Cyclic olefin polymers, monomers for cyclic olefin polymers, and optical products

Abstract

Cyclic olefin polymers, monomers for cyclic olefin polymers, and optical articles using said cyclic olefin polymers are provided. [C5] The cyclic olefin polymer contains a repeating unit represented by formula (1) and / or a repeating unit represented by formula (2). In formula (1), 0≦p and q≦6; x≧0 and y≧0; 0≦p1 and q1≦6, and p1 and q1 are not simultaneously 0; and R1 to R 12 , R a , R b , R c , R d , R 13 , R 14 , R 15 , and R 16 are each independently selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amino group, a thiol group, and an atom or atomic group capable of substituting the aforementioned groups; R 13 , R 14 , R 15 , and R 16 Any two, three, or four of the groups may be bonded to form a cyclic structure. The groups at corresponding positions in formula (2) and formula (1) are essentially the same. Cyclic olefin polymers have both excellent mechanical properties and excellent optical properties.

Description

[Technical field]

[0001] This application claims priority to Chinese Patent Application No. 202011175631.9, filed with the State Intellectual Property Office of the People's Republic of China on October 28, 2020, and entitled "Cyclic Olefin Polymers, Monomers for Cyclic Olefin Polymers, and Optical Products," the entire contents of which are incorporated herein by reference.

[0002] FIELD OF THE DISCLOSURE

[0002] Embodiments of the present application relate to the field of cyclic olefin polymer technology, and in particular to cyclic olefin polymers, monomers for cyclic olefin polymers, and optical articles. [Background technology]

[0003] Cyclic olefin polymers are thermoplastic resin materials with excellent optical properties and are widely used in fields such as electronic products and packaging. There are mainly two types of cyclic olefin polymer materials. One is cyclic olefin copolymers (Cyclic Olefin Copolymers), which are polymer products obtained after addition polymerization (vinyl addition polymerization, VAP) of multiple olefin monomers such as cyclic olefins and α-olefins (monoolefins with double bonds at the ends of the molecular chain). Copolymer Specifically, COC can be obtained by synthesizing norbornene and ethylene using VAP, as shown in chemical equation (1). Another type is ring-opening metathesis polymerization for a single cyclic olefin monomer. (Ring-opening metathesis polymerization, ROMP) Cyclo Olefin Polymer (COP) is a polymer product obtained by hydrogenation after the above reaction. Specifically, COP is synthesized by ROMP-hydrogenation performed on norbornene, as shown in chemical equation (2).

[0004] Cyclic olefin polymers contain both rigid cyclic structures and flexible aliphatic group chain segments. Based on the aliphatic group chain segments, cyclic olefin polymer materials can have characteristics such as excellent chemical resistance, excellent water resistance, good mechanical strength, and good electrical insulation. In addition, based on the rigid cyclic structure, cyclic olefin polymer materials can have a high glass transition temperature (Tg). This improves heat resistance, destroys the crystallization of polyethylene, and provides excellent optical properties. From the chemical equation, it can be seen that by adjusting the relative content of the two monomers, norbornene and ethylene, the relative content of cyclic olefins and α-olefins can be controlled, and COC can obtain good mechanical properties. However, in the polymerization process, homopolymerization of multiple ethylene monomers inevitably causes stacking of ethylene chains. This stacking causes the generation of polyethylene crystallization regions in the polymer. As a result, optical properties including haze and birefringence are reduced. In the process of synthesizing COP, the cyclic structure of norbornene is destroyed, and a structure of five-membered ring structures and ethylene chain segments alternately arranged according to (1:1) is formed, realizing the sequence distribution of cyclic olefins and α-olefins. In this structure, stacking of ethylene chain segments does not occur. In this way, good optical properties can be obtained. However, the molar ratio of cyclic structure monomers in COP is 50%, and the proportion of rigid groups is high. In this case, the material has high internal stress after injection molding, mechanical properties are affected, and the rigidity-flexibility ratio is fixed and cannot be adjusted.

[0005] The above-mentioned synthesis methods of cyclic olefin polymers do not allow simultaneous control of the sequence distribution and relative content of cyclic olefins and α-olefins (i.e., rigid cyclic structures and flexible aliphatic chain segments) in the polymers. Therefore, it is difficult to simultaneously optimize the mechanical and optical properties of cyclic olefin polymers. This limits the application of cyclic olefin polymers in electronic products. Summary of the Invention

[0006] In this regard, embodiments of the present application provide cyclic olefin polymers for controlling both the sequence distribution and relative content of rigid cyclic structures and flexible aliphatic chain segments in the polymer, and thus the cyclic olefin polymers have both excellent mechanical properties and excellent optical properties.

[0007] Specifically, according to a first aspect, an embodiment of the present application provides a cyclic olefin polymer, the cyclic olefin polymer comprising a repeat unit of the structural formula shown in formula (1) and / or a repeat unit of the structural formula shown in formula (2). [ka] [ka]

[0008] In formula (1), p and q are integers of 0 to 6; x and y are integers of 0 or more; p1 and q1 are integers of 0 to 6, but not 0 at the same time; R1 to R 12 , R a , R b , R c , and R d are each independently selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amino group, a thiol group, and an atom or an atomic group capable of substituting the aforementioned groups; R 13 , R 14 , R 15 , and R 16 are each independently selected from hydrogen, halogen, alkyl, aryl, alkoxy, hydroxy, ester, cyano, amino, thiol, and any atom or group of atoms which may substitute for the foregoing groups; or R 13 , R 14 , R 15 , and R 16 any two, three, or four of R 13 , R 14 , R 15, and R 16 The groups not involved in the formation of the cyclic structure are each independently selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amino group, a thiol group, and an atom or an atomic group capable of substituting the above-mentioned groups.

[0009] In formula (2), p' and q' are integers of 0 or more and 6 or less; x' and y' are integers of 0 or more; p1' and q1' are integers of 0 or more and 6 or less, and p1' and q1' are not 0 at the same time; R1' to R 12 ', R a ', R b ', R c ', and R d R ′ are each independently selected from hydrogen atoms, halogen atoms, alkyl groups, aryl groups, alkoxy groups, hydroxyl groups, ester groups, cyano groups, amino groups, thiol groups, and atoms or atomic groups capable of substituting the aforementioned groups; 13 ', R 14 ', R 15 ', and R 16 R ′ are each independently selected from hydrogen atoms, halogen atoms, alkyl groups, aryl groups, alkoxy groups, hydroxyl groups, ester groups, cyano groups, amino groups, thiol groups, and atoms or atomic groups capable of substituting the aforementioned groups; or R 13 ', R 14 ', R 15 ', and R 16 any two, three, or four of R ' may be joined to form a cyclic structure; 13 ', R 14 ', R 15 ', and R 16 The groups not involved in the formation of the cyclic structure in ' are each independently selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amino group, a thiol group, and an atom or an atomic group capable of substituting the above groups.

[0010] According to the cyclic olefin polymer provided in this embodiment of the present application, the molecular structure of the cyclic olefin polymer contains both flexible aliphatic radical segments and rigid bicyclic structures. Based on the aliphatic radical segments, the internal stress and glass transition temperature (T g ) can be effectively reduced, and the cyclic olefin polymer has characteristics such as good mechanical strength, good electrical insulation, excellent chemical resistance, and excellent water resistance. Based on the bicyclic structure, the rigidity, heat resistance, and glass transition temperature of the cyclic olefin polymer can be improved, and the crystallization of the aliphatic radical segment can be destroyed, so that the cyclic olefin polymer obtains excellent optical properties. In the cyclic olefin polymer provided in this embodiment of the present application, the sequence distribution and relative content of the bicyclic structure and the aliphatic radical segment in the molecular structure can be controlled. Therefore, the cyclic olefin polymer has both excellent mechanical properties and excellent optical properties, and also has good processability.

[0011] In the implementation of the present application, the total mass percentage of the repeating unit of the structural formula shown in formula (1) and the repeating unit of the structural formula shown in formula (2) in the cyclic olefin polymer is 50% or more. The higher the total mass percentage of the repeating unit of formula (1) and the repeating unit of formula (2), the higher the optical properties of the cyclic olefin polymer.

