH, -C8H 16 COOH, -C9H 18 COOH, -OCOCH3, -COOCH3, -COOC2H5, -OCOC2H5, -CH2COOCH3, -CH2OCOCH3, -COOC3H7, -OCOC3H7, -CH2COOC2H5, -CH2OCOC2H5, -C2H4COOCH3 , -C2H4OCOCH3, -COOC4H9, -OCOC4H9, -CH2COOC3H7, -CH2OCOC3H7, -C2H4COOC2H5, -C2H4OCOCC2H5, -C3H6COOCH3, -C3H6OCOCCH3, -COOC5H11 、-OCOC5H 11 、-CH2COOC4H9、-CH2OCOC4H9、-C2H4COOC3H7、-C2H4OCOCC3H7、-C3H6COOC2H5、-C3H6OCOCC2H5、-C4H7COOCH3、-C4H7OCOCCH3、-COOC6H 13 、-OCOC6H 13 、-CH2COOC5H 11 、-CH2OCOC5H 11 、-C2H4COOC4H9、-C2H4OCOCC4H9、-C3H6COOC3H7、-C3H6OCOCC3H7、-C4H8COOC2H5、-C4H8OCOCC2H5、-C5H 10 COOCH3、-C5H 10 OCOCCH3、-COOC7H 15 、-OCOC7H 15 、-CH2COOC6H 13 、-CH2OCOC6H 13 、-C2H4COOC5H 11 、-C2H4OCOCC5H 11 、-C3H6COOC4H9、-C3H6OCOCC4H9、-C4H8COOC3H7、-C4H8OCOCC3H7、-C5H 10 COOC2H5、-C5H 10 OCOCC2H5、-C6H 12 COOCH3、-C6H 12 OCOCH3、-COOC8H 17 、-OCOC8H 17 、-CH2COOC7H 15 、-CH2OCOC7H 15 、-C2H4COOC6H 13 、-C2H4OCOCC6H 13 、-C3H6COOC5H 11 、-C3H6OCOCC5H 11 、-C4H8COOC4H9、-C4H8OCOCC4H9、-C5H 10 COOC3H7、-C5H 10 OCOCC3H7、-C6H 12 COOC2H5、-C6H 12 OCOC2H5、-C7H 14 COOCH3、-C7H14 OCOCH3, -CH2CN, -C2H4CN, -C3H6CN, -C4H8CN, -C5H 10 CN, -C6H 12 CN, -C7H 14 CN, -C8H 16 CN, -C9H 18 CN, -C 10 H 20 CN, -CH2NH2, -C2H4NH2, -C3H6NH2, -C4H8NH2, -C5H 10 NH2, -C6H 12 NH2, -C7H 14 NH2, -C8H 16 NH2, -C9H 18 NH2, -C 10 H 20 NH2, -CH2SH, -C2H4SH, -C3H6SH, -C4H8SH, -C5H 10 SH, -C6H 12 SH, -C7H 14 SH, -C8H 16 SH, -C9H 18 SH, -C 10 H 20 SH.

[0099] As a possible implementation, the number of carbon atoms in the heteroalkyl group is less than or equal to 20, and the heteroatoms in the heteroalkyl group are at least one of oxygen atoms, nitrogen atoms, sulfur atoms, and phosphorus atoms. In this case, the above-mentioned heteroalkyl group can increase the volume of the MDMON monomer, prompting the MDMON monomer to produce a volume effect, which is conducive to improving the glass transition temperature of the cycloolefin polymer; At the same time, the number of carbon atoms in the heteroalkyl group is within a suitable range, and the influence of steric hindrance on the reactivity of the MDMON monomer can be reduced. Not only that, the skeleton structure of the cycloolefin copolymer itself has excellent affinity, and after introducing oxygen atoms, nitrogen atoms, sulfur atoms, and phosphorus atoms in A and B, the polarity of the cycloolefin copolymer can be increased, thereby improving the compatibility between the cycloolefin copolymer and the polar material, so that the cycloolefin copolymer can be compatible with other polar materials or materials containing polar materials, thereby widening the scope of application of the cycloolefin copolymer. In some embodiments, the number of carbon atoms in the heteroalkyl group is less than or equal to 10.

[0100] As a possible implementation, the aryl group is selected from an aryl group having a carbon number less than or equal to 30. The aryl group includes an aromatic group and an aralkyl group. Exemplarily, the aryl group is selected from an aromatic group or an aralkyl group such as phenyl, phenyl, tolyl, naphthyl, benzyl and phenethyl. By introducing an aromatic group into the MDMON monomer structure of the cycloolefin polymer, the volume of the MDMON monomer can be increased, and the MDMON monomer is prompted to produce a volume effect, which is beneficial to improving the glass transition temperature of the cycloolefin polymer; moreover, the introduction of the benzene ring is beneficial to improving the refractive index of the cycloolefin polymer, thereby improving the optical properties of the cycloolefin polymer.

[0101] As a possible implementation, the number of carbon atoms in the substituted aryl is less than or equal to 30. Exemplarily, the aryl in the substituted aryl is selected from aromatic groups or aralkyl groups such as phenyl, phenyl, tolyl, naphthyl, benzyl and phenethyl. The substituent in the substituted aryl is at least one of an alkyl, hydroxyl, carboxyl, ester, cyano, amino, thiol, and halogen atom. Among them, the aryl in the substituted aryl is conducive to improving the glass transition temperature and refractive index of the cycloolefin polymer; and polar groups such as hydroxyl, carboxyl, ester, cyano, amino, and thiol are conducive to adjusting the polarity of the cycloolefin polymer, thereby improving the compatibility between the cycloolefin polymer and other polar materials, so that it has a broader application prospect.

