Cycloolefin copolymer with improved optical performance and preparation method thereof
By introducing high-refractive-index aromatic groups and sulfur atoms, the molecular structure of cyclic olefin copolymers is optimized, solving the problems of low refractive index and poor flexibility of existing cyclic olefin copolymers, and realizing optical materials with high refractive index, low birefringence and high transparency.
Patent Information
- Application Number
- CN202511118855.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-11
- Publication Date
- 2025-10-21
AI Technical Summary
Existing cycloolefin copolymers have a low refractive index, strong molecular chain rigidity, poor elongation at break, and are prone to microcracks under high temperature and high humidity conditions, making it difficult to meet the needs of high-performance optical materials.
By introducing aromatic groups with high refractive index and sulfur atoms, conjugated polymers are prepared through polymerization in organic solvents using Ru catalysts. The molecular structure is then optimized to improve polarizability and flexibility.
It significantly improves the refractive index and transparency of cyclic olefin copolymers, enhances their UV protection capabilities, and improves the light transmission efficiency and chemical stability of optical materials.
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Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of polymer materials, and particularly relates to a cycloolefin copolymer with improved optical properties and a preparation method thereof. Background Art
[0002] With the rapid development of optical technology, demand for high-refractive-index polymer materials is growing in fields such as optical components, optical coatings, display devices, fiber-optic communications, and sensors. High-refractive-index materials can significantly enhance the performance of optical devices, such as improving imaging quality, enhancing light focusing, and reducing device size and weight. Therefore, the development of polymer materials that combine high refractive index with excellent light transmittance and thermal stability has become a current research hotspot.
[0003] Cyclic olefin copolymers (COC / COP) are widely used in the optical field due to their high transparency, low birefringence, excellent mechanical properties, and thermal stability, such as high-refractive-index optical components, optical coatings, and high-end optical devices. However, their generally low refractive index (approximately 1.53-1.55) makes them difficult to meet the growing demand for high-performance optical materials. Furthermore, existing cycloolefin copolymers have relatively high molecular chain rigidity and relatively poor elongation at break. Furthermore, COC / COP is prone to microcracks after high-temperature and high-humidity testing, which can degrade the optical properties of molded products. Summary of the Invention
[0004] The purpose of the present invention is to provide a cycloolefin copolymer with improved optical properties and a preparation method thereof, thereby improving its refractive index while maintaining good light transmittance, low birefringence and high transparency, so as to meet the demand for high refractive index and high transparency optical materials in the fields of optical elements, optical coatings, display devices, optical fiber communications, etc.
[0005] The present invention provides a cycloolefin copolymer with improved optical properties, wherein the structure of the cycloolefin copolymer is:
[0006] Wherein n is the degree of polymerization, which is 1000≤n≤5000; y is 0 or 1; R1 and R2 are each independently selected from diphenylmethyl, triphenylmethyl, carbazolyl, fluorenyl, biphenyl, naphthyl, pyrenyl, anthracenyl, phenanthrenyl, acenaphthenyl, phenyl or phenyl derivatives.
[0007] Preferably, the cycloolefin copolymer is polymerized from monomer A, and the molecular formula of monomer A is:
[0008] wherein y is 0 or 1; R1 and R2 are each independently selected from diphenylmethyl, triphenylmethyl, diphenylmethane, carbazolyl, fluorenyl, biphenyl, naphthyl, pyrenyl, anthracenyl, phenanthrenyl, acenaphthenyl, phenyl or a phenyl derivative.
[0009] Preferably, the molecular formula of the monomer A can be any one of the following formulas (1) to (19):
[0010] .
[0011] The present invention also provides a method for preparing the cycloolefin copolymer described in the above technical solution, comprising the following steps: adding monomer A to a reaction vessel, then adding a catalyst in an amount of 0.1% to 1% of the total molar amount of monomer A, and conducting a polymerization reaction in an organic solvent, wherein the polymerization reaction temperature is 40°C to 100°C; and the polymerization reaction time is 20 to 40 hours.
[0012] Preferably, in the polymerization reaction system, the concentration of monomer A is 0.1~1M.
[0013] Preferably, the organic solvent is tetrahydrofuran, toluene, dimethyl sulfoxide, N-methylpyrrolidone, propylene glycol monomethyl ether acetate, ethyl acetate or methyl ethyl ketone.
[0014] Preferably, the catalyst is a Ru catalyst.
[0015] Preferably, the Ru catalyst is a ruthenium carbene catalyst or ruthenium trichloride.
[0016] The cycloolefin copolymer of the present invention introduces an aromatic group with a high refractive index, which has a larger conjugated system and can significantly increase the polarizability of the molecule, thereby achieving improvements in the refractive index and optical properties of the cycloolefin copolymer.
[0017] Based on the technical effects brought about by the above technical solution, the use of the cycloolefin copolymer described in the above technical solution or the cycloolefin copolymer prepared by the method described in the above technical solution in the preparation of optical products should also fall within the protection scope of the present invention.