[0012] In the implementation of the present application, the cyclic olefin polymer further comprises a repeat unit of the structural formula shown in formula (3). [ka]

[0013] In formula (3), m is an integer of 0 to 10, A1 and A2 are each independently selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxy group, an ester group, a cyano group, an amino group, a thiol group, and an atom or an atomic group that can replace the above groups; A3, A4, A5, and A6 are each independently selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxy group, an ester group, a cyano group, an amino group, a thiol group, and an atom or an atomic group that can replace the above groups; or any two, three, or four of A3, A4, A5, and A6 are bonded to form a cyclic structure, and the groups in A3, A4, A5, and A6 that are not involved in the formation of the cyclic structure are each independently selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxy group, an ester group, a cyano group, an amino group, a thiol group, and an atom or an atomic group that can replace the above groups. The monomer of the repeating unit shown in formula (3) can be easily obtained. By using a simple commercially available monomer, the cost of the cyclic olefin polymer can be reduced. Furthermore, the rigidity of the material can be improved to a certain extent, and the mechanical properties can be compatible.

[0014] In the implementation of the present application, the cyclic olefin polymer has a weight percentage of repeat units of the structural formula shown in formula (3) of 50% or less.

[0015] In the implementation of the present application, the weight average molecular weight of the cyclic olefin polymer is 10000 to 200000. The molecular weight is appropriately controlled to obtain a better balance between the mechanical properties and the moldability of the polymer.

[0016] In the implementation of the present application, the refractive index of the cyclic olefin polymer is 1.53 to 1.58. The cyclic olefin polymer has a high refractive index. When an optical lens is made of the cyclic olefin polymer, the lens thickness of the optical lens can be reduced.

[0017] In the implementation of the present application, the Abbe number of the cyclic olefin polymer is equal to or greater than 53. Since the cyclic olefin polymer has an appropriate Abbe number, the dispersion phenomenon of the material can be controlled to a low level.

[0018] In the implementation of the present application, the haze of the cyclic olefin polymer is less than 0.2%. Due to the small haze, when the optical lens is made of the cyclic olefin polymer, the visual effect of the optical lens can be improved.

[0019] In the implementation of this application, the visible transmittance of the cyclic olefin polymer is 90% or greater.

[0020] In the implementation of the present application, the glass transition temperature of the cyclic olefin polymer is above 100° C. The cyclic olefin polymer has a suitable glass transition temperature, which improves the moldability and processability of the cyclic olefin polymer material.

[0021] In the implementation of this application, the cyclic olefin polymer has a tensile strength of 30 MPa or more, an elongation at break of 6% or more, and a flexural modulus of greater than 2000 MPa.

[0022] In the implementation of this application, the flexural strength of the cyclic olefin polymer is 40 MPa or more.

[0023] The cyclic olefin polymer provided in this embodiment of the present application has excellent mechanical properties. When an optical lens is made of the cyclic olefin polymer, the optical lens can better resist external forces, so that the life of the optical lens can be extended.

[0024] According to a second aspect, an embodiment of the present application provides a monomer for a cyclic olefin polymer. The chemical structure of the monomer for a cyclic olefin polymer is shown in formula (4). [ka]

[0025] In formula (4), p and q are integers of 0 to 6; x and y are integers of 0 or more; p1 and q1 are integers of 0 to 6, but not 0 at the same time; R1 to R 12 , R a , R b , R c , and R d are each independently selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amino group, a thiol group, and an atom or an atomic group capable of substituting the aforementioned groups; R 13 , R 14 , R 15 , and R 16 are each independently selected from hydrogen, halogen, alkyl, aryl, alkoxy, hydroxy, ester, cyano, amino, thiol, and any atom or group of atoms which may substitute for the foregoing groups; or R 13 , R 14 , R 15 , and R 16 any two, three, or four of R 13 , R 14 , R 15 , and R 16 The groups not involved in the formation of the cyclic structure are each independently selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amino group, a thiol group, and an atom or an atomic group capable of substituting the above-mentioned groups.

[0026] The monomer of the cyclic olefin polymer provided in this embodiment of the present application contains both saturated bicyclic structures and unsaturated aliphatic cyclic structures. The cyclic olefin polymer of the first aspect of the embodiment of the present application can be obtained by the ROMP process or the ROMP-hydrogenation process carried out on the monomer of the cyclic olefin polymer. The cyclic olefin polymer is prepared by the ROMP process or the ROMP-hydrogenation process carried out on the monomer of the cyclic olefin polymer, ensuring excellent optical properties and realizing the adjustability of mechanical properties. The details are as follows: (1) The cyclic olefin polymer obtained by polymerization contains both flexible aliphatic group chain segments and rigid bicyclic structure chain segments, reducing birefringence. (2) The relative content of the rigid bicyclic structure can be controlled, so that the rigidity and flexibility, mechanical properties, and processability of the cyclic olefin polymer can be controlled. (3) The alternating arrangement of the rigid bicyclic structure and the flexible aliphatic group chain segments can be controlled, reducing or avoiding the stacking of the aliphatic group chain segments, and reducing microcrystallization. In this way, good optical properties can be obtained.

[0027] According to a third aspect, an embodiment of the present application provides an optical material comprising a cyclic olefin polymer of the first aspect of an embodiment of the present application.

[0028] In the implementation of the present application, the optical material further comprises additives, the additives comprising one or more of an antioxidant, a plasticizer, a thermal stabilizer, and an anti-degradation agent.

[0029] In the implementation of the present application, in the optical material, the weight percentage of the cyclic olefin polymer is 60% or more.

[0030] According to a fourth aspect, an embodiment of the present application provides an optical article comprising a cyclic olefin polymer according to the first aspect of the embodiment of the present application, or comprising an optical material according to the third aspect of the embodiment of the present application.

[0031] In the implementation of the present application, the optical product includes an optical lens, an optical film, an optical disk, a light guide plate, or a display panel.

[0032] In the implementation of this application, the optical lens includes a spectacle lens, a camera lens, a sensor lens, an illumination lens, and an imaging lens.

[0033] An embodiment of the present application further provides an apparatus including the optical product of the fourth aspect of an embodiment of the present application. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0034] The technical solutions in the embodiments of the present application are specifically described below.

[0035] An embodiment of the present application provides a cyclic olefin polymer. The cyclic olefin polymer comprises a repeat unit of the structural formula shown in formula (1) and / or a repeat unit of the structural formula shown in formula (2). [ka]

[0036] In formula (1), p and q are integers of 0 or more and 6 or less; x and y are integers of 0 or more; p1 and q1 are integers of 0 or more and 6 or less, and p1 and q1 are not 0 at the same time; R1 to R 12 , R a , R b , R c , and R d are each independently selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amino group, a thiol group, and an atom or an atomic group capable of substituting the aforementioned groups; R 13 , R 14 , R 15 , and R 16 are each independently selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amino group, a thiol group, and any atom or group of atoms which may substitute for the foregoing groups; or R 13 , R 14 , R 15 , and R 16any two, three, or four of R 13 , R 14 , R 15 , and R 16 The groups not involved in the formation of the cyclic structure are each independently selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amino group, a thiol group, and an atom or an atomic group capable of substituting the above-mentioned groups.

[0037] In formula (2), p' and q' are integers of 0 or more and 6 or less; x' and y' are integers of 0 or more; p1' and q1' are integers of 0 or more and 6 or less, and p1' and q1' are not 0 at the same time; R1' to R 12 ', R a ', R b ', R c ', and R d R ′ are each independently selected from hydrogen atoms, halogen atoms, alkyl groups, aryl groups, alkoxy groups, hydroxyl groups, ester groups, cyano groups, amino groups, thiol groups, and atoms or atomic groups capable of substituting the aforementioned groups; 13 ', R 14 ', R 15 ', and R 16 R ′ are each independently selected from hydrogen atoms, halogen atoms, alkyl groups, aryl groups, alkoxy groups, hydroxyl groups, ester groups, cyano groups, amino groups, thiol groups, and atoms or atomic groups capable of substituting the aforementioned groups; or R 13 ', R 14 ', R 15 ', and R 16 any two, three, or four of R ' may be joined to form a cyclic structure; 13 ', R 14 ', R 15 ', and R 16 The groups not involved in the formation of the cyclic structure in ' are each independently selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amino group, a thiol group, and an atom or an atomic group capable of substituting the above groups.