[0102] As a possible implementation, the number of carbon atoms in the heterocyclic group is less than or equal to 30. Exemplarily, the heteroaryl group is selected from furan, pyran, pyridine or thiophene. The above groups have certain aromaticity, which is beneficial to improve the glass transition temperature and refractive index of the cycloolefin polymer; and the oxygen atoms, nitrogen atoms, sulfur atoms, and phosphorus atoms are beneficial to adjust the polarity of the cycloolefin polymer, thereby improving the compatibility between the cycloolefin polymer and other polar materials, so that it has a broader application prospect.

[0103] As a possible implementation, A and B are each independently selected from a hydrogen atom, a halogen atom, an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amino group, a thiol group, an -OC n H m 、-OCOC n H m , -C n H m 、-C6H5、-C6H4CH3、-C 10 H7, -CH2C6H5, -CH2CH2C6H5, -C n H mC6H5; wherein n is a positive integer less than or equal to 10, and m≤2n+1, that is, m is a positive integer less than or equal to 21. Since A and B are not hydrogen atoms at the same time, the introduction of at least one of the above-mentioned substituted alkyl groups in formula (1-1) or formula (1-2) can increase the volume of the MDMON monomer, prompting the MDMON monomer to produce a volume effect, which is beneficial to increasing the glass transition temperature of the cycloolefin polymer; the introduction of the aromatic group is beneficial to increasing the glass transition temperature and refractive index of the cycloolefin polymer; and the introduction of the polar group or polar atom can increase the polarity of the cycloolefin copolymer, thereby improving the compatibility between the cycloolefin copolymer and the polar material, so that the cycloolefin copolymer can be compatible with other polar materials or materials containing polar materials, thereby broadening the application range of the cycloolefin copolymer.

[0104] As a possible implementation method, A and B are connected to form a ring. In the embodiments of the present application, the so-called "A and B are connected to form a ring" means that A and B are bonded so that A and B are in a ring structure. After A and B are connected to form a ring, the volume of the MDMON monomer increases, and the volume effect increases, which is conducive to increasing the glass transition temperature of the cycloolefin polymer.

[0105] As a possible implementation, the ring is an aromatic ring, a cycloalkane or a ring structure containing an aromatic ring and a cycloalkane simultaneously. In this case, the cycloolefin polymer has a higher glass transition temperature. When the ring is an aromatic ring or a ring structure containing an aromatic ring and a cycloalkane simultaneously, the refractive index of the cycloolefin copolymer can be improved, and the Abbe number of the cycloolefin copolymer can not be reduced, and the optical property of the cycloolefin polymer can be improved to a certain extent.

[0106] As a possible implementation, the ring is one of the following ring structures:

[0107]

[0108] When A and B are connected to form the above ring structure, not only can the glass transition temperature of the cycloolefin polymer be increased, but also the refractive index of the cycloolefin copolymer can be increased without reducing the Abbe number, thereby improving the overall optical properties of the cycloolefin copolymer.

[0109] Exemplarily, the MDMON monomer may be INDDMON or StDMON, but is not limited thereto.

[0110] As a possible implementation, the cyclic olefin copolymer is a polymer shown in the following structure:

[0111]

[0112] The cycloolefin copolymer has a good glass transition temperature, thereby giving the glass transition temperature a good high temperature resistance. In addition, since the cycloolefin copolymer contains a benzene ring structure, the refractive index of the cycloolefin copolymer can be increased without reducing the Abbe number, thereby improving the overall optical properties of the cycloolefin copolymer.

[0113] In the embodiment of the present application, cycloolefin copolymers of different molecular weights can be obtained according to the application scenarios of the cycloolefin copolymers. As a possible implementation, the number average molecular weight of the cycloolefin copolymer is less than or equal to 80,000, and the weight average low molecular weight is less than or equal to 150,000. In this case, the cycloolefin copolymer has a lower viscosity and has good fluidity at low temperatures, which is conducive to improving the processing properties of the polymer.

[0114] The cycloolefin copolymer provided in the embodiments of the present application can be prepared by the following method.

[0115] Correspondingly, the embodiment of the present application provides a method for preparing a cycloolefin copolymer, comprising the following steps:

[0116] The solution system containing DMON, MDMON, ethylene, catalyst and co-catalyst is heated for reaction to prepare cycloolefin copolymer.

[0117] In the present embodiment, two cycloolefin monomers DMON and MDMON (such as INDDMON or StDMON) and ethylene are used as polymerization monomers. Under the action of a catalyst and a co-catalyst, the three monomers undergo random copolymerization to obtain a cycloolefin copolymer shown in the structure of formula (1-1) or formula (1-2).

[0118] Among them, the cycloolefin monomer IndDMON was originally a by-product produced during the synthesis of IndNB, with very little output and almost no application. The structure of the cycloolefin monomer IndDMON refers to Example 1 and Example 2. In one possible implementation, the yield of the cycloolefin monomer IndDMON is increased by changing the ratio of the two raw materials for synthesizing IndNB. In this way, IndNB and IndDMON are mainly synthesized, and both of them, as important cycloolefin monomers, can be more effectively applied.

[0119] The embodiment of the present application can achieve the effect of greatly improving the glass transition temperature of the cycloolefin copolymer by introducing a very small amount of cycloolefin monomer MDMON, and on this basis, maintain the excellent optical properties of the prepared cycloolefin copolymer and the high heat-resistant cycloolefin copolymer.

[0120] In the embodiment of the present application, when the three reaction monomers undergo random polymerization, the activity of MDMON is slightly reduced. Therefore, the feed content of the reaction monomer is appropriately adjusted according to the molar ratio of the three monomers in the expected copolymer. In a possible implementation, when preparing a cycloolefin polymer, the feed molar ratio of ethylene, DMON and MDMON is (0.57-0.67): (0.32-0.39): (0.01-0.04). In this case, the three can participate in the reaction in a suitable ratio to prepare a cycloolefin copolymer shown in the structure of formula (1-1) or formula (1-2).