[0018] Beneficial effects of the present invention: According to the Lorentz-Lorenz equation, an increase in molecular polarizability directly leads to an increase in refractive index. The cycloolefin copolymer of the present invention introduces a high-refractive-index aromatic group, which has a larger conjugated system and can significantly increase the molecular polarizability, thereby achieving an improvement in the refractive index and optical properties of the cycloolefin copolymer.
[0019] The present invention introduces sulfur atoms into the conjugated polymer, which can change the electron distribution and spatial structure of the molecule, thereby increasing the refractive index of the polymer; the presence of sulfur atoms can also effectively improve the material's protection against ultraviolet rays and increase the flexibility of the molecular chain.
[0020] The cycloolefin copolymer provided by the present invention has extremely high light transmittance in the visible light range, can effectively reduce light scattering and absorption, and can significantly improve light transmission efficiency and reduce signal loss when manufacturing products such as optical lenses and optical fibers, thereby improving the overall performance of the optical system.
[0021] The aromatic and heterocyclic groups contained in the molecular structure of the cycloolefin copolymer of the present invention have high chemical bond energy and resistance to chemical corrosion. In common chemical solvents and corrosive environments, such as acids, alkalis, organic solvents, etc., they can maintain good chemical stability and are not prone to hydrolysis, oxidation or degradation reactions. DETAILED DESCRIPTION
[0022] In order to further illustrate the present invention, the solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be understood as limiting the scope of protection of the present invention.
[0023] The catalysts used in the examples of the present invention, RuCl3, were purchased from Shanghai Aoji Chemical Co., Ltd., with a CAS number of 10049-08-8; the ruthenium carbene catalyst was purchased from Eastman Chemical (Shanghai) Co., Ltd., Grubbs catalyst, with a CAS number of 246047-72-3.
[0024] The sources of the monomers involved in the embodiments of the present invention are not particularly limited and can be obtained using preparation techniques well known to those skilled in the art.
[0025] Unless otherwise specified, the substances used in the examples of the present invention are conventional commercially available products.
[0026] Example 1 Monomer A Add to the reactor and add 1L of toluene to mix evenly; The final concentration of monomer A in the toluene solution is 0.5 M; then, a catalyst (RuCl3) with a molar ratio of 0.1% of monomer A is added, and the reaction is carried out at 80°C for 30 hours, followed by stopping the heating and adding 10 mL of ethanol acidified with hydrochloric acid to terminate the reaction. The product is washed, filtered, and dried at 30°C for 12 hours to obtain a cycloolefin copolymer.
[0027] Example 2 Monomer A Add to the reactor and add 1L of toluene to mix evenly; The final concentration of monomer A in toluene solution is 0.6 M, and then a catalyst (ruthenium carbene catalyst) is added at a molar ratio of 0.5% of monomer A. After reacting at 100°C for 24 minutes, heating is stopped and 10 mL of ethanol acidified with hydrochloric acid is added to terminate the reaction. The product is washed, filtered, and vacuum dried at 25°C for 18 hours to obtain a cycloolefin copolymer.
[0028] Example 3 Monomer A Add to the reactor and add 1L of toluene to mix evenly; The final concentration of monomer A in toluene solution is 0.8 M, and then a catalyst (RuCl3) with a molar ratio of 0.5% of monomer A is added. After reacting at 100°C for 22 hours, heating is stopped and 10 mL of ethanol acidified with hydrochloric acid is added to terminate the reaction. The product is washed, filtered, and vacuum dried at 25°C for 18 hours to obtain a cycloolefin copolymer.
[0029] Example 4 Monomer A Add to the reactor and add 1L of toluene to mix evenly; The final concentration of monomer A in toluene solution is 1M, and then a catalyst (RuCl3) with a molar percentage of 1% of monomer A is added. After reacting at 100°C for 28 hours, heating is stopped and 10 mL of ethanol acidified with hydrochloric acid is added to terminate the reaction. The product is washed, filtered, and vacuum dried at 30°C for 18 hours to obtain a cycloolefin copolymer.
[0030] Example 5 Monomer A Add to the reactor and add 1L of toluene to mix evenly; The final concentration of monomer A in the toluene solution was 0.6 M. Then, a catalyst (ruthenium carbene catalyst) was added at 1 mol% of monomer A. After reacting at 60°C for 40 hours, heating was stopped and 10 mL of ethanol acidified with hydrochloric acid was added to terminate the reaction. The product was washed, filtered, and vacuum dried at 30°C for 15 hours to obtain a cycloolefin copolymer.
[0031] Example 6 Monomer A Add to the reactor and add 1L of toluene to mix evenly; The final concentration of monomer A in toluene solution is 0.8 M. Then, a catalyst (RuCl3) with a molar ratio of 0.8% of monomer A is added. After reacting at 60°C for 40 hours, heating is stopped and 10 mL of ethanol acidified with hydrochloric acid is added to terminate the reaction. The product is washed, filtered, and vacuum dried at 30°C for 15 hours to obtain a cycloolefin copolymer.