[0038] In the implementation of the present application, the atoms or atomic groups that can substitute the above-mentioned groups are atoms or atomic groups that can substitute hydrogen atoms, halogen atoms, alkyl groups, aryl groups, alkoxy groups, hydroxyl groups, ester groups, cyano groups, amino groups, and thiol groups; specifically, for example, hydrogen atoms (deuterium, etc.), Boron It can be an isotope atom or a metal ligand of the formula:

[0039] In the implementation of the present application, the halogen atom can be fluorine, chlorine, bromine, or iodine. In the implementation of the present application, the alkyl group can be an alkyl group having an amount of carbon atoms of 1 to 20. In some implementations, the amount of carbon atoms of the alkyl group is 2 to 10. In some other implementations, the amount of carbon atoms of the alkyl group is 8 to 20. In some other implementations, the amount of carbon atoms of the alkyl group is 8 to 15. The alkyl group can be an alkyl group having a linear, branched, or cyclic structure. Specifically, the alkyl group can be, for example, a methyl group, an ethyl group, a propyl group, or a butyl group. The alkyl group can be an unsubstituted alkyl group or a substituted alkyl group. In the implementation of the present application, the aryl group can be an aryl group having an amount of carbon atoms of 6 to 20. Furthermore, the amount of carbon atoms of the aryl group can be 6 to 10. Or, the amount of carbon atoms of the aryl group can be 7 or 8. The aryl group can be an unsubstituted aryl group or a substituted aryl group. In implementations of the present application, the amount of carbon atoms in the alkoxy group can be 1 to 20. In some implementations, the amount of carbon atoms in the alkoxy group can be 2 to 10. In some other implementations, the amount of carbon atoms in the alkoxy group is 8 to 20. In some other implementations, the amount of carbon atoms in the alkoxy group is 8 to 15. The alkoxy group can be an alkoxy group having a straight chain, branched chain, or cyclic structure.

[0040] In the implementation of the present application, the substituents R1 to R2 in the repeating unit shown in formula (1) 12 , R a , R b , R c , R d , R13 , R 14 , R 15 , and R 16 and the substituents in the repeating unit represented by formula (2): R1′ to R 12 ', R a ', R b ', R c ', R d ', R 13 ', R 14 ', R 15 ', and R 16 ' can be specifically selected according to the actual functional requirements. Select a long-chain alkyl group having 6 or more carbon atoms in the main chain to increase the flexibility of the chain segment, adjust the mechanical properties of the polymer, and reduce internal stress. Select a polar group such as an ester group or an amino group to increase the affinity of the cyclic olefin polymer with other polymers and improve the binding of the cyclic olefin polymer. Select a substituent containing a cyclic structure and an aryl group to improve the rigidity and heat resistance of the material.

[0041] In the implementation of the present application, in formula (1), p and q are integers of 0 to 6. In formula (2), p' and q' are integers of 0 to 6. Specifically, p, q, p', and q' are 0, 1, 2, 3, 4, 5, or 6, respectively. By controlling the values ​​of p, q, p', and q' to be small, the length of the aliphatic group chain segment can be controlled to be short, and microcrystallization due to stacking of the aliphatic group chain segment can be effectively avoided. This allows the cyclic olefin polymer to have good optical properties such as haze and light transmittance. In some other implementations of the present application, p=q=1. In some other implementations of the present application, p+q=1. In some other implementations of the present application, p=q=2. In some other implementations of the present application, p=q=0. Similarly, in some other implementations of the present application, p'=q'=1. In some other implementations of the present application, p'+q'=1. In some other implementations of the present application, p'=q'=2. In some other implementations of the present application, p'=q'=0. In some implementations of the present application, when p1, q1, p1', and q1' are equal to 0, there is a single bond at the corresponding position.

[0042] In some other implementations of the present application, the cyclic olefin polymer contains only the repeat units shown in formula (1), where both p and q are equal to 0. In this case, the cyclic olefin polymer corresponds to the product of alternating copolymerization of a bicyclic structure with ethylene.

[0043] In the implementation of the present application, in formula (1), p1 and q1 are integers of 0 to 6, and p1 and q1 are not 0 at the same time. In formula (2), p1' and q1' are integers of 0 to 6, and p1' and q1' are not 0 at the same time. Specifically, p1, q1, p1', and q1' can be 0, 1, 2, 3, 4, 5, or 6, respectively.

[0044] In implementations of the present application, in formula (1), x and y are integers equal to or greater than 0. In some implementations, x is an integer equal to or greater than 0 and equal to 3. In some implementations, y is an integer equal to or greater than 0 and equal to 5. Specifically, x can be, for example, 0 or 1, and y can be, for example, 0, 1, or 2. In some implementations, x and y are both equal to 0. In some other implementations, x and y are both equal to 1.

[0045] In implementations of the present application, in formula (2), x' and y' are integers equal to or greater than 0. In some implementations, x' is an integer equal to or greater than 0 and equal to 3. In some implementations, y' is an integer equal to or greater than 0 and equal to 5. Specifically, x' can be, for example, 0 or 1, and y' can be, for example, 0, 1, or 2. In some implementations, x' and y' are both equal to 0. In some other implementations, x' and y' are both equal to 1.

[0046] In the implementation of this application, R 13 , R 14 , R 15 , and R 16The ring structure formed by joining any two, three, or four of R can be a saturated or unsaturated carbocyclic ring, or a saturated or unsaturated heterocyclic ring. The heteroatoms in the heterocyclic ring can be nitrogen, sulfur, oxygen, boron, silicon, etc. For example, R 13 and R 15 , R 13 and R 16 , R 14 and R 15 , or R 14 and R 16 are bonded to form a cyclic structure, and the other two groups not involved in forming the cyclic structure are separately and independently selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amino group, a thiol group, and an atom or an atomic group that can substitute the aforementioned groups. 13 , R 14 , and R 15 are linked together to form a ring structure.

[0047] In the implementation of this application, R 13 ', R 14 ', R 15 ', and R 16 The ring structure formed by joining any two, three, or four of R′ can be a saturated or unsaturated carbocyclic ring, or a saturated or unsaturated heterocyclic ring. The heteroatoms in the heterocyclic ring can be nitrogen, sulfur, oxygen, boron, silicon, etc. For example, R 13 ' and R 15 ', R 13 ' and R 16 ', R 14 ' and R 15 ' or R 14 ' and R 16 ' are bonded together to form a ring structure, and R 13 ', R 14 ', R 15 ', and R 16In the formula (I), the other two groups not involved in the formation of the cyclic structure are independently selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amino group, a thiol group, and an atom or an atomic group that can substitute the above-mentioned groups. 13 ', R 14 ', and R 15 ' are linked to form a ring structure.

[0048] In the implementation of the present application, the cyclic olefin polymer can be a cyclic olefin homopolymer or can be a cyclic olefin copolymer.

[0049] In some other implementations of the present application, the cyclic olefin polymer comprises a repeat unit as shown in formula (1), but does not comprise a repeat unit as shown in formula (2). Specifically, the cyclic olefin polymer can comprise a repeat unit comprising one or more different structures as shown in formula (1). In some other implementations of the present application, the cyclic olefin polymer comprises a repeat unit as shown in formula (2), but does not comprise a repeat unit as shown in formula (1). Similarly, the cyclic olefin polymer can comprise a repeat unit comprising one or more different structures as shown in formula (2).

[0050] In some other implementations of the present application, the cyclic olefin polymer can include both the repeating unit shown in formula (1) and the repeating unit shown in formula (2), specifically, it can be obtained by carrying out partial hydrogenation on the same cyclic olefin polymer monomer after the ROMP process. The repeating unit having the structure shown in formula (1) is formed after the ROMP process. After hydrogenation, some repeating units shown in formula (1) are hydrogenated to obtain the repeating unit shown in formula (2). The main structure of the two repeating units is the same. The only difference is that the unsaturated carbon bond of the aliphatic chain segment shown in formula (1) and the unsaturated carbon bond of each substituent in the repeating unit are saturated carbon bonds in the repeating unit shown in formula (2). When other substituents do not contain unsaturated carbon bonds, the difference between the repeating unit shown in formula (1) and the repeating unit shown in formula (2) is only in the aliphatic chain segment (i.e., the olefin bond is hydrogenated or not hydrogenated). The substituents at corresponding positions between the repeating unit shown in formula (1) and the repeating unit shown in formula (2) are completely the same. In some embodiments, the cyclic olefin polymer may contain both the repeating unit shown in formula (1) and the repeating unit shown in formula (2), or may be obtained by performing partial hydrogenation on two or more different monomers after the ROMP process. In this case, the cyclic olefin polymer may contain both the repeating unit having multiple different structures shown in formula (1) and the repeating unit having multiple different structures shown in formula (2).