[0121] In the embodiment of the present application, when DMON, MDMON, and ethylene are added to the reaction device, DMON and MDMON can be added to the reaction device first, and then ethylene is connected to the reaction device through a pipeline. This method can control the content of ethylene monomer and adjust the reaction efficiency by controlling the ethylene pressure when pumping.

[0122] In the embodiment of the present application, a metallocene catalyst is used to catalyze random polymerization of DMON, MDMON, and ethylene to form a cycloolefin copolymer having a structure shown in formula (1-1) or formula (1-2). In one possible implementation, the general structural formula of the catalyst is as follows:

[0123]

[0124] In formula (2), M 1 is selected from scandium, titanium, vanadium, zirconium, hafnium, niobium or tantalum, M 2 、M 3 Each independently selected from carbon, silicon, germanium or tin;

[0125] X represents carbon or silicon;

[0126] R1 and R2 are each independently selected from a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an aryloxy group, an aralkyl group, an alkaryl group or an aralkenyl group;

[0127] R3 and R4 are each independently selected from a hydrogen atom or a hydrocarbon group;

[0128] R5, R6, R7, and R8 are each independently selected from a hydrogen atom, a hydrocarbon group, or a silicon-containing group, wherein the silicon-containing group is connected to the carbon atom at the corresponding substitution position through a silicon atom;

[0129] R 10 , R 11 , R 12 , R 15 , R 16 , R 17 are each independently selected from alkyl, alkoxy, alkenyl, aryl, aryloxy, aralkyl, alkaryl or aralkenyl;

[0130] R9, R 13 , R 14 , R 18 are each independently selected from a hydrogen atom, a hydrocarbon group or a hydrocarbonoxy group;

[0131] Wherein, at least one of R5, R6, R7, and R8 is a silicon-containing group, and / or the M 2 、M 3 At least one of them is silicon.

[0132] The catalyst shown in formula (2) is a cyclopentadienylfluorene-bridged transition metal catalyst. A silicon-containing heteroatom group is introduced into the cyclopentadienyl or fluorene group of the catalyst. During the ternary copolymerization process, the metal center M of the catalyst 1 Synergistic effects are produced with the silicon atoms introduced on the cyclopentadienyl or fluorenyl groups, which can promote chain transfer in the polymerization process and increase the insertion rate of cycloolefin monomers, so that cycloolefin copolymers with low molecular weight (weight average molecular weight less than or equal to 150,000) and moderate glass transition temperature can be obtained by chain addition copolymerization without the additional introduction of molecular weight regulators such as hydrogen or propylene. The obtained cycloolefin copolymer has a lower melt flow index due to its lower molecular weight and good processing performance, making the cycloolefin copolymer suitable for various application scenarios. In addition, the silicon-containing group can control the selectivity of the reaction monomers through the steric effect, thereby controlling the ratio of the three reaction monomers.

[0133] As a possible implementation, at least one of R5, R6, R7, and R8 is a silicon-containing group, and M 2 、M 3 In some other embodiments of the present application, R5, R6, R7, and R8 are independently selected from hydrogen atoms or hydrocarbon groups, and M 2 、M 3 In some other embodiments of the present application, at least one of R5, R6, R7, and R8 is a silicon-containing group, and M 2 、M 3 At least one of them is silicon. The silicon-containing group is beneficial to controlling the selectivity of the reaction monomers, and then controlling the ratio of the three reaction monomers, and finally obtaining a cycloolefin polymer having the ratio of each monomer in the structure of formula (1-1) or formula (1-2).

[0134] In some embodiments of the present application, R5, R6, R7, and R8 are independently selected from hydrocarbon groups or silicon-containing groups having carbon atoms less than or equal to 6. For example, the silicon-containing group can be selected from trimethylsilyl, triethylsilyl, and triphenylsilyl, but is not limited thereto.

[0135] In some embodiments of the present application, at least one of R6 and R7 is a silicon-containing group, or M 2 、M 3At least one of them is silicon. The silicon-containing groups are located at the 3 and 4 positions of the cyclopentadiene, which are closer to the metal center M than the 2 and 5 positions. 1 Furthermore, the introduction of silicon-containing groups at the 3- and 4-positions of cyclopentadiene can not only achieve 1 The formation of weak coordination promotes chain transfer, reduces polymer molecular weight, and can avoid affecting the polymerization activity of the catalyst due to strong coordination.

[0136] In some embodiments of the present application, the R 10 , R 11 , R 12 , R 15 , R 16 , R 17 The number of carbon atoms is less than or equal to 10. In this case, the catalyst has a suitable spatial size, which is beneficial to improving its catalytic activity.

[0137] In the embodiment of the present application, the catalyst for preparing the cycloolefin copolymer also includes a co-catalyst, and the co-catalyst includes but is not limited to at least one of methylaluminoxane, modified methylaluminoxane, and an organic boron compound. In some embodiments of the present application, the organic boron compound includes one or more of tris(pentafluorophenyl)boron, triphenylcarbonium tetrakis(pentafluorophenyl)borate, and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate. Using methylaluminoxane, modified methylaluminoxane, and an organic boron compound as a co-catalyst is conducive to ensuring the copolymerization activity of the cycloolefin copolymer preparation.

[0138] As a possible implementation, the molar ratio of the catalyst and the co-catalyst shown in formula (2) is 1: (10-10000). The molar amount of the two is within the above range, which is beneficial to the activation performance of the co-catalyst to the catalyst. Exemplarily, the molar ratio of the catalyst and the co-catalyst shown in formula (1-1) or formula (1-2) is 1: 100, 1: 200, 1: 300, 1: 400, 1: 500, 1: 600, 1: 700, 1: 800, 1: 900, 1: 1000, 1: 1200, 1: 1500, 1: 1800, 1: 2000, 1: 2200, 1: 2500, 1: 2800, 1: 3000, 1: 3200, 1: 3500, 1: 3800, 1: 4000 and other specific molar ratios.

