Cycloolefin copolymer and method for producing cycloolefin copolymer

Abstract

This application provides a cyclic olefin copolymer and a method for preparing the cyclic olefin copolymer. The chemical formula of the cyclic olefin copolymer is: where x is the number of nitrogen-containing heterocyclic polymerizing monomers, y is the number of norbornene monomers, n is 1 or 2, and R is a nitrogen-containing heterocyclic group; by introducing the nitrogen-containing heterocyclic group into the cyclic olefin copolymer, the application range of the cyclic olefin copolymer is effectively expanded.

Description

Technical Field

[0001] This invention relates to the field of optical technology, and more specifically, to a cyclic olefin copolymer and a method for preparing the cyclic olefin copolymer. Background Technology

[0002] Cyclic olefin copolymers (COCs) are thermoplastics with excellent properties such as high transparency, superior heat resistance, excellent chemical resistance, low density, and minimized dispersion. However, existing cyclic olefin copolymers typically do not contain nitrogen, sulfur, or aromatic groups, resulting in a mismatch in their refractive index with other optical materials, which limits their application in the optical field.

[0003] Therefore, a new technical solution is needed to solve the above-mentioned technical problems. Summary of the Invention

[0004] One object of the present invention is to provide a new technical solution for the preparation method of cyclic olefin copolymers and cyclic olefin copolymers.

[0005] According to a first aspect of the present invention, a cyclic olefin copolymer is provided, wherein the chemical formula of the cyclic olefin copolymer is:

[0006]

[0007] Where x is the number of nitrogen-containing heterocyclic monomers, y is the number of norbornene monomers, n is 1 or 2, and R is a nitrogen-containing heterocyclic group.

[0008] Optionally, the raw materials for preparing the cyclic olefin copolymer include a nitrogen-containing heterocyclic polymer monomer and norbornene, wherein the nitrogen-containing heterocyclic polymer monomer and the norbornene are polymerized in a first solvent.

[0009] Optionally, the raw materials for preparing the nitrogen-containing heterocyclic polymeric monomer include monomer A and monomer B, wherein monomer A and monomer B are polymerized in a second solvent;

[0010] The monomer A includes at least one of allyl bromide and 4-bromobutene;

[0011] The monomer B includes at least one of morpholine, thiomorpholine, phenoxazine, and phenothiazine.

[0012] Optionally, the first solvent includes at least one of acetonitrile, n-hexane, toluene, dichloromethane, and ethyl acetate;

[0013] The second solvent includes at least one of acetonitrile, n-hexane, toluene, dichloromethane, and ethyl acetate.

[0014] Optionally, the nitrogen-containing heterocyclic monomer and the norbornene are polymerized under the catalysis of a catalyst;

[0015] The catalyst includes a main catalyst and a co-catalyst. The main catalyst includes a metallocene catalyst. The co-catalyst reacts with the main catalyst to enable the main catalyst to acquire catalytic activity.

[0016] Optionally, the metallocene catalyst is Me2Si(Flu)(NtBu)TiMe2.

[0017] Optionally, the co-catalyst is methylchlorooxyalkane.

[0018] Optionally, the weight-average molecular weight of the cyclic olefin copolymer is between 50,000 and 150,000.

[0019] Optionally, the refractive index of the cyclic olefin copolymer is greater than or equal to 1.56.

[0020] According to a second aspect of the present invention, a method for preparing a cyclic olefin copolymer is provided, wherein the preparation method comprises:

[0021] The nitrogen-containing heterocyclic monomer, norbornene, and the first solvent are mixed;

[0022] A catalyst was added, and the polymerization reaction was carried out at a set temperature and pressure.

[0023] Optionally, the set temperature ranges from 50°C to 120°C, the set pressure ranges from 0.1 MPa to 1 MPa, and the polymerization reaction time ranges from 30 min to 60 min.

[0024] According to an embodiment of the present invention, a cyclic olefin copolymer is provided, wherein the chemical formula of the cyclic olefin copolymer is: Where x is the number of nitrogen-containing heterocyclic monomers, y is the number of norbornene monomers, n is 1 or 2, and R is a nitrogen-containing heterocyclic group; by introducing the nitrogen-containing heterocyclic group into the cyclic olefin copolymer, the application range of the cyclic olefin copolymer is effectively expanded.