[0051] In some other implementations of the present application, in the repeating unit shown in formula (2), R1', R2', R3', and R4' are hydrogen atoms. In this case, the structural formula of the repeating unit shown in formula (2) is shown in formula (5). [ka]

[0052] The repeating unit shown in formula (5) has a bicyclic structure and

number

number

[0053] In this embodiment of the present application, the structural formula of the repeating unit shown in formula (5) can be specifically represented by formulas (A) to (K). [ka]

[0054] The mole percentage of the bicyclic structure of the repeating unit shown in formula (A) is 50%. The mole percentage of the bicyclic structure of the repeating unit shown in formula (C), formula (F), formula (G), and formula (H) is 40%. The mole percentage of the bicyclic structure of the repeating unit shown in formula (B), formula (D), formula (I), formula (J), and formula (K) is 33%. The mole percentage of the bicyclic structure of the repeating unit shown in formula (E) is 25%.

[0055] When the cyclic olefin polymer contains only repeat units represented by formula (5), the cyclic olefin polymer contains a bicyclic structure and

number

[0056] In the implementation of the present application, the cyclic olefin polymer can only include the repeating unit shown in formula (1) and / or the repeating unit shown in formula (2), or can include repeating units with other structures according to the actual property requirements. In the implementation of the present application, in the cyclic olefin polymer, the total mass percentage of the repeating unit of the structural formula shown in formula (1) and the repeating unit of the structural formula shown in formula (2) is 50% or more. Specifically, the total mass percentage of the repeating unit of the structural formula shown in formula (1) and the repeating unit of the structural formula shown in formula (2) can be 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, and 100%. The higher the total mass percentage of the repeating unit of formula (1) and the repeating unit of formula (2), the higher the optical properties (e.g., haze) of the cyclic olefin polymer. In some implementations, the total mass percentage of the two repeating units of formula (1) and formula (2) in the cyclic olefin polymer can be 100%. Specifically, in some implementations, the cyclic olefin polymer may include only the repeat units shown in formula (1). In some other implementations, the cyclic olefin polymer may include only the repeat units shown in formula (2). In some other implementations, the cyclic olefin polymer may include only the repeat units shown in formula (1) and the repeat units shown in formula (2).

[0057] In some other implementations of the present application, the cyclic olefin polymer further comprises a repeat unit of the structural formula shown in formula (3). [ka]

[0058] In formula (3), m is an integer of 0 to 10, A1 and A2 are each independently selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxy group, an ester group, a cyano group, an amino group, a thiol group, and an atom or an atomic group that can replace the above groups; A3, A4, A5, and A6 are each independently selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxy group, an ester group, a cyano group, an amino group, a thiol group, and an atom or an atomic group that can replace the above groups; or any two, three, or four of A3, A4, A5, and A6 are bonded to form a cyclic structure, and the groups in A3, A4, A5, and A6 that are not involved in the formation of the cyclic structure are each independently selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxy group, an ester group, a cyano group, an amino group, a thiol group, and an atom or an atomic group that can replace the above groups. The specific selection range of the substituents such as halogen atoms, alkyl groups, aryl groups, alkoxy groups, hydroxyl groups, ester groups, cyano groups, amino groups, or thiol groups can be the same as those of the substituents of formula (1) and formula (2). The monomer of the repeating unit shown in formula (3) can be easily obtained. By using a simple commercially available monomer, the cost of the cyclic olefin polymer can be reduced. Furthermore, the rigidity of the material can be improved to a certain extent, and mechanical properties can be compatible.

[0059] In this implementation of the present application, in formula (3), the larger the value of m, the higher the glass transition temperature and the larger the internal stress of the resulting cyclic olefin polymer. In order for the cyclic olefin polymer to obtain an appropriate glass transition temperature, control the internal stress at a low level, and improve moldability and processability, in this embodiment of the present application, the value of m is controlled within the range of 0 to 10. In some other implementations of the present application, m is an integer of 0 to 5. Specifically, m is 0, 1, 2, 3, 4, or 5. The cyclic structure formed by combining any two, three, or four of A3, A4, A5, and A6 can be a saturated or unsaturated carbocyclic ring, or a saturated or unsaturated heterocyclic ring. The heteroatom in the heterocyclic ring can be nitrogen, sulfur, oxygen, boron, silicon, etc.

[0060] In the implementation of the present application, the cyclic olefin polymer has a mass percentage of the repeating unit of the structural formula shown in formula (3) of 50% or less. Specifically, the mass percentage of the repeating unit of the structural formula shown in formula (3) of the cyclic olefin polymer can be, but is not limited to, 50%, 40%, 30%, 20%, 10%, and 5%.

[0061] In the implementation of the present application, the weight average molecular weight of the cyclic olefin polymer is 10,000 to 200,000. The higher the molecular weight, the better the mechanical properties and the higher the strength of the material. However, in this case, the difficulty of processing increases and the viscosity increases in the molten state. This is disadvantageous for processing and molding. A smaller molecular weight is easier to process and has a higher molding yield. In order to balance the mechanical properties and moldability, in some other implementations of the present application, the weight average molecular weight of the cyclic olefin polymer is controlled within 30,000 to 60,000.

[0062] In the implementation of the present application, the refractive index of the cyclic olefin polymer is 1.53 to 1.58, and specifically can be 1.53, 1.54, 1.55, 1.56, 1.57, or 1.58. The cyclic olefin polymer has a high refractive index. When an optical lens is made of the cyclic olefin polymer, the lens thickness of the optical lens can be reduced. The refractive index of the cyclic olefin polymer can be tested according to the ASTM D542 test standard.

[0063] In the implementation of the present application, the Abbe number of the cyclic olefin polymer is 53 or more. Specifically, the Abbe number can be, for example, 53, 54, 55, 56, or 57. The Abbe number indicates the index of the dispersion ability of the transparent material. The lower the Abbe number, the larger the dispersion. If the Abbe number is appropriate, it indicates that the dispersion phenomenon of the material can be controlled to a low level.

[0064] In the implementation of the present application, the haze of the cyclic olefin polymer is less than 0.2%. Haze, or haziness, is defined as the ratio of the scattered light flux of a material to the transmitted light flux of the material. Haze can be used to measure the degree of obscuration or haze of a transparent or translucent material, and is an indicator of scattering. Haze is caused by a cloudy or hazy appearance due to light scattering inside the material or on the external surface of the material. Based on the low haze, the optical lens can be made of the cyclic olefin polymer to improve the visual effect of the optical lens. In some other implementations of the present application, the haze of the cyclic olefin polymer is less than 0.1%. In some other implementations of the present application, the haze of the cyclic olefin polymer is less than 0.05%.

[0065] In some implementations of the present application, the visible transmittance of the cyclic olefin polymer is 90% or greater. In some other implementations of the present application, the visible transmittance of the cyclic olefin polymer is 92% or greater. In some other implementations of the present application, the visible transmittance of the cyclic olefin polymer is 95% or greater.

[0066] In the implementation of the present application, the glass transition temperature of the cyclic olefin polymer is greater than 100° C. Specifically, the glass transition temperature can be greater than 100° C. and not greater than 160° C. More specifically, the glass transition temperature can be 110° C., 120° C., 130° C., 140° C., 150° C., or 160° C. The cyclic olefin polymer has an appropriate glass transition temperature, which improves the moldability and processability of the cyclic olefin polymer material.

[0067] In this implementation of the present application, the cyclic olefin polymer further has excellent mechanical properties.

[0068] In the implementation of the present application, the tensile strength of the cyclic olefin polymer is 30 MPa or more. Specifically, the tensile strength can be, for example, 30 MPa to 150 MPa. Tensile strength indicates the stress of a material at maximum uniform plastic deformation. In a tensile test, the maximum tensile stress of a sample before the sample breaks is the tensile strength. The higher the tensile strength, the stronger the damage resistance of the material.

[0069] In the implementation of the present application, the elongation at break of the cyclic olefin polymer is 6% or more. Specifically, the elongation at break can be, for example, 6% to 15%. The elongation at break indicates the tensile speed. When a material is elongated by an external force and breaks, the ratio of the elongation length after elongation to the length before elongation is called the elongation at break. A high elongation at break indicates that the material has high toughness, low brittleness, and small internal stress, which makes it easy to perform injection molding.