[0139] In the embodiment of the present application, the solvent used to disperse the raw materials and the catalyst in the solution system containing DMON, MDMON, ethylene, a catalyst and a co-catalyst is an inert solvent. In a possible implementation, the solvent is a non-polar solvent, which has good dispersibility for DMON, MDMON and ethylene, and is reactively inert and does not affect the reaction effect of the polymerization reaction. In some embodiments, the solvent is a straight-chain alkane compound, a cyclic hydrocarbon compound or an aromatic hydrocarbon compound. Exemplarily, the solvent is toluene, but is not limited thereto.

[0140] In the embodiments of the present application, the polymerization reaction is carried out in an inert environment. The inert environment can be a nitrogen atmosphere or an inert atmosphere. In some embodiments, before the reaction, the gas environment in the reaction environment is replaced with an inert environment. Exemplarily, the reaction environment gas is replaced with nitrogen.

[0141] In the embodiment of the present application, the polymerization reaction is carried out under the condition of heating. As a possible implementation method, the temperature of the heating reaction is 50-90°C, and the time is 2-60min. In this case, the catalyst has good catalytic activity, which is conducive to improving the efficiency of the polymerization reaction. Exemplary, the temperature of the heating reaction is 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C and other specific temperatures, and the heating time can be 2min, 5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60min and other specific times. Usually, the higher the heating temperature, the shorter the heating time. In some embodiments, the temperature of the heating reaction is 2-20min.

[0142] In a possible implementation, a solution system containing DMON, MDMON, ethylene, a catalyst and a co-catalyst is heated to react under a pressure of 1 to 3 atmospheres. The reaction can be promoted by appropriately increasing the pressure. However, when the pressure is too high, the safety performance of the equipment is required to be higher, which is not conducive to improving the safety performance.

[0143] After the polymerization reaction, an aqueous solution of inorganic acid is added to the obtained solution system to remove the catalyst and co-catalyst in the solution system, especially to remove the co-catalyst present in large quantities in the solution system. Specifically, the catalyst and co-catalyst are dissolved in the aqueous solution of inorganic acid. After the aqueous solution of inorganic acid and the obtained cycloolefin polymer are layered, the catalyst and co-catalyst dissolved in the aqueous solution of inorganic acid are removed by collecting the organic phase. In some embodiments, the mass percentage of the inorganic acid in the aqueous solution of inorganic acid is 2 to 10%. Exemplarily, the inorganic acid is preferably hydrochloric acid, which is cheap and does not cause side reactions. The oxidizing property of nitric acid and the reactivity of sulfuric acid may cause other miscellaneous side reactions.

[0144] After collecting the organic phase, the organic phase is washed with water to further remove residual water-soluble impurities. The organic phase is purified with acetone and / or ethanol, and after drying, the white cycloolefin copolymer is collected. When acetone and ethanol are used to purify the organic phase, acetone and ethanol can be mixed in any proportion to form a mixed solution. Purifying the organic phase with acetone and / or ethanol can remove unreacted monomers in the organic phase and improve the purity of the cycloolefin polymer.

[0145] In some embodiments, the method of purifying the organic phase with acetone is: the obtained organic layer is fully stirred with acetone and / or ethanol, and after standing and settling, filtered; acetone and / or ethanol is added to the solution collected by filtration, refluxed, filtered and washed again. In some embodiments, the drying method is vacuum drying.

[0146] In the examples of the present application, the general structural formula of the prepared cycloolefin copolymer is as shown in the following formula (1-1) or formula (1-2):

[0147]

[0148] In formula (1-1) or formula (1-2), the values ​​of x, y, and z satisfy: 0.57≤x / (x+y+z)≤0.67, 0.32≤y / (x+y+z)≤0.39, 0.01≤z / (x+y+z)≤0.04; R1 is an atom or an atomic group, R2 is an atom or an atomic group, and R1 and R2 are not hydrogen atoms at the same time. The case of the cycloolefin polymer of the structure shown in formula (1-1) or formula (1-2) is as described above. In order to save space, the structure of the cycloolefin polymer is not repeated here.

[0149] The preparation method of the cycloolefin copolymer provided in the embodiment of the present application selects DMON and the four-membered ring-shaped cycloolefin monomer MDMON as the cycloolefin monomer, wherein the polymer formed by the ring-opening metathesis polymerization and hydrogenation of the MDMON monomer itself has a high glass transition temperature, which can reach above 230°C. Therefore, the embodiment of the present application uses ethylene, DMON and MDMON monomers as raw materials for polymerization reaction, which can increase the glass transition temperature of the ternary cycloolefin polymer, thereby improving the heat resistance of the cycloolefin copolymer. Since the glass transition temperature of the MDMON polymer is high, adding a small amount (0.01 to 0.04 of the total molar amount of the sticky polymer) of MDMON monomer in the combination reaction can significantly increase the glass transition temperature of the cycloolefin polymer. At the same time, the preparation method of the cycloolefin copolymer provided in the present application, since the MDMON monomer does not contain a benzene ring substituent or the benzene ring substituent is far away from the reaction site-norbornene ring, can reduce the negative impact of the reaction on the optical properties of the cycloolefin copolymer and maintain good optical properties. In addition, the embodiment of the present application can achieve the effect of significantly increasing the glass transition temperature of the cycloolefin polymer by introducing a small amount of MDMON monomer, which is conducive to improving the economic efficiency of preparing cycloolefin polymers.

[0150] A third aspect of an embodiment of the present application provides an application of a cyclic olefin copolymer as a camera lens material, wherein the cyclic olefin copolymer is the cyclic olefin copolymer of the first aspect or the cyclic olefin copolymer prepared by the method of the second aspect.

[0151] The cyclic olefin copolymer provided in the embodiment of the present application has a high glass transition temperature, and therefore has good high temperature resistance and maintains good optical properties. It can be used as a camera lens material, giving the camera lens good high temperature resistance and optical properties.