[0025] Other features and advantages of the invention will become clear from the following detailed description of exemplary embodiments of the invention with reference to the accompanying drawings. Attached Figure Description

[0026] The accompanying drawings, which are incorporated in and form part of this specification, illustrate embodiments of the invention and, together with their description, serve to explain the principles of the invention.

[0027] Figure 1 This is a flowchart of the method for preparing cyclic olefin copolymers according to the present invention. Detailed Implementation

[0028] Various exemplary embodiments of the present invention will now be described in detail with reference to the accompanying drawings. It should be noted that, unless otherwise specifically stated, the relative arrangement, numerical expressions, and values ​​of the components and steps set forth in these embodiments do not limit the scope of the invention.

[0029] The embodiments of this application will now be described in detail, examples of which are illustrated in the accompanying drawings. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain this application, and should not be construed as limiting this application. All other embodiments obtained by those skilled in the art based on the embodiments of this application without inventive effort are within the scope of protection of this application.

[0030] It should be noted that similar labels and letters in the following figures indicate similar items; therefore, once an item is defined in one figure, it does not need to be discussed further in subsequent figures.

[0031] According to one embodiment of this application, a cyclic olefin copolymer is provided, wherein the chemical formula of the cyclic olefin copolymer is:

[0032]

[0033] Where x is the number of nitrogen-containing heterocyclic monomers, y is the number of norbornene monomers, n is 1 or 2, and R is a nitrogen-containing heterocyclic group.

[0034] Specifically, in the chemical formula of the cyclic olefin copolymer described in the embodiments of this application, x represents the number of nitrogen-containing heterocyclic polymeric monomers in the cyclic olefin copolymer, y represents the number of norbornene monomers in the cyclic olefin copolymer, n represents the number of carbon chains in the cyclic olefin copolymer, and R represents a nitrogen-containing heterocyclic group, wherein the nitrogen-containing heterocyclic group includes at least one of morpholino, thiomorpholino, phenoxazino, and phenothiazino.

[0035] The number of carbon chains in the monomer's molecular structure has a significant impact on the performance of the cyclic olefin copolymer. For example, a larger number of carbon chains in the monomer's molecular structure results in a larger molecular volume, making it difficult for nitrogen-containing heterocyclic groups to be introduced into the cyclic olefin copolymer's chain segments. Conversely, a smaller number of carbon chains in the monomer's molecular structure leads to easier crystallization of the cyclic olefin copolymer, resulting in lower structural strength, easier breakage, and also making it difficult for nitrogen-containing heterocyclic groups to be introduced into the cyclic olefin copolymer's chain segments. Therefore, this application sets the number of carbon chains n to 1 or 2. On the one hand, this avoids the problem of excessively large n leading to an excessively large monomer molecular volume, making it difficult to introduce nitrogen-containing heterocyclic groups into the cyclic olefin copolymer's chain segments. On the other hand, it also ensures that n is not zero, which is beneficial for the formation of amorphous cyclic olefin copolymers and facilitates the introduction of nitrogen-containing heterocyclic groups into the cyclic olefin copolymer's chain segments.

[0036] Furthermore, the cyclic olefin copolymer described in this application, by introducing the nitrogen-containing heterocyclic group into the chain segment of the cyclic olefin copolymer, enables the refractive index of the cyclic olefin copolymer to be better adapted to other optical materials, effectively expanding the application range of the cyclic olefin copolymer.

[0037] Optionally, the raw materials for preparing the cyclic olefin copolymer include a nitrogen-containing heterocyclic polymer monomer and norbornene, wherein the nitrogen-containing heterocyclic polymer monomer and the norbornene are polymerized in a first solvent.

[0038] Specifically, the nitrogen-containing heterocyclic polymer monomers described in the embodiments of this application include at least one of N-allylmorpholine, N-allylthiomorpholine, N-allylphenoxazine, N-allylphenothiazine, N-allylbutyromorpholine, N-allylthiomorpholine, N-allylbutyromorpholine, and N-allylphenothiazine.

[0039] Therefore, by introducing the above-mentioned nitrogen-containing heterocyclic polymeric monomer into the chain segments of the cyclic olefin copolymer, this application effectively improves the optical properties of the cyclic olefin copolymer, ensures that the refractive index of the cyclic olefin copolymer can be better adapted to other optical materials, and significantly expands the application range of the cyclic olefin copolymer.