[0070] In the implementation of this application, the flexural modulus of the cyclic olefin polymer is greater than 2000 MPa. Flexural modulus is the ratio of bending stress to bending strain.

[0071] In the implementation of the present application, the flexural strength of the cyclic olefin polymer is 40 MPa or more. Specifically, the flexural strength can be, for example, 40 MPa to 120 MPa. The flexural strength indicates the maximum stress that the material can withstand before it is bent and broken, or when the material reaches a specified bending moment. This stress is the maximum positive stress when bending. The flexural strength reflects the bending resistance ability of the material and can be used to measure the flexibility of the material. The higher the flexural strength, the stronger the bending resistance ability of the material.

[0072] In this implementation of the application, the haze and light transmittance of the cyclic olefin polymer are tested according to the ASTM D1003 test standard. The tensile strength and elongation at break of the cyclic olefin polymer are tested according to the ASTM D638 test standard. The flexural strength of the cyclic olefin polymer is tested according to the ASTM D790 test standard. The flexural modulus of the cyclic olefin polymer is tested according to the ASTM D256 test standard.

[0073] From the above, it can be seen that the cyclic olefin polymer provided in this embodiment of the present application has both excellent optical properties and excellent mechanical properties, and has excellent processability and excellent moldability.

[0074] Correspondingly, an embodiment of the present application further provides a monomer for a cyclic olefin polymer. The chemical structural formula of the monomer for a cyclic olefin polymer is shown in Formula (4). [ka]

[0075] In formula (4), p and q are integers of 0 to 6; x and y are integers of 0 or more; p1 and q1 are integers of 0 to 6, but not 0 at the same time; R1 to R 12 , R a , R b , R c , and R dare each independently selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amino group, a thiol group, and an atom or an atomic group capable of substituting the aforementioned groups; R 13 , R 14 , R 15 , and R 16 are each independently selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amino group, a thiol group, and any atom or group of atoms which may substitute for the foregoing groups; or R 13 , R 14 , R 15 , and R 16 Any two, three, or four of R 13 , R 14 , R 15 , and R 16 The groups not involved in the formation of the cyclic structure are each independently selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amino group, a thiol group, and an atom or an atomic group capable of substituting the above-mentioned groups.

[0076] In this implementation of the present application, the substituents in the monomer of the cyclic olefin polymer: R1 to R 12 , R a , R b , R c , R d , R 13 , R 14 , R 15 , and R 16 can be specifically selected according to the actual functional requirements. Cyclic olefin polymers with different properties can be obtained by modifying the polymers by introducing different substituents at different positions in the monomers of the cyclic olefin polymer.

[0077] In the implementation of the present application, the atoms or atomic groups that can substitute the above-mentioned groups are atoms or atomic groups that can substitute hydrogen atoms, halogen atoms, alkyl groups, aryl groups, alkoxy groups, hydroxyl groups, ester groups, cyano groups, amino groups, and thiol groups; specifically, for example, hydrogen atoms (deuterium, etc.), Boron It can be an isotope atom or a metal ligand of the formula:

[0078] In the implementation of the present application, the halogen atom can be fluorine, chlorine, bromine, or iodine. In the implementation of the present application, the alkyl group can be an alkyl group having an amount of carbon atoms of 1 to 20. In some implementations, the amount of carbon atoms of the alkyl group is 2 to 10. In some other implementations, the amount of carbon atoms of the alkyl group is 8 to 20. In some other implementations, the amount of carbon atoms of the alkyl group is 8 to 15. The alkyl group can be an alkyl group having a linear, branched, or cyclic structure. Specifically, the alkyl group can be, for example, a methyl group, an ethyl group, a propyl group, or a butyl group. The alkyl group can be an unsubstituted alkyl group or a substituted alkyl group. In the implementation of the present application, the aryl group can be an aryl group having an amount of carbon atoms of 6 to 20. Furthermore, the amount of carbon atoms of the aryl group can be 6 to 10. Or, the amount of carbon atoms of the aryl group can be 7 or 8. The aryl group can be an unsubstituted aryl group or a substituted aryl group. In implementations of the present application, the amount of carbon atoms in the alkoxy group can be 1 to 20. In some implementations, the amount of carbon atoms in the alkoxy group can be 2 to 10. In some other implementations, the amount of carbon atoms in the alkoxy group is 8 to 20. In some other implementations, the amount of carbon atoms in the alkoxy group is 8 to 15. The alkoxy group can be an alkoxy group having a straight chain, branched chain, or cyclic structure.

[0079] In the implementation of the present application, in formula (4), p and q are integers from 0 to 6. Specifically, p and q can be 0, 1, 2, 3, 4, 5, or 6, respectively. Here, p and q can be 0 at the same time. In some other implementations of the present application, p=q=1, i.e., the cyclic structure in which the olefinic bond is located is a 6-membered cyclic structure. In some other implementations of the present application, p+q=1, i.e., the cyclic structure in which the olefinic bond is located is a 5-membered cyclic structure. In some other implementations of the present application, p=q=2, i.e., the cyclic structure in which the olefinic bond is located is an 8-membered cyclic structure.

[0080] In the implementation of the present application, in formula (4), p1 and q1 are integers from 0 to 6, and p1 and q1 are not 0 at the same time. Specifically, p1 and q1 can be 0, 1, 2, 3, 4, 5, or 6, respectively. In some other implementations of the present application, p1=q1=1, that is, the corresponding cyclic structure is a 6-membered cyclic structure. In some other implementations of the present application, p1+q1=1, that is, the corresponding cyclic structure is a 5-membered cyclic structure. In some other implementations of the present application, p1=q1=2, that is, the corresponding cyclic structure is an 8-membered cyclic structure.

[0081] In the implementation of the present application, when p, q, p1, and q1 are equal to 0, there is a single bond at the corresponding position.

[0082] In implementations of the present application, in formula (4), x and y are integers equal to or greater than 0. In some implementations, x is an integer equal to or greater than 0 and equal to 3. In some implementations, y is an integer equal to or greater than 0 and equal to 5. Specifically, x can be, for example, 0 or 1, and y can be, for example, 0, 1, or 2. In some implementations, x and y are both equal to 0. In some other implementations, x and y are both equal to 1.

[0083] In the implementation of this application, R 13 , R 14 , R 15 , and R 16Any two, three, or four of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 , R 39 , R 40 , R 41 , R 42 , R 43 13 and R 15 , R 13 and R 16 , R 14 and R 15 , or R 14 and R 16 are bonded to form a cyclic structure, and the other two groups not involved in the formation of the cyclic structure are separately and independently selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amino group, a thiol group, and an atom or an atomic group capable of substituting the aforementioned groups.

[0084] The cyclic olefin polymer monomer provided in this embodiment of the present application includes both saturated bicyclic structures and aliphatic cyclic structures with unsaturated double bonds. The cyclic olefin polymer comprising the repeating unit shown in formula (1) and / or the repeating unit shown in formula (2) in this embodiment of the present application can be prepared by the ROMP process or the ROMP-hydrogenation process carried out on the cyclic olefin polymer monomer. The process is shown in formula (a). In the ROMP-polymerization reaction process, the rigid bicyclic structure is retained in the polymer structure, and the aliphatic cyclic structure with unsaturated double bonds is opened to form a flexible aliphatic chain segment. In the hydrogenation process, the unsaturated double bonds are converted into saturated carbon bonds. [ka]

[0085] In the hydrogenation process, the substituents: R1 to R 12 , R a , R b , R c , R d , R 13 , R 14 , R 15 , and R 16It should be noted that the unsaturated carbon bonds in the formula (a) can be converted to saturated carbon bonds. Therefore, in the repeating units of the cyclic olefin polymer before and after hydrogenation shown in formula (a), the substituents R1 to R 12 , R a , R b , R c , R d , R 13 , R 14 , R 15 , and R 16 R1'~R 12 ', R a ', R b ', R c ', R d ', R 13 ', R 14 ', R 15 ', and R 16 It should be understood that ' may be the same as or different from '. If the substituents in the monomer contain unsaturated carbon bonds, the unsaturated carbon bonds can be partially or completely converted to saturated carbon bonds after hydrogenation.