[0152] As a possible implementation of the application of the cyclic olefin copolymer of the present application, the camera lens material is a vehicle-mounted camera lens material or a security camera lens material. Compared with the currently commercially available cyclic olefin copolymer material, the cyclic olefin copolymer provided by the present application is used as a vehicle-mounted camera lens material or a security camera lens material, which has better heat resistance without affecting the optical performance of the camera lens.

[0153] The following describes the invention in conjunction with specific embodiments.

[0154] Example 1

[0155] The preparation method of cycloolefin monomer IndDMON comprises:

[0156] In a stainless steel autoclave, add 58g of cyclopentadiene, 33g of indene and 0.5g of butynedioic acid, and react at 190°C for 15 hours. After cooling, perform vacuum distillation to obtain 22g of IndNB and 10g of IndDMON as crude products. The crude product is dissolved in hexane and placed in a refrigerator for recrystallization, and 8g of white solid is obtained after filtration.

[0157] The 1H-NMR spectrum of the cycloolefin monomer IndDMON obtained in Example 1 is as follows: Figure 1 As shown, the 13C-NMR spectrum of the prepared cycloolefin monomer IndDMON is as follows Figure 2 shown.

[0158] Example 2

[0159] A method for preparing a cycloolefin copolymer comprises:

[0160] A glass reactor containing 2.5g of cycloolefin monomer DMON, 0.25g of cycloolefin monomer IndDMON, 2.5mL of MAO (1.5mol / L) and 45mL of toluene was connected to an ethylene pipeline, and the gas in the ethylene pipeline was replaced with nitrogen. After three replacements, the ethylene gas was opened and stirred to make the toluene solution in the glass reactor saturated with ethylene. The polymerization temperature was adjusted to 90°C, and 2mL toluene solution of 2.0mg of the catalyst A with the following structure was added under the condition of passing ethylene. The pressure of ethylene was adjusted and maintained to be one atmosphere, and the polymerization reaction was carried out for 5 minutes. After the polymerization was completed, the obtained reaction solution was poured into a hydrochloric acid aqueous solution with a mass percentage of 10%, and the liquid was separated after sufficient stirring. The organic layer was collected and washed twice with water; the obtained organic layer was precipitated under sufficient stirring with acetone, filtered, added with an appropriate amount of acetone and refluxed for 2 hours, the collected polymer was filtered and washed three times with acetone, and the product was placed in a vacuum drying oven and dried at 130°C for 18 hours to obtain a white cycloolefin copolymer P1.

[0161]

[0162] The glass transition temperature of the cycloolefin copolymer obtained in Example 2 was measured by differential scanning calorimetry (DSC). Figure 3 shown. Figure 3 The results show that the glass transition temperature of the cycloolefin copolymer prepared in Example 2 is 142.81°C.

[0163] The cycloolefin copolymer obtained in Example 2 was subjected to high temperature NMR carbon spectrum detection, and the results were as follows: Figure 4 shown. Figure 4 The results show that the insertion rates of the cycloolefin monomers DMON and IndDMON in the cycloolefin copolymer prepared in Example 2 are 32% and 1%, respectively.

[0164] The cycloolefin copolymer obtained in Example 2 was weighed to have a mass of 3.42 g and an activity of 2.05×10 7 g mol -1 h -1 The number average molecular weight of the cycloolefin copolymer obtained in Example 2 was measured by high temperature gel chromatography and was 47 kg / mol, and the molecular weight distribution index was 1.73.

[0165] The cycloolefin copolymer prepared in Example 2 was prepared into a cycloolefin copolymer film by a solution film laying method. The cycloolefin copolymer film was tested by an optical instrument, and the refractive index, Abbe number and transmittance of the cycloolefin copolymer P1 were measured to be 1.54, 55.1 and 90.7%.

[0166] Example 3

[0167] A method for preparing a cycloolefin copolymer comprises:

[0168] A glass reactor containing 2.5g of cycloolefin monomer DMON, 0.5g of cycloolefin monomer IndDMON, 2.5mL of MAO (1.5mol / L) and 45mL of toluene was connected to an ethylene pipeline, and the gas in the ethylene pipeline was replaced with nitrogen. After replacing three times, the ethylene gas was opened and stirred to make the toluene solution in the glass reactor saturated with ethylene. The polymerization temperature was adjusted to 90°C, and 2mL toluene solution of 2.0mg of catalyst A (same as Example 1) was added under the condition of passing ethylene, and the pressure of ethylene was adjusted and maintained to be one atmosphere, and the polymerization reaction was carried out for 5 minutes. After the polymerization was completed, the obtained reaction solution was poured into a hydrochloric acid aqueous solution with a mass percentage of 10%, and the liquid was separated after sufficient stirring, and the organic layer was collected and washed twice with water; the obtained organic layer was fully stirred with acetone and precipitated, and an appropriate amount of acetone was added after filtering and refluxed for 2 hours, and the collected polymer was filtered and washed three times with acetone, and the product was placed in a vacuum drying oven and dried at 130°C for 18 hours to obtain a white cycloolefin copolymer P2.

[0169] The glass transition temperature of the cycloolefin copolymer obtained in Example 3 was measured by differential scanning calorimetry (DSC). Figure 5 shown. Figure 5 The results show that the glass transition temperature of the cycloolefin copolymer prepared in Example 3 is 150.58°C.

[0170] The cycloolefin copolymer obtained in Example 3 was subjected to high temperature NMR carbon spectrum detection, and the results are as follows: Figure 6 shown. Figure 6 The results show that the insertion rates of the cycloolefin monomers DMON and IndDMON in the cycloolefin copolymer prepared in Example 3 are 35.4% and 1.6%, respectively.

[0171] The cycloolefin copolymer obtained in Example 3 was weighed to have a mass of 2.82 g and an activity of 1.69×10 7 g mol -1 h -1 The number average molecular weight of the cycloolefin copolymer obtained in Example 3 was detected by high temperature gel chromatography and was 37 kg / mol, and the molecular weight distribution index was 1.78.