[0040] Furthermore, since norbornene has a simple structure and small molecular volume, it can effectively increase the insertion rate of norbornene in the cyclic olefin copolymer, thus ensuring the stability of the cyclic olefin copolymer in an amorphous state.

[0041] In this application, norbornene described in the embodiments can be synthesized from various norbornene derivatives, for example, it can be synthesized by the Adler reaction of cyclopentadiene and ethylene.

[0042] In addition, the first solvent in the embodiments of this application can also enable the nitrogen-containing heterocyclic polymer monomer to react better with norbornene, thereby significantly improving the preparation efficiency of the cyclic olefin copolymer.

[0043] Optionally, the raw materials for preparing the nitrogen-containing heterocyclic polymeric monomer include monomer A and monomer B, wherein monomer A and monomer B are polymerized in a second solvent;

[0044] The monomer A includes at least one of allyl bromide and 4-bromobutene;

[0045] The monomer B includes at least one of morpholine, thiomorpholine, phenoxazine, and phenothiazine.

[0046] Specifically, when monomer A is allyl bromide and monomer B is morpholine, the chemical formula of the cyclic olefin copolymer is:

[0047]

[0048] When monomer A is allyl bromide and monomer B is thiomorpholine, the chemical formula of the cyclic olefin copolymer is:

[0049]

[0050] When monomer A is allyl bromide and monomer B is phenoxazine, the chemical formula of the cyclic olefin copolymer is:

[0051]

[0052] When monomer A is allyl bromide and monomer B is phenothiazine, the chemical formula of the cyclic olefin copolymer is:

[0053]

[0054] When monomer A is 4-bromobutene and monomer B is morpholine, the chemical formula of the cyclic olefin copolymer is:

[0055]

[0056] When monomer A is 4-bromobutene and monomer B is thiomorpholine, the chemical formula of the cyclic olefin copolymer is:

[0057]

[0058] When monomer A is 4-bromobutene and monomer B is phenoxazine, the chemical formula of the cyclic olefin copolymer is:

[0059]

[0060] When monomer A is 4-bromobutene and monomer B is phenothiazine, the chemical formula of the cyclic olefin copolymer is:

[0061]

[0062] Since monomers A and B have simple structures and small molecular volumes, they can effectively increase the insertion rate of monomers A and B in the nitrogen-containing heterocyclic polymer monomers, thereby effectively ensuring the compatibility of the refractive index of the cyclic olefin copolymer with other optical materials and expanding the application range of the cyclic olefin copolymer.

[0063] Of course, while meeting the requirements for preparing the cyclic olefin copolymer, monomer A and monomer B can also be selected from other chemical substances. Those skilled in the art can make selections according to actual needs, and this application does not impose specific restrictions here.

[0064] Furthermore, the second solvent in the embodiments of this application can also enable monomer A to react better with monomer B, thereby significantly improving the preparation efficiency of the nitrogen-containing heterocyclic polymer monomer.

[0065] Optionally, the first solvent includes at least one of acetonitrile, n-hexane, toluene, dichloromethane, and ethyl acetate;

[0066] The second solvent includes at least one of acetonitrile, n-hexane, toluene, dichloromethane, and ethyl acetate.

[0067] Specifically, in this embodiment of the application, by selecting at least one of acetonitrile, n-hexane, toluene, dichloromethane, and ethyl acetate as the first solvent, the insertion rate of the nitrogen-containing heterocyclic polymeric monomer and the norbornene in the cyclic olefin copolymer is effectively improved, thereby ensuring the preparation quality of the cyclic olefin copolymer.

[0068] Furthermore, in the embodiments of this application, the insertion rate of monomer A and monomer B can be effectively improved by selecting at least one of acetonitrile, n-hexane, toluene, dichloromethane, and ethyl acetate as the second solvent, thereby ensuring the preparation quality of the nitrogen-containing heterocyclic polymer monomer.

[0069] Of course, while meeting the preparation requirements of the cyclic olefin copolymer and the nitrogen-containing heterocyclic polymer monomer, the first solvent and the second solvent can also be selected from other chemical substances. Those skilled in the art can make selections according to actual needs, and this application does not impose specific restrictions here.