[0086] The monomer of the new cyclic olefin polymer provided in this embodiment of the present application contains both unsaturated aliphatic cyclic structure and saturated bicyclic structure.When preparing cyclic olefin polymer by polymerization carried out on the monomer, the relative content and sequence distribution of rigid bicyclic structure and flexible aliphatic chain segment in the cyclic olefin polymer can be controlled at the same time, and an olefin polymer in which rigid bicyclic structure and aliphatic chain segment of a specific length are alternately arranged can be obtained.In this way, the thermodynamic property and optical property of the cyclic olefin polymer can be controlled at the same time, and a cyclic olefin polymer having both excellent thermodynamic property and excellent optical property can be obtained.

[0087] In a specific implementation of the present application, the structural formula of the monomer of the cyclic olefin polymer is shown in formula (6), which includes an unsaturated cyclohexene structure and a saturated dimethanooctahydronaphthalene structure. [ka]

[0088] After the ROMP-hydrogenation process, in the monomer of the cyclic olefin polymer shown in formula (6), an alternating copolymerization structure of dimethanooctahydronaphthalene and C4 chain segments in the polymer is obtained, and the resulting cyclic olefin polymer corresponds to the product of alternating copolymerization of dimethanooctahydronaphthalene and two ethylenes.

[0089] In the implementation of this application, the main raw materials used to prepare the monomers of cyclic olefin polymers include, but are not limited to, ethylene, norbornene, cyclopentadiene, butadiene, alicyclic diolefins, α-substituted olefins, methyl propiolate, acrylates, etc.

[0090] In the implementation of this application, the monomers of cyclic olefin polymers can be mainly synthesized by Diels-Alder reaction ([4+2] cycloaddition reaction). Certainly, other existing well-known methods can also be used to synthesize the monomers of cyclic olefin polymers.

[0091] In the implementation of the present application, when the ROMP polymerization reaction is carried out on the monomer of the cyclic olefin polymer, the ROMP polymerization reaction occurs in an inert atmosphere. The inert gas can be selected as nitrogen, argon, etc. The polymerization reaction system mainly includes a cyclic olefin monomer, a catalyst, a solvent, and a terminator. In the present application, the cyclic olefin monomer includes the monomer of the cyclic olefin polymer mentioned above. Alternatively, other cyclic olefin monomers, such as norbornene and its derivatives, or alicyclic olefins, can also be selected for copolymerization. The catalyst can be one or more of W compounds, Ru compounds, Mo compounds, Re compounds, V compounds, etc. The Ru compound can be a Grubbs catalyst, etc., for example, a first generation catalyst: benzylidene-bis(tricyclohexylphosphine)dichlororuthenium, or a second generation catalyst: (1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(o-isopropoxyphenylmethylene)ruthenium. The Mo compound can be a Schrock catalyst, MoO3, MoCl5, etc. The W compound can be WCl6, WOCl4, W(CO)6, etc. The Re compound can be ReCl5, Re2O7, ReOCl3, etc. The V compound can be VCl4, VOCl3, V2O5, etc. The solvent can be a common organic solvent capable of dissolving all the reactants and the produced polymer, for example, one or more solvents such as branched alkanes, cycloalkanes, aromatic hydrocarbons (such as benzene and toluene), chlorinated paraffins (such as dichloromethane, chlorobutane, and bromohexane), saturated carboxylates (such as ethyl acetate, n-butyl acetate, isobutyl acetate, and methyl propionate), ethers (such as dibutyl ether, tetrahydrofuran, and 1,1-dimethoxyethane), etc. In some other implementations of the present application, the solvent is an alicyclic hydrocarbon such as cyclohexane, an aromatic hydrocarbon such as toluene, or a mixture of multiple solvents capable of dissolving the aforementioned cyclic olefin monomer, catalyst, and the produced cyclic olefin polymer. The main function of the terminator is twofold. One is to selectively remove the transition metal from the ends of the polymer chain segments, thus terminating the reaction.The other is to introduce a specific functional group at the end of the chain segment. The terminator selected in this application can be a vinyl ether compound.

[0092] In the implementation of the present application, the mass concentration of the cyclic olefin monomer in the ROMP reaction system can be 2wt%-20wt%, and further can be 5wt%-15wt%. The ratio of the total mole number of the cyclic olefin monomer to the mole number of the catalyst can be more than 500 / 1, and further can be more than 1000 / 1. The reaction temperature of the ROMP can be 25°C-180°C, and further can be 40°C-100°C. The reaction time can be set according to the actual requirements, specifically, can be 0.1 hours-10 hours, further can be 0.1 hours-5 hours, and further can be 0.1 hours-3 hours.

[0093] In the implementation of the present application, well-known methods can also be used for the hydrogenation step of the unsaturated polymer obtained after the ROMP polymerization reaction. In the implementation of the present application, the hydrogenation rate of the unsaturated polymer is more than 80%. In some other implementations of the present application, the hydrogenation rate is more than 90%, even more than 95%, and even more than 99%.

[0094] In the implementation of the present application, the preparation process for preparing the cyclic olefin polymer containing the repeating units shown in formula (A) to formula (E) can be as follows: [ka]

[0095] In the implementation of the present application, the monomer of cyclic olefin polymer having two or more different structures can be copolymerized to obtain cyclic olefin polymer. In the specific implementation of the present application, the monomer of cyclic olefin polymer having two different structures can be copolymerized to obtain cyclic olefin polymer. The chemical equation is shown in formula (b). [ka]

[0096] In this specification, k and p represent the degree of polymerization, and r represents random copolymerization. Furthermore, k:p can range from 1:4 to 4:1. The mechanical properties and heat resistance of the material can be controlled by adjusting the ratio of k:p. Specifically, k:p can be 1:4, 1:3, 1:2, 1:1, 2:1, 3:1, or 4:1.

[0097] The cyclic olefin polymer provided in this embodiment of the present application has both excellent mechanical properties and excellent optical properties, as well as excellent processability and excellent moldability.Cyclic olefin polymer can be used to prepare various optical materials.Embodiments of the present application further provide optical materials comprising the above-mentioned cyclic olefin polymer in embodiments of the present application.

[0098] In the implementation of the present application, the optical material can further include additives. The additives can include one or more of antioxidants, plasticizers, anti-degradation agents, and heat stabilizers; and can further include one or more of fillers, dyes, light stabilizers, UV absorbers, flame retardants, antistatic agents, release agents, and antibacterial agents. Certainly, the optical material can further include another polymer. The other polymer can be another cyclic olefin polymer different from that of the embodiment of the present application, or can be a non-cyclic olefin polymer. Specifically, an appropriate amount of polymer can be added according to need.

[0099] In the implementation of the present application, in the optical material, the mass percentage of the cyclic olefin polymer in this embodiment of the present application is 60% or more.Specifically, in the optical material, the mass percentage of the cyclic olefin polymer in this embodiment of the present application is 60%, 70%, 80% or 90%.

[0100] The embodiments of the present application further provide an optical product. The optical product includes the aforementioned cyclic olefin polymer in the embodiments of the present application, or includes the aforementioned optical material in the embodiments of the present application. The aforementioned cyclic olefin polymer or optical material can be processed to obtain an optical product using various known molding methods. The optical product can be partially obtained by processing the aforementioned cyclic olefin polymer or optical material, or can be completely obtained by processing the aforementioned cyclic olefin polymer or optical material.

[0101] In the implementation of the present application, the optical product may specifically include an optical lens, an optical film, an optical disk, a light guide plate, or a display panel.

[0102] In the implementation of the present application, the optical lens can specifically include a spectacle lens, a camera lens, a sensor lens, an illumination lens, an imaging lens, etc. The camera lens can specifically be a mobile phone camera lens, a laptop camera lens, a desktop camera lens, a vehicle camera lens, etc. The spectacle lens can include a myopia eyeglass lens, a reading eyeglass lens, a sunglasses lens, a contact lens correction lens, a goggle lens, etc. The sensor lens can be a motion detector lens, a proximity sensor lens, a posture control lens, an infrared sensor lens, etc. The illumination lens can be an indoor illumination lens, an outdoor illumination lens, a vehicle headlight lens, a vehicle fog light lens, a vehicle taillight lens, a vehicle running light lens, a vehicle fog light lens, a vehicle interior lens, a light emitting diode (LED) lens, an organic light emitting diode (OLED) lens, etc. The imaging lens can be a scanner lens, a projector lens, a telescope lens, a microscope lens, a magnifying lens, etc.

[0103] In the implementation of the present application, the optical film can include a light guiding film, a reflective film, an anti-reflective film, a diffusion film, a light filter film, a polarizing film, a light splitting film, a phase film, etc. The optical film can be used in the display field, the lighting field, etc. For example, the optical film can be used as a film of a liquid crystal substrate.