[0172] The cycloolefin copolymer prepared in Example 3 was prepared into a cycloolefin copolymer film by a solution film laying method. The cycloolefin copolymer film was tested by an optical instrument, and the refractive index of the cycloolefin copolymer P2 was measured to be 1.54, the Abbe number was 53.2, and the transmittance was 90.6%.

[0173] Example 4

[0174] A method for preparing a cycloolefin copolymer comprises:

[0175] A glass reactor containing 2.5g of cycloolefin monomer DMON, 1g of cycloolefin monomer IndDMON, 2.5mL of MAO (1.5mol / L) and 45mL of toluene was connected to an ethylene pipeline, and the gas in the ethylene pipeline was replaced with nitrogen. After three replacements, the ethylene gas was opened and stirred to make the toluene solution in the glass reactor saturated with ethylene. The polymerization temperature was adjusted to 90°C, and 2mL toluene solution of 1.5mg of catalyst B with the following structure was added under the condition of passing ethylene, and the pressure of ethylene was adjusted and maintained to be one atmosphere, and the polymerization reaction was carried out for 5 minutes. After the polymerization was completed, the obtained reaction solution was poured into a hydrochloric acid aqueous solution with a mass percentage of 10%, and the liquid was separated after sufficient stirring, and the organic layer was collected and washed twice with water; the obtained organic layer was precipitated under sufficient stirring with acetone, filtered, and an appropriate amount of acetone was added and refluxed for 2 hours, the collected polymer was filtered and washed three times with acetone, and the product was placed in a vacuum drying oven and dried at 130°C for 18 hours to obtain a white cycloolefin copolymer P3.

[0176]

[0177] The glass transition temperature of the cycloolefin copolymer obtained in Example 4 was measured by differential scanning calorimetry (DSC). Figure 7 shown. Figure 7 The results show that the glass transition temperature of the cycloolefin copolymer prepared in Example 4 is 164.89°C.

[0178] The cycloolefin copolymer obtained in Example 4 was subjected to high temperature NMR carbon spectrum detection, and the results were as follows: Figure 8 shown. Figure 8 The results show that the insertion rates of the cycloolefin monomers DMON and IndDMON in the cycloolefin copolymer prepared in Example 4 are 39% and 4%, respectively.

[0179] The cycloolefin copolymer obtained in Example 4 was weighed to have a mass of 1.78 g and an activity of 1.07×10 7 g mol -1 h -1 The number average molecular weight of the cycloolefin copolymer obtained in Example 4 was detected by high temperature gel chromatography and was 38 kg / mol, and the molecular weight distribution index was 1.77.

[0180] The cycloolefin copolymer prepared in Example 4 was prepared into a cycloolefin copolymer film by a solution film laying method. The cycloolefin copolymer film was tested by an optical instrument, and the refractive index of the cycloolefin copolymer P3 was measured to be 1.55, the Abbe number was 53.5, and the transmittance was 91.4%.

[0181] Example 5

[0182] A method for preparing a cycloolefin copolymer comprises:

[0183] A glass reactor containing 2.5g of cycloolefin monomer DMON, 0.5g of cycloolefin monomer StDMON, 2.5mL of MAO (1.5mol / L) and 45mL of toluene was connected to an ethylene pipeline, and the gas in the ethylene pipeline was replaced with nitrogen. After replacing three times, the ethylene gas was opened and stirred to make the toluene solution in the glass reactor saturated with ethylene. The polymerization temperature was adjusted to 90°C, and 2mL toluene solution of 1.5mg of structure catalyst B (same as Example 4) was added under the condition of passing ethylene, and the pressure of ethylene was adjusted and maintained to be one atmosphere, and the polymerization reaction was carried out for 5 minutes. After the polymerization was completed, the obtained reaction solution was poured into a hydrochloric acid aqueous solution with a mass percentage of 10%, and the liquid was separated after sufficient stirring, and the organic layer was collected and washed twice with water; the obtained organic layer was fully stirred with acetone and settled, and an appropriate amount of acetone was added after filtering and refluxed for 2 hours, and the collected polymer was filtered and washed three times with acetone, and the product was placed in a vacuum drying oven and dried at 130°C for 18 hours to obtain a white cycloolefin copolymer P4.

[0184]

[0185] The glass transition temperature of the cycloolefin copolymer obtained in Example 2 was measured by differential scanning calorimetry (DSC). Fig. 9 shown. Fig. 9 The results show that the glass transition temperature of the cycloolefin copolymer prepared in Example 5 is 157°C.

[0186] The cycloolefin copolymer obtained in Example 5 was tested by high temperature nuclear magnetic resonance carbon spectrum. The insertion rates of cycloolefin monomers DMON and StDMON in the cycloolefin copolymer were 35.8% and 2%, respectively.

[0187] The cycloolefin copolymer obtained in Example 5 was weighed to have a mass of 2.66 g and an activity of 1.60×10 7 g mol -1 h -1 The number average molecular weight of the cycloolefin copolymer obtained in Example 5 was measured by high temperature gel chromatography and was 36 kg / mol, and the molecular weight distribution index was 1.78.

[0188] The cycloolefin copolymer prepared in Example 5 was prepared into a cycloolefin copolymer film by a solution film laying method. The cycloolefin copolymer film was tested by an optical instrument, and the refractive index of the cycloolefin copolymer P4 was measured to be 1.55, the Abbe number was 53.2, and the transmittance was 90.1%.