[0070] Optionally, the nitrogen-containing heterocyclic monomer and the norbornene are polymerized under the catalysis of a catalyst;

[0071] The catalyst includes a main catalyst and a co-catalyst. The main catalyst includes a metallocene catalyst. The co-catalyst reacts with the main catalyst to enable the main catalyst to acquire catalytic activity.

[0072] Specifically, during the polymerization reaction, since the metallocene catalyst itself has no catalytic activity, in order to make the main catalyst catalytically active, the embodiments of this application first alkylate the metallocene catalyst, and then remove one alkyl ligand from the metallocene catalyst. At this time, the metallocene catalyst is fully activated to form an active center, and then the active center coordinates with the nitrogen-containing heterocyclic polymer monomer and the norbornene to undergo a polymerization reaction.

[0073] Furthermore, by utilizing a catalyst with higher catalytic activity, the structure and properties of the cyclic olefin copolymer can be more easily controlled, and the composition of the formed cyclic olefin copolymer can be more uniform.

[0074] Optionally, the metallocene catalyst is Me2Si(Flu)(NtBu)TiMe2.

[0075] Specifically, Me2Si(Flu)(NtBu)TiMe2 can improve the optical properties and quality of the prepared cyclic olefin copolymer.

[0076] Of course, while meeting the requirements for preparing the cyclic olefin copolymer, the metallocene catalyst can also be selected from Cp2ZrCl2 or (Ind)2ZrCl2, etc. Those skilled in the art can make the selection according to actual needs, and this application does not impose specific restrictions here.

[0077] Optionally, the co-catalyst is methylchlorooxyalkane.

[0078] Specifically, in this embodiment, methylchlorooxyalkane is selected to activate the metallocene catalyst to form active centers, thereby effectively improving the activation performance of the metallocene catalyst.

[0079] Of course, while meeting the requirements for preparing the cyclic olefin copolymer, the cocatalyst can also be selected from methylaluminoxane or organoborides, etc. Those skilled in the art can make the selection according to actual needs, and this application does not impose specific restrictions here.

[0080] Optionally, the weight-average molecular weight of the cyclic olefin copolymer is between 50,000 and 150,000.

[0081] Specifically, the cyclic olefin copolymers described in the embodiments of this application are used to prepare optical devices, such as lenses, displays, sensors, and bioimaging devices.

[0082] When the weight-average molecular weight of the cyclic olefin copolymer is between 50,000 and 150,000, it can effectively improve the processing efficiency of processing the cyclic olefin copolymer into optical devices and reduce the processing difficulty of processing the cyclic olefin copolymer into optical devices.

[0083] Optionally, the refractive index of the cyclic olefin copolymer is greater than or equal to 1.56.

[0084] Specifically, under the condition that the wavelength of the incident light is 589 nanometers, the refractive index of the cyclic olefin copolymer is greater than or equal to 1.56, which enables the optical devices made from the cyclic olefin copolymer to be thinner, thereby better meeting the needs of miniaturization, micro-miniaturization and ultra-thinning of optical devices.

[0085] Optionally, the haze of the cyclic olefin copolymer is less than or equal to 0.14.

[0086] Specifically, haze is the percentage of transmitted light intensity that deviates from the incident light by more than 2.5° from the total transmitted light intensity. The greater the haze, the lower the transparency of the optical lens and the lower the imaging accuracy. Therefore, when the haze of the cyclic olefin copolymer is less than or equal to 0.14, the optical device made from the cyclic olefin copolymer can have higher transparency and better imaging effect.

[0087] Optionally, the cyclic olefin copolymer has an Abbe number of 27 to 44.

[0088] Specifically, the Abbe number is an index used to represent the dispersion capability of a transparent medium. The higher the refractive index of the medium, the more severe the dispersion, and the smaller the Abbe number; conversely, the lower the refractive index of the medium, the less severe the dispersion, and the larger the Abbe number. Therefore, when the Abbe number of the cyclic olefin copolymer is between 27 and 44, the optical devices made from the cyclic olefin copolymer can have minimized dispersion.

[0089] Optionally, the visible light transmittance of the cyclic olefin copolymer is greater than or equal to 90.1%.