[0104] The embodiment of the present application further provides an apparatus including the above-mentioned optical product in the embodiment of the present application. The apparatus may specifically include a mobile terminal, glasses, a camera, a vehicle (e.g., an automobile, a motorcycle, a train, etc.), a lighting device (e.g., a desk lamp, a ceiling lamp, a street lamp, etc.), an imaging device (e.g., a microscope, a telescope, a projector, or a scanner), etc. The mobile terminal may specifically include various portable devices with wireless communication capabilities (e.g., various mobile phones, tablet computers, mobile notebook computers, and netbooks), wearable devices (e.g., smart watches, etc.), or other processing devices connected to wireless modems, and various forms of user equipment (UE), mobile station (MS), terminal device, etc.

[0105] In a particular embodiment of the present application, the device is a mobile terminal, the mobile terminal includes a camera module, the camera module includes a camera lens, and the camera lens is prepared using the aforementioned cyclic olefin polymer in the embodiments of the present application.

[0106] In a particular embodiment of the present application, the device is a vehicle, the vehicle includes a camera module, the camera module includes a camera lens, and the camera lens is prepared using the aforementioned cyclic olefin polymers in the embodiments of the present application.

[0107] Hereinafter, the embodiments of the present application will be further described through several embodiments. EMBODIMENT 1

[0108] The method for preparing a cyclic olefin polymer comprises the following steps.

[0109] (1) Dicyclopentadiene is placed in a flask, distilled under reduced pressure at 210°C, and the fraction is collected to obtain cyclopentadiene. Norbornene and cyclopentadiene are placed in a flask in a molar ratio of 1:1.1, heated and stirred at 200°C for 10 hours, and distilled under reduced pressure to obtain tetracyclo[4.4.0.1 2,5 .1 7,10 ]dodec-3-ene(tetracyclo[4.4.0.1 2,5 .1 7,10 ]dodec-3-ene, TCD), which is shown in Equation 3.

[0110] (2) TCD, 4-methylbenzenemethanol (1 wt%), and butadiene (the molar ratio of norbornene to butadiene is 1:1.2) were placed in a flask, heated and stirred at 250°C for 10 hours, and then distilled under reduced pressure to obtain pentacyclo[6.6.1.1 10,13 .0 2,7 .0 9,14 ]-Hexadec-4-ene (pentacyclo[6.6.1.1 10,13 .0 2,7 .0 9,14 ]-hexadec-4-ene, PCH), which is shown in Equation 3. [ka]

[0111] (3) Dissolve PCH in toluene in a round-bottom flask, add Grubbs' catalyst (0.5 wt%), replace the air in the flask with nitrogen, and keep the reaction system in a nitrogen atmosphere. After the reaction proceeds at room temperature for 2 hours, add excess ethyl vinyl ether and stir at room temperature for another 20 minutes.

[0112] Post-treatment: The reaction solution is slowly dropped into methanol to reprecipitate, and the precipitate is eluted three times with methanol and dried overnight in a vacuum oven at 40°C to obtain an unsaturated cyclic olefin polymer.

[0113] (4) Hydrogenation: Add unsaturated cyclic olefin polymer, p-toluenesulfonyl hydrazide, and tripropylamine in a molar ratio of 1:5:5.5 to a round-bottom flask, add a small amount of butylhydroxytoluene, replace the air in the flask with nitrogen, and add a specific amount of toluene in a nitrogen atmosphere. For re-distillation, stir and heat the reaction system at 110°C for 6 hours. The mixed solution after the reaction is further precipitated in methanol and filtered to obtain a white solid. The white solid is washed with deionized water and then dissolved in hot toluene. Then, re-precipitate in toluene. The above filtration, dissolution, and re-precipitation steps are repeated twice. The white solid obtained after filtration is dried in a vacuum oven at 50°C for 24 hours, and the obtained solid is a saturated cyclic olefin polymer. This process is shown in chemical equation 4. [ka]

[0114] The cyclic olefin polymer obtained in embodiment 1 of the present application corresponds to the product of alternating copolymerization of dimethanooctahydronaphthalene with two ethylene molecules. The molar percentage of dimethanooctahydronaphthalene is 33%. The weight average molecular weight Mw of the cyclic olefin polymer is 50000. The PDI (polymer dispersity index, polymer dispersion index) is 2.0. The cyclic olefin polymer has excellent injection moldability. Here, the Tg is about 135°C. The obtained injection molded parts have low internal stress. Furthermore, the cyclic olefin polymer has excellent optical properties (visible transmittance >90%, refractive index 1.53-1.5, Abbe number 56, haze <0.1%). Furthermore, the cyclic olefin polymer material further has excellent mechanical properties. The tensile strength is 60 MPa, the elongation at break is 7%, the flexural strength is 100 MPa, and the flexural modulus is 2900 MPa. EMBODIMENT 2

[0115] (1) Dicyclopentadiene is placed in a flask, distilled under reduced pressure at 210°C, and the fraction is collected to obtain cyclopentadiene. 1,4-Cyclohexadiene and cyclopentadiene (1.1 equivalents) are placed in a flask in the appropriate ratio, heated at 200°C for 10 hours, and distilled under reduced pressure to obtain tricyclo[4.4.0.1 2,5 ]-Undeca-3,8-diene (tricyclo[4.4.0.1 2,5 ]-Undeca-3,8-diene, TCUD).

[0116] (2) TCUDE, cyclopentadiene (molar ratio 1:1.2), and 4-methylbenzenemethanol (1 wt%) were placed in a flask in the appropriate ratio, heated at 200°C for 10 hours, and distilled under reduced pressure to obtain pentacyclo[6.6.1.1 3,6 .0 2,7 .0 9,14 ]-Hexadeca-4,11-diene (pentacyclo[6.6.1.1 3,6 .0 2,7 .0 9,14 ]-Hexadeca-4,11-diene, PCHD).

[0117] (3) In a 250 mL round-bottom flask, PCHD is dissolved in cyclohexane and a catalyst (Pd-B / γ-Al2O3 amorphous mixture, 1 wt%) is added. After replacing the air in the reaction system with nitrogen, hydrogen is introduced into the reaction system and the hydrogen pressure is maintained at 1.5 MPa. After vigorously stirring the reaction system at 110 °C for 4 hours, pure pentacyclo[6.6.1.1] is obtained by vacuum distillation. 10,13 .0 2,7 .0 9,14 ]-Hexadec-4-ene (pentacyclo[6.6.1.1 10,13 .0 2,7 .0 9,14 ]-hexadec-4-ene, PCH) is obtained. The process is shown in Equation 5. The subsequent aggregation steps are similar to those in embodiment 1. The details will not be described again here. [ka]

[0118] The cyclic olefin polymer obtained in embodiment 2 of the present application is the same as that in embodiment 1. EMBODIMENT 3

[0119] (1) Dicyclopentadiene is placed in a flask, and distilled under reduced pressure at 210°C. The fraction is collected to obtain cyclopentadiene. 1,5-cyclooctadiene and cyclopentadiene are added to a flask in a molar ratio of 1:2.2, 4-methylbenzenemethanol (1 wt%) is added, and the mixture is heated at 200°C for 10 hours. Pentacyclo[8.6.1.1] is obtained by distillation under reduced pressure. 12,15 .0 2,9 .0 11,16 ]-Octadeca-5,13-diene (pentacyclo[8.6.1.1 12,15 .0 2,9 .0 11,16 ]-Octadeca-5,13-diene, PCOD).