[0189] Comparative Example 1

[0190] A method for preparing a cycloolefin copolymer comprises:

[0191] A glass reactor containing 2.5g of cycloolefin monomer DMON, 2.5mL of MAO (1.5mol / L) and 45mL of toluene was connected to an ethylene pipeline, and the gas in the ethylene pipeline was replaced with nitrogen. After replacing three times, the ethylene gas was opened and stirred to make the toluene solution in the glass reactor saturated with ethylene. The polymerization temperature was adjusted to 90°C, and 2mL toluene solution of 1.2mg of metallocene catalyst B (same as Example 4) was added under the condition of passing ethylene, and the pressure of ethylene was adjusted and maintained to be one atmosphere, and the polymerization reaction was carried out for 5 minutes. After the polymerization was completed, the obtained reaction solution was poured into a 10% hydrochloric acid aqueous solution by mass percentage, and the liquid was separated after sufficient stirring, and the organic layer was collected and washed twice with water; the obtained organic layer was fully stirred with acetone and settled, and an appropriate amount of acetone was added after filtering and refluxed for 2 hours, and the collected polymer was filtered and washed three times with acetone, and the product was placed in a vacuum drying oven and dried at 130°C for 18 hours to obtain a white cycloolefin copolymer P5.

[0192] The glass transition temperature of the cycloolefin copolymer obtained in Comparative Example 1 was measured by differential scanning calorimetry (DSC). Fig.10 shown. Fig.10 The results show that the glass transition temperature of the cycloolefin copolymer prepared in Comparative Example 1 is 128°C.

[0193] The cycloolefin copolymer obtained in Comparative Example 1 was subjected to high temperature NMR carbon spectrum detection, and the results were as follows: Fig.11 shown. Fig.11 The results show that the insertion rate of the cycloolefin monomer DMON in the cycloolefin copolymer prepared in the comparative example is 30%.

[0194] The cycloolefin copolymer obtained in Comparative Example 1 was weighed to have a mass of 3.72 g and an activity of 2.23×10 7 g mol-1 h -1 The relative number average molecular weight of the cycloolefin copolymer obtained in Comparative Example 1 was detected by high temperature gel chromatography and was 54 kg / mol, and the molecular weight distribution index was 1.62.

[0195] The cycloolefin copolymer prepared in Comparative Example 1 was prepared into a cycloolefin copolymer film by a solution film laying method. The cycloolefin copolymer film was tested by an optical instrument, and the refractive index, Abbe number and transmittance of the cycloolefin copolymer P5 were measured to be 1.54, 59.1 and 91.0%.

[0196] Comparative Example 2

[0197] The cycloolefin copolymer P6 prepared in Table 3 Example 5 in patent US20200369812A1 has a glass transition temperature of 154°C. The insertion rates of cycloolefin monomers DMON and IndNB of the cycloolefin copolymer prepared in Comparative Example 2 are 21.3% and 15.4%, respectively, and the refractive index and Abbe number are 1.56 and 47, respectively.

[0198] In the preparation methods of Examples 2 to 4 and Comparative Examples 1 to 2, the selection and dosage of the cycloolefin monomers DMON and IndNB, the reaction activity, the number of the obtained cycloolefin copolymers, the insertion amounts of the ethylene monomer, the cycloolefin monomer DMON and IndNB, Mn, the glass transition temperature, the Abbe number, and the transmittance are shown in Table 1 below.

[0199] Table 1

[0200]

[0201] It can be seen from Table 1 that, compared with Comparative Example 1, after the introduction of cycloolefin monomers IndDMON and StDMON, the Abbe number and transmittance of the embodiment of the present application did not decrease significantly, but the glass transition temperature increased. It can be seen that the cycloolefin copolymer prepared in the embodiment of the present application has improved heat resistance while maintaining good optical properties.

[0202] Compared with Comparative Example 2, the Abbe number of the cycloolefin copolymer obtained by the embodiment of the present application is improved after using a very small amount of IndDMON and StDMON as cycloolefin monomers, and a good refractive index can be maintained, and the glass transition temperature is 143°C to 165°C. It can be seen that the cycloolefin copolymer obtained by the embodiment of the present application has both good optical properties and heat resistance, that is, the cycloolefin copolymer provided by the embodiment of the present application does not increase the glass transition temperature at the expense of sacrificing optical properties. In particular, the cycloolefin copolymer obtained in Example 4 has an insertion amount of the cycloolefin monomer IndDMON that is only about one-fourth of that in Comparative Example 2, but because the cycloolefin monomer IndDMON has a polycyclic structure and the benzene ring structure that affects the Abbe number is far away from the polymerization site, the Abbe number of the cycloolefin copolymer obtained in Example 4 is higher than the Abbe number of the cycloolefin copolymer provided in Comparative Example 2, and the glass transition temperature is higher than the glass transition temperature of the cycloolefin copolymer provided in Comparative Example 2.

[0203] The test methods of the embodiments and comparative cases of this application are as follows:

[0204] The test method of refractive index refers to ASTM D542;

[0205] The test method of transmittance refers to ASTM D1003;

[0206] Insertion rate refers to the molar ratio of cycloolefin monomer in the polymer, and its calculation method through high temperature nuclear magnetic resonance is: Insertion rate = a / (a+b+c)·100%, where a is the molar amount of cycloolefin monomer in the polymer, b is the molar amount of other cycloolefin monomers in the polymer, and c is the molar amount of polyethylene in the polymer;

[0207] Mn refers to the number average molecular weight of the polymer, and its value is directly measured by high temperature GPC.

[0208] The above are only preferred embodiments of the present application and are not intended to limit the present application. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present application should be included in the protection scope of the present application.

Claims

1. A cycloolefin copolymer, characterized in that The general structural formula of the cycloolefin copolymer is shown in the following formula (1-1) or formula (1-2): Formula (1-1) Formula (1-2) In formula (1-1) or formula (1-2), the values ​​of x, y, and z satisfy: 0.57≤x / (x+y+z)≤0.67, 0.32≤y / (x+y+z)≤0.39, 0.01≤z / (x+y+z)≤0.04; A is an atom or an atomic group, B is an atom or an atomic group, and A and B are not hydrogen atoms at the same time, and A and B may or may not be connected to form a ring; the glass transition temperature of the cycloolefin copolymer is between 143°C and 165°C.