[0090] Specifically, the visible light transmittance at 0° angle refers to the percentage of energy of light transmitted through the cyclic olefin copolymer to the energy of the incident light when visible light is incident perpendicularly to the surface of the cyclic olefin copolymer. A higher visible light transmittance results in better imaging performance from the camera module; conversely, a lower transmittance leads to poorer imaging performance. Therefore, when the visible light transmittance of the cyclic olefin copolymer is greater than or equal to 90.1%, more visible light can be received by the optical device made from the cyclic olefin copolymer, resulting in better imaging performance.

[0091] Optionally, the glass transition temperature of the cyclic olefin copolymer is greater than or equal to 120°C.

[0092] Specifically, the glass transition temperature is the temperature at which a material transitions from a glassy state to a highly elastic state. Optical devices need to maintain a stable shape and stability during operation, therefore, optical lenses need to remain in a glassy state during operation. Thus, by setting the glass transition temperature of the cyclic olefin copolymer to be greater than or equal to 120°C, this embodiment of the application enables the optical device to maintain a glassy state over a wider temperature range, significantly improving the applicability of the cyclic olefin copolymer.

[0093] According to another embodiment of this application, a method for preparing a cyclic olefin copolymer is provided, comprising the following steps S1 to S2, see below. Figure 1 As shown:

[0094] S1, mixing nitrogen-containing heterocyclic monomer, norbornene, and a second solvent;

[0095] S2, with the addition of a catalyst, undergoes a polymerization reaction at a set temperature and pressure.

[0096] Specifically, in this preparation method, the nitrogen-containing heterocyclic polymer monomer is first dissolved in the second solvent, then norbornene is added and mixed, and finally a catalyst is added. The polymerization reaction is carried out under a set temperature and a set pressure, and the reaction product is the cyclic olefin copolymer.

[0097] Optionally, the set temperature ranges from 50°C to 120°C, the set pressure ranges from 0.1 MPa to 1 MPa, and the polymerization reaction time ranges from 30 min to 60 min.

[0098] Specifically, in this embodiment of the application, by selecting a set temperature range of 50°C to 120°C, a set pressure range of 0.1 MPa to 1 MPa, and a polymerization reaction time range of 30 min to 60 min, the preparation efficiency and quality of the cyclic olefin copolymer are significantly improved.

[0099] The present invention will be further described below with reference to specific embodiments.

[0100] Example 1

[0101] Preparation process of nitrogen-containing heterocyclic monomers:

[0102] At room temperature, 100 mmol of allyl bromide was dissolved in 100 ml of acetonitrile. After stirring until fully dissolved, 100 mmol of morpholine was added. The solution was placed in an oil bath at a constant temperature of 60 °C and refluxed for 24 h. The solvent was removed by rotary evaporation. The solid was washed with ethyl acetate, filtered three times, and dried under vacuum to obtain the polymer monomer N-allylmorpholine.

[0103] Preparation process of cyclic olefin copolymers:

[0104] The reactor was purged three times with high-purity nitrogen to remove air. 50 mmol of norbornene, 50 mmol of N-allylmorpholine, and 150 ml of dehydrated toluene were added to the reactor. 10 μmol of the main catalyst Me2Si(Flu)(NtBu)TiMe2 and 3 mmol of the co-catalyst methylchlorooxyane were dissolved in 10 ml of dehydrated toluene and added to the reactor. The temperature was raised to 70 °C and maintained at 0.1 MPa for 30 min under constant temperature and pressure. The reaction was terminated by injecting 10 ml of hydrochloric acid to acidify the ethanol. The product was washed, dried under reduced pressure, and then vacuum dried at 60 °C for 8 h to obtain the cyclic olefin copolymer a.

[0105] Example 2

[0106] In this embodiment, the preparation method differs from that in Example 1 in that:

[0107] In the preparation of the nitrogen-containing heterocyclic monomer, "100 mmol morpholine" was replaced with "100 mmol thiomorpholine". Other conditions remained the same as in Example 1, resulting in cyclic olefin copolymer b.

[0108] Example 3

[0109] In this embodiment, the preparation method differs from that in Example 1 in that:

[0110] In the preparation of nitrogen-containing heterocyclic monomers, the process of "dissolving 100 mmol of allyl bromide in 100 ml of acetonitrile, stirring until fully dissolved, and then adding 100 mmol of morpholine" is replaced with "dissolving 150 mmol of allyl bromide in 200 ml of acetonitrile, stirring until fully dissolved, and then adding 150 mmol of phenoxazine".