[0120] (2) In a 250 mL round-bottom flask, PCOD is dissolved in cyclohexane and a catalyst (Pd-B / γ-Al2O3 amorphous mixture, 1 wt%) is added. After replacing the air in the reaction system with nitrogen, hydrogen is introduced into the reaction system and the hydrogen pressure is maintained at 1.5 MPa. After vigorously stirring the reaction system at 110 °C for 4 hours, pure pentacyclo[8.6.1.1] is obtained by vacuum distillation. 12,15 .0 2,9 .0 11,16 ]-Octadec-5-ene (pentacyclo[8.6.1.1 12,15 .0 2,9 .0 11,16 ]-octadec-5-ene, PCO), which is shown in Equation 6. The subsequent polymerization, hydrogenation, and post-treatment steps of PCO are similar to those in embodiment 1. [ka]

[0121] The cyclic olefin polymer obtained in this embodiment of the present application corresponds to the product of alternating copolymerization of dimethanooctahydronaphthalene with three ethylene molecules. The mole percentage of dimethanooctahydronaphthalene is 25%. The weight average molecular weight Mw of the cyclic olefin polymer is 48000. The PDI is 1.8. The cyclic olefin polymer has excellent injection moldability. Here, the Tg is about 130°C. The obtained injection molded parts have low internal stress. Furthermore, the cyclic olefin polymer has excellent optical properties (visible transmittance is greater than 90%, refractive index is 1.53-1.55, Abbe number is 55, haze is less than 0.2%). Furthermore, the cyclic olefin polymer material further has excellent mechanical properties. The tensile strength is 57 MPa, the elongation at break is 8%, the flexural strength is 88 MPa, and the flexural modulus is 2800 MPa. EMBODIMENT 4

[0122] (1) In a 250 mL round-bottom flask, dicyclopentadiene is dissolved in cyclohexane and a catalyst (Pd-B / γ-Al2O3 amorphous mixture, 1 wt%) is added. After replacing the air in the reaction system with nitrogen, hydrogen is introduced into the reaction system and the hydrogen pressure is maintained at 1.5 MPa. After vigorously stirring the reaction system at 110°C for 4 hours, pure tricyclo[4.3.0.1] is obtained by vacuum distillation. 2,5 ]-Deca-7-ene (tricyclo[4.3.0.1 2,5 ]-dec-7-ene, TCDE) was obtained. The process is shown in Equation 7. The subsequent polymerization, hydrogenation and work-up steps of TCDE are similar to those in embodiment 1. [ka]

[0123] The cyclic olefin polymer obtained in this embodiment of the present application corresponds to the product of alternating copolymerization of norbornene with 1.5 ethylene molecules. The molar percentage of norbornene is 40%. The weight average molecular weight Mw of the cyclic olefin polymer is 44000. The PDI is 2.0. The cyclic olefin polymer has excellent injection moldability. Here, the Tg is about 125°C. The obtained injection molded parts have low internal stress. Furthermore, the cyclic olefin polymer has excellent optical properties (visible transmittance is greater than 90%, refractive index is 1.53-1.55, Abbe number is 54, and haze is less than 0.1%). Furthermore, the cyclic olefin polymer material further has excellent mechanical properties. The tensile strength is 52 MPa, the elongation at break is 12%, the flexural strength is 70 MPa, and the flexural modulus is 2100 MPa. EMBODIMENT 5

[0124] (1) Dicyclopentadiene is placed in a flask, distilled under reduced pressure at 210°C, and the fraction is collected to obtain cyclopentadiene. Dicyclopentadiene and cyclopentadiene are added to a flask in a molar ratio of 1:1.1, heated at 200°C for 10 hours, and distilled under reduced pressure to obtain pentacyclo[6.5.1.1 3,6 .0 2,7 .0 9,13 ]-Pentadeca-4,10-diene (pentacyclo[6.5.1.1 3,6 .0 2,7 .0 9,13 ]-Pentadeca-4,10-diene, PCPD).

[0125] (2) In a 250 mL round-bottom flask, PCPD is dissolved in cyclohexane and a catalyst (Pd-B / γ-Al2O3 amorphous mixture, 1 wt%) is added. After replacing the air in the reaction system with nitrogen, hydrogen is introduced into the reaction system and the hydrogen pressure is maintained at 1.5 MPa. After vigorously stirring the reaction system at 110 °C for 4 hours, pure pentacyclo[6.5.1.1] is obtained by vacuum distillation. 3,6 .0 2,7 .0 9,13 ]-Pentadec-10-ene (pentacyclo[6.5.1.1 3,6 .02,7 .0 9,13 ]-pentadec-10-ene, PCP, is obtained. The process is shown in Equation 8. The subsequent polymerization, hydrogenation, and post-treatment steps of PCP are similar to those in embodiment 1. [ka]

[0126] The cyclic olefin polymer obtained in this embodiment of the present application corresponds to the product of alternating copolymerization of dimethanooctahydronaphthalene with 1.5 ethylene molecules. The mole percentage of dimethanooctahydronaphthalene is 40%. The weight average molecular weight Mw of the cyclic olefin polymer is 60000. The PDI is 2.4. The cyclic olefin polymer has a high Tg. Here, the Tg is about 160°C. Furthermore, the cyclic olefin polymer has excellent optical properties (visible transmittance is greater than 90%, refractive index is 1.53-1.5, Abbe number is 56, and haze is less than 0.1%). Furthermore, the cyclic olefin polymer material further has excellent mechanical properties. The tensile strength is 82 MPa, the elongation at break is 6%, the flexural strength is 137 MPa, and the flexural modulus is 3300 MPa. EMBODIMENT 6

[0127] As shown in chemical equation 9, TCDE and PCP are placed in a 250 mL round-bottom flask in a certain ratio (molar ratio TCDE / PCP is equal to 1 / 9 to 9 / 1), toluene is added to dissolve TCDE and PCP, and then Grubbs Catalyst® M102 (0.5 wt%) is added. The air in the flask is replaced with nitrogen, and the reaction system is placed in a nitrogen atmosphere. After the reaction proceeds at room temperature for 2 hours, excess ethyl vinyl ether is added and stirred at room temperature for another 20 minutes. After that, the post-treatment and hydrogenation process of the polymer are the same as those in Example 1. [ka]

[0128] The cyclic olefin polymer obtained in this embodiment of the present application corresponds to the product of alternating copolymerization of dimethanooctahydronaphthalene, norbornene, and 1.5 ethylene molecules. The total mole percentage of dimethanooctahydronaphthalene and norbornene is 40%. The weight average molecular weight Mw of the cyclic olefin polymer is 42000-65000. The PDI is 1.9-2.5. The cyclic olefin polymer material has excellent optical properties (visible transmittance is more than 90%, refractive index is 1.53-1.55, Abbe number is 54-56, and haze is less than 0.1%). The ratio of the two kinds of cyclic olefin monomers is adjusted. Specifically, the ratio of k to p can be controlled to adjust the Tg of the polymer within the range of 125°C-160°C. In addition, the cyclic olefin polymer material further has excellent mechanical properties. The tensile strength is 52 MPa to 82 MPa, the elongation at break is 6% to 12%, the flexural strength is 70 MPa to 137 MPa, and the flexural modulus is 2100 MPa to 3300 MPa.

[0129] In the cyclic olefin polymer obtained in this embodiment of the present application, the relative content and sequence distribution of rigid bicyclic structure and flexible aliphatic radical segment in the cyclic olefin polymer can be adjusted at the same time.Good optical properties are obtained, the internal stress of the material is reduced, the mechanical properties can be adjusted, and good processability and moldability are realized.

Claims

1. Structural formula (6) 【Chemistry 1】 and containing a structure derived from an unsaturated cyclohexene structure and saturated dimethanooctahydronaphthalene, wherein the cyclic olefin polymer is an alternating copolymer of the saturated dimethanooctahydronaphthalene and a C4 chain segment, and has a weight average molecular weight of 42,000 to 65,000.

2. 2. The cyclic olefin polymer according to claim 1, wherein the total mass percentage of the repeating units of the structural formula shown in formula (6) in the cyclic olefin polymer is 50% or more.

3. The cyclic olefin polymer according to claim 1 or 2, wherein the refractive index of the cyclic olefin polymer is from 1.53 to 1.

58.

4. The cyclic olefin polymer according to any one of claims 1 to 3, wherein the cyclic olefin polymer has an Abbe number of 53 or more.

5. The cyclic olefin polymer according to any one of claims 1 to 4, wherein the haze of the cyclic olefin polymer is less than 0.2%.

6. The cyclic olefin polymer according to any one of claims 1 to 5, wherein the cyclic olefin polymer has a visible light transmittance of 90% or more.

7. An optical material comprising the cyclic olefin polymer according to any one of claims 1 to 6.

8. The optical material of claim 7 , further comprising an additive, the additive comprising one or more of an antioxidant, a plasticizer, a thermal stabilizer, and an anti-degradation agent.

9. 8. The optical material of claim 7, wherein the weight percent of the cyclic olefin polymer in the optical material is 60% or greater.

10. An optical product comprising the cyclic olefin polymer according to any one of claims 1 to 6 or the optical material according to any one of claims 7 to 9.

11. An apparatus comprising the optical article of claim 10.

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