[0032] Comparative Example 1 The difference from Example 1 is that the structure of monomer A is different, as follows: Monomer A Add to the reactor and add 1L of toluene to mix evenly; The final concentration of monomer A in the toluene solution is 0.5 M; then, a catalyst (RuCl3) with a molar ratio of 0.1% of monomer A is added, and the reaction is carried out at 80°C for 30 hours, followed by stopping the heating and adding 10 mL of ethanol acidified with hydrochloric acid to terminate the reaction. The product is washed, filtered, and dried at 30°C for 12 hours to obtain a cycloolefin copolymer.
[0033] Comparative Example 2 The difference from Example 1 is that the structure of monomer A is different, as follows: Monomer A Add to the reactor and add 1L of toluene to mix evenly; The final concentration of monomer A in the toluene solution is 0.5 M; then, a catalyst (RuCl3) with a molar ratio of 0.1% of monomer A is added, and the reaction is carried out at 80°C for 30 hours, followed by stopping the heating and adding 10 mL of ethanol acidified with hydrochloric acid to terminate the reaction. The product is washed, filtered, and dried at 30°C for 12 hours to obtain a cycloolefin copolymer.
[0034] Comparative Example 3 The difference from Example 1 is that the structure of monomer A is different, as follows: Monomer A Add to the reactor and add 1L of toluene to mix evenly; The final concentration of monomer A in the toluene solution is 0.5 M; then, a catalyst (RuCl3) with a molar ratio of 0.1% of monomer A is added, and the reaction is carried out at 80°C for 30 hours, followed by stopping the heating and adding 10 mL of ethanol acidified with hydrochloric acid to terminate the reaction. The product is washed, filtered, and dried at 30°C for 12 hours to obtain a cycloolefin copolymer.
[0035] Test Example 1 The cycloolefin copolymers prepared in Examples 1 to 6 and Comparative Examples 1 to 3 were used as samples, and their refractive index, Abbe number, visible light transmittance, haze, and glass transition temperature (Tg) were measured. The results are shown in Table 1.
[0036] Table 1 Optical properties of cycloolefin copolymers
[0037] As can be seen from Table 1, compared with the comparative example, the cycloolefin copolymer prepared in the embodiment of the present invention has the characteristics of high refractive index and low Abbe number; low haze and high visible light transmittance, indicating that it has good transparency.
[0038] Although the above embodiment provides a detailed description of the present invention, it is only a part of the embodiments of the present invention, not all of the embodiments. People can also obtain other embodiments based on this embodiment without creativity, and these embodiments all fall within the scope of protection of the present invention.
Claims
1. A cycloolefin copolymer with improved optical properties, characterized in that: The structure of the cycloolefin copolymer is: Where n is the degree of polymerization, which is 1000≤n≤5000; y is 0 or 1; R1 and R2 are each independently selected from diphenylmethyl, triphenylmethyl, carbazolyl, fluorenyl, biphenyl, naphthyl, pyrenyl, anthracenyl, phenanthrenyl, acenaphthenyl, phenyl or a phenyl derivative.
2. The cyclic olefin copolymer according to claim 1, characterized in that The cycloolefin copolymer is formed by polymerizing monomer A, and the molecular formula of monomer A is: wherein y is 0 or 1; R1 and R2 are each independently selected from diphenylmethyl, triphenylmethyl, diphenylmethane, carbazolyl, fluorenyl, biphenyl, naphthyl, pyrenyl, anthracenyl, phenanthrenyl, acenaphthenyl, phenyl or a phenyl derivative.
3. The cyclic olefin copolymer according to claim 2, characterized in that The molecular formula of the monomer A can be any one of the following formulas (1) to (19): 。 4. The method for preparing the cycloolefin copolymer according to any one of claims 1 to 3, wherein The method comprises the following steps: Add monomer A to a reaction container, then add 0.1% to 1% of the total molar amount of monomer A into a catalyst, and carry out a polymerization reaction in an organic solvent. The polymerization reaction temperature is 40° C. to 100° C., and the polymerization reaction time is 20 to 40 hours.
5. The method according to claim 4, characterized in that In the polymerization reaction system, the concentration of monomer A is 0.1~1M.
6. The method according to claim 4, characterized in that The organic solvent is tetrahydrofuran, toluene, dimethyl sulfoxide, N-methylpyrrolidone, propylene glycol monomethyl ether acetate, ethyl acetate or methyl ethyl ketone.
7. The method according to claim 4, characterized in that The catalyst is a Ru catalyst.
8. The method according to claim 7, characterized in that The Ru catalyst is a ruthenium carbene catalyst or ruthenium trichloride.
9. Use of the cycloolefin copolymer according to any one of claims 1 to 3 or the cycloolefin copolymer prepared by the method according to any one of claims 4 to 8 in the preparation of optical products.