2. The cycloolefin copolymer according to claim 1, wherein The A and B are each independently selected from a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, a heteroalkyl group, an aryl group, a substituted aryl group, a heterocyclic group, an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amino group, and a thiol group.

3. The cycloolefin copolymer according to claim 2, characterized in that The alkyl group is selected from alkyl groups having less than or equal to 20 carbon atoms; The number of carbon atoms of the substituted alkyl group is less than or equal to 20, and the substituent in the substituted alkyl group is at least one of a hydroxyl group, a carboxyl group, an ester group, a cyano group, an amino group, a thiol group, and a halogen atom; The number of carbon atoms in the heteroalkyl group is less than or equal to 20, and the heteroatom in the heteroalkyl group is at least one of an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom.

4. The cycloolefin copolymer according to claim 2, characterized in that The aryl group is selected from phenyl, tolyl, naphthyl, benzyl or phenethyl; The aryl group in the substituted aryl group is selected from phenyl, tolyl, naphthyl, benzyl or phenethyl, and the substituent in the substituted aryl group is at least one of an alkyl group, a hydroxyl group, a carboxyl group, an ester group, a cyano group, an amino group, a thiol group, and a halogen atom; The heterocyclic group is selected from furan, pyran, pyridine or thiophene.

5. The cycloolefin copolymer according to any one of claims 1 to 4, characterized in that A and B are each independently selected from a hydrogen atom, a halogen atom, an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amino group, a thiol group, an alkyl group, a substituted alkyl group, -C6H5, -C6H4CH3, -C 10 H7, -CH2C6H5, -CH2CH2C6H5.

6. The cycloolefin copolymer according to claim 1, wherein The A and the B are connected to form a ring.

7. The cyclic olefin copolymer according to claim 6, characterized in that The ring is an aromatic ring, a cycloalkane, or a ring structure containing both an aromatic ring and a cycloalkane.

8. The cycloolefin copolymer according to claim 7, wherein The ring is one of the following ring structures: 。 9. The cycloolefin copolymer according to any one of claims 1, 6 to 8, characterized in that The cycloolefin copolymer is a copolymer shown in the following structure: 。 10. The cycloolefin copolymer according to any one of claims 1, 2 or 4, characterized in that The cycloolefin copolymer is a copolymer shown in the following structure: 。 11. The cyclic olefin copolymer according to claim 1, wherein The number average molecular weight of the cycloolefin copolymer is less than or equal to 80,000, and the weight average molecular weight is less than or equal to 150,000.

12. A method for preparing a cycloolefin copolymer, characterized in that: The steps include: The solution system containing DMON, MDMON, ethylene, catalyst and co-catalyst is heated for reaction to prepare the cycloolefin copolymer; the structural formula of the DMON is , the structural formula of the MDMON is or ; The general structural formula of the cycloolefin copolymer is as shown in the following formula (1-1) or formula (1-2): Formula (1-1) Formula (1-2) In formula (1-1) or formula (1-2), the values ​​of x, y, and z satisfy: 0.57≤x / (x+y+z)≤0.67, 0.32≤y / (x+y+z)≤0.39, 0.01≤z / (x+y+z)≤0.04; A is an atom or an atomic group, B is an atom or an atomic group, and A and B are not hydrogen atoms at the same time, and A and B may or may not be connected to form a ring; the glass transition temperature of the cycloolefin copolymer is between 143°C and 165°C; The catalyst is a metallocene catalyst.

13. The method for preparing a cycloolefin copolymer according to claim 12, characterized in that: The general structural formula of the catalyst is shown in the following formula (2): Formula (2) In formula (2), M 1 is selected from scandium, titanium, vanadium, zirconium, hafnium, niobium or tantalum, M 2 、M 3 Each independently selected from carbon, silicon, germanium or tin; X represents carbon or silicon; R1 and R2 are each independently selected from a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an aryloxy group, an aralkyl group, an alkaryl group or an aralkenyl group; R3 and R4 are each independently selected from a hydrogen atom or a hydrocarbon group; R5, R6, R7, and R8 are each independently selected from a hydrogen atom, a hydrocarbon group, or a silicon-containing group, wherein the silicon-containing group is connected to the carbon atom at the corresponding substitution position through a silicon atom; R 10 , R 11 , R 12 , R 15 , R 16 , R 17 are each independently selected from alkyl, alkoxy, alkenyl, aryl, aryloxy, aralkyl, alkaryl or aralkenyl; R9, R 13 , R 14 , R 18 are each independently selected from a hydrogen atom, a hydrocarbon group or a hydrocarbonoxy group; Wherein, at least one of R5, R6, R7, and R8 is a silicon-containing group, and / or the M 2 、M 3 At least one of them is silicon.

14. The method for preparing a cycloolefin copolymer according to claim 13, characterized in that: At least one of the R6 and R7 is the silicon-containing group, or the M 2 、M 3 At least one of them is silicon.

15. The method for preparing a cycloolefin copolymer according to claim 13 or 14, characterized in that: The R5, R6, R7 and R8 are independently selected from hydrocarbon groups or silicon-containing groups having carbon atoms less than or equal to 6.

16. The method for preparing a cycloolefin copolymer according to claim 13, characterized in that: The R 10 , R 11 , R 12 , R 15 , R 16 , R 17 The number of carbon atoms is less than or equal to 10.

17. The method for preparing a cycloolefin copolymer according to claim 12, wherein: The co-catalyst is at least one of methylaluminoxane, modified methylaluminoxane and an organic boron compound.

18. The method for preparing a cycloolefin copolymer according to claim 12, wherein: The heating reaction temperature is 50-90°C and the time is 2-60 min.

19. Application of cycloolefin copolymer as camera lens material, characterized in that: The cycloolefin copolymer is the cycloolefin copolymer according to any one of claims 1 to 11 or the cycloolefin copolymer prepared by the method according to any one of claims 12 to 18.

20. The use according to claim 19, characterized in that The camera lens material is a vehicle-mounted camera lens material or a security camera lens material.

Images