[0111] In the preparation of the cyclic olefin copolymer, the process of "heating to 70°C, maintaining at 0.1 MPa, and reacting under constant temperature and pressure for 30 min" was changed to "heating to 80°C, maintaining at 0.5 MPa, and reacting under constant temperature and pressure for 60 min". Other conditions remained the same as in Example 1, and cyclic olefin copolymer c was obtained.

[0112] Example 4

[0113] In this embodiment, the preparation method differs from that in Example 3 in that:

[0114] In the preparation of the nitrogen-containing heterocyclic monomer, "150 mmol phenoxazine" was replaced with "150 mmol phenthiazine". Other conditions remained the same as in Example 3, resulting in the cyclic olefin copolymer d.

[0115] Example 5

[0116] In this embodiment, the preparation method differs from that in Example 1 in that:

[0117] In the preparation of nitrogen-containing heterocyclic monomers, "100 mmol of allyl bromide" was replaced with "100 mmol of 4-bromobutene", and "the solution was refluxed in an oil bath at a constant temperature of 60°C for 24 hours" was replaced with "the solution was refluxed in an oil bath at a constant temperature of 70°C for 24 hours".

[0118] In the preparation of the cyclic olefin copolymer, "heating to 70°C" was replaced with "heating to 80°C". Other conditions remained the same as in Example 1, resulting in cyclic olefin copolymer e.

[0119] Example 6

[0120] In this embodiment, the preparation method differs from that in Example 5 in that:

[0121] In the preparation of nitrogen-containing heterocyclic monomers, "100 mmol morpholine" was replaced with "100 mmol thiomorpholine". Other conditions remained the same as in Example 5, resulting in cyclic olefin copolymer f.

[0122] Example 7

[0123] In this embodiment, the preparation method differs from that in Example 5 in that:

[0124] In the preparation of nitrogen-containing heterocyclic monomers, the process of "dissolving 100 mmol of 4-bromobutene in 200 ml of acetonitrile, stirring until fully dissolved, and then adding 100 mmol of morpholine" is replaced with "dissolving 150 mmol of 4-bromobutene in 200 ml of acetonitrile, stirring until fully dissolved, and then adding 150 mmol of phenoxazine".

[0125] In the preparation of the cyclic olefin copolymer, the process of "heating to 80°C, maintaining at 0.1 MPa, and reacting under constant temperature and pressure for 30 min" was replaced with "heating to 100°C, maintaining at 0.5 MPa, and reacting under constant temperature and pressure for 60 min". Other conditions remained the same as in Example 5, and g of cyclic olefin copolymer was obtained.

[0126] Example 8

[0127] In this embodiment, the preparation method differs from that in Example 7 in that:

[0128] In the preparation of the nitrogen-containing heterocyclic monomer, "150 mmol phenoxazine" was replaced with "150 mmol phenthiazine". Other conditions remained the same as in Example 7, and the cyclic olefin copolymer h was obtained.

[0129] Comparative Example 1

[0130] Preparation process of cyclic olefin copolymers:

[0131] The reactor was purged three times with high-purity nitrogen to remove air. 50 mmol of norbornene and 100 ml of dehydrated toluene were added to the reactor. Then, 10 μmol of the main catalyst Me2Si(Flu)(NtBu)TiMe2 and 3 mmol of the co-catalyst methylchlorooxyalkane were dissolved in 10 ml of dehydrated toluene and added to the reactor. The pressure was maintained at 0.2 MPa, the temperature was raised to 70 °C, and the reaction was carried out under constant temperature and pressure for 30 min. The reaction was terminated by injecting 10 ml of hydrochloric acid to acidify the ethanol. The product was washed, dried under reduced pressure, and then vacuum dried at 60 °C for 8 h to obtain the cyclic olefin copolymer z.

[0132] The cyclic olefin copolymers prepared in Examples 1 to 8 and Comparative Example 1 were used to prepare plates with lengths, widths, and heights of 100 mm × 50 mm × 3 mm.

[0133] The monomer insertion rate, glass transition temperature (Tg), weight-average molecular weight (Mw), transmittance, haze, and refractive index (n) of the above-mentioned plates were measured. D The numbers and Abbe numbers are shown in Table 1:

[0134] Table 1

[0135]

[0136] As can be seen from Table 1 above, compared with the cyclic olefin copolymer z, the glass transition temperatures of the cyclic olefin copolymers a to h are all greater than 120°C. This allows the optical devices prepared from the cyclic olefin copolymers a to h to maintain a glassy state over a wider temperature range, effectively ensuring the stability of the optical devices during operation.

[0137] Furthermore, the haze and Abbe number of the cyclic olefin copolymers a to h are lower than those of the cyclic olefin copolymer z, while the transmittance and refractive index of the cyclic olefin copolymers a to h are higher than those of the cyclic olefin copolymer z. This results in optical devices made from the cyclic olefin copolymers a to h having higher transparency, better imaging effect, minimized dispersion, and better meeting the needs of miniaturization, micro-miniaturization, and ultra-thinning of optical devices.

[0138] The above embodiments mainly describe the differences between the various embodiments. As long as the different optimization features between the various embodiments are not contradictory, they can be combined to form a better embodiment. For the sake of brevity, they will not be elaborated here.

[0139] While specific embodiments of the invention have been described in detail by way of examples, those skilled in the art should understand that the examples are for illustrative purposes only and not intended to limit the scope of the invention. Those skilled in the art should understand that modifications can be made to the above embodiments without departing from the scope and spirit of the invention. The scope of the invention is defined by the appended claims.

Claims

1. A cyclic olefin copolymer, characterized in that, The chemical formula of the cyclic olefin copolymer is: Where x is the number of nitrogen-containing heterocyclic monomers, y is the number of norbornene monomers, n is 1 or 2, and R is a nitrogen-containing heterocyclic group; The nitrogen-containing heterocyclic monomers include at least one of N-allylmorpholine, N-allylthiomorpholine, N-allylphenoxazine, N-allylphenothiazine, N-allylbutyromorpholine, N-allylthiomorpholine, N-allylphenothiazine, and N-allylphenothiazine.

2. The cyclic olefin copolymer according to claim 1, characterized in that, The raw materials for preparing the cyclic olefin copolymer include nitrogen-containing heterocyclic polymeric monomers and norbornene, which are polymerized in a first solvent to prepare the cyclic olefin copolymer.

3. The cyclic olefin copolymer according to claim 2, characterized in that, The raw materials for preparing the nitrogen-containing heterocyclic polymer monomer include monomer A and monomer B, wherein monomer A and monomer B react in a second solvent to prepare the nitrogen-containing heterocyclic polymer monomer; The monomer A includes at least one of allyl bromide and 4-bromobutene; The monomer B includes at least one of morpholine, thiomorpholine, phenoxazine, and phenothiazine.

4. The cyclic olefin copolymer according to claim 3, characterized in that, The first solvent includes at least one of acetonitrile, n-hexane, toluene, dichloromethane, and ethyl acetate; The second solvent includes at least one of acetonitrile, n-hexane, toluene, dichloromethane, and ethyl acetate.

5. The cyclic olefin copolymer according to claim 2, characterized in that, The nitrogen-containing heterocyclic monomer and the norbornene are polymerized under the catalysis of a catalyst; The catalyst includes a main catalyst and a co-catalyst. The main catalyst includes a metallocene catalyst. The co-catalyst reacts with the main catalyst to enable the main catalyst to acquire catalytic activity.

6. The cyclic olefin copolymer according to claim 5, characterized in that, The metallocene catalyst is .

7. The cyclic olefin copolymer according to claim 5, characterized in that, The cocatalyst is methylchlorooxyalkane.

8. The cyclic olefin copolymer according to claim 1, characterized in that, The weight-average molecular weight of the cyclic olefin copolymer is between 50,000 and 150,000.

9. The cyclic olefin copolymer according to claim 1, characterized in that, The refractive index of the cyclic olefin copolymer is greater than or equal to 1.

56.

10. A method for preparing a cyclic olefin copolymer, applied to the cyclic olefin copolymer as described in any one of claims 1-9, characterized in that, The preparation method includes: The nitrogen-containing heterocyclic monomer, norbornene, and the first solvent are mixed; A catalyst was added, and the polymerization reaction was carried out at a set temperature and pressure.

11. The preparation method according to claim 10, characterized in that, The set temperature ranges from 50°C to 120°C, the set pressure ranges from 0.1 MPa to 1 MPa, and the polymerization reaction time ranges from 30 min to 60 min.

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