A method for improving the weather resistance of a cyclic olefin polymer

Abstract

The application belongs to the technical field of high polymer materials, and particularly relates to a method for improving the weather resistance of a cyclic olefin polymer. The application first provides a monomer A for improving the weather resistance of a cyclic olefin polymer, the molecular formula of the monomer A is shown in formula (I), the introduction of a fluorine-containing heterocycle into the monomer A changes the electronic distribution and spatial structure of the monomer A, effectively improves the protection ability of the corresponding material to hygrothermal aging and flexibility, and is beneficial to the improvement of the weather resistance of the subsequent polymer. The monomer A is used in the preparation of a cyclic olefin polymer or an optical product containing the cyclic olefin polymer, which is beneficial to the improvement of the tensile strength and tear strength of the corresponding product, and the reduction of the degree of hygrothermal aging of the corresponding product. Therefore, the technical scheme of the application provides a new solution for improving the weather resistance of the cyclic olefin polymer.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to a method for improving the weather resistance of cyclic olefin polymers. Background Technology

[0002] Cyclic olefin polymers (COPs) possess many excellent properties, such as good transparency, high refractive index, low birefringence, high chemical stability, good biocompatibility and water vapor barrier properties, as well as low dielectric constant and low dielectric loss. Therefore, they can be widely used in optical devices, medical packaging materials and thin film capacitors.

[0003] However, in practical applications, the weather resistance of cyclic olefin polymers still faces some challenges. For example, in the field of optical devices, cyclic olefin polymers need to be exposed to various environmental conditions for a long time, so good weather resistance is beneficial to ensuring their optical performance. Similarly, in the field of medical packaging, physical and chemical stability needs to be maintained under different environmental conditions to prevent packaging failure due to aging. In existing technologies, the weather resistance of cyclic olefin polymers is often improved by modifying the preparation process. For example, Chinese Patent CN 119930991 A describes a cyclic olefin polymer with low volatile content obtained through processes such as raw material preparation, polymerization, hydrogenation, devolatilization, and devolatilization extrusion granulation. This cyclic olefin polymer is non-crosslinked, has stable structure and properties, does not turn yellow, and is easy to process. However, the above process is cumbersome and has relatively poor weather resistance. Therefore, how to improve the weather resistance of cyclic olefin polymers while ensuring a simple preparation method is a pressing problem to be solved in this field. Summary of the Invention

[0004] The purpose of this invention is to provide a method for improving the weather resistance of cyclic olefin polymers. A polymerization reaction system is constructed using monomer A to obtain cyclic olefin polymers, thereby improving the weather resistance of cyclic olefin polymers. The above method is not only simple, but the cyclic olefin polymers prepared by it are also resistant to stretching, tearing, and aging.

[0005] This invention provides a monomer A for improving the weather resistance of cyclic olefin polymers, wherein the molecular formula of monomer A is shown in formula (I): Equation (I); ; R1 and R2 are independently selected from fluorine atoms or perfluoroalkyl groups; m is 0-2.

[0006] Preferably, the molecular formula of monomer A is any one of formulas (II)-(III): Formula (II): ; Formula (III): .

[0007] This invention provides the application of monomer A, as described in the above technical solution, in improving the weather resistance of cycloolefin products.

[0008] Preferably, the cyclic olefin product includes: cyclic olefin polymers or optical articles containing cyclic olefin polymers.

[0009] Preferably, the cyclic olefin polymer has the structure shown in formula (V): Formula (V): ; n represents the degree of aggregation, with a value of 1000≤n≤5000; m is 0-2.

[0010] Preferably, the indicators for improving the weather resistance include one or more of the following (1)-(3): (1) Improve tensile strength; (2) Improve tear strength; (3) Reduce the degree of damp heat aging.

[0011] This invention provides a method for improving the weather resistance of cyclic olefin polymers, comprising the following steps: A polymerization reaction system is constructed using monomer A as described in the above technical solution. After hydrogenation, a cyclic olefin polymer is obtained to improve the weather resistance of the cyclic olefin polymer.

[0012] Preferably, the concentration of monomer A in the polymerization reaction system is 0.4~0.8M.

[0013] Preferably, the polymerization reaction system also includes: Grubbs catalyst and organic solvent; The Grubbs catalyst includes: Grubbs second-generation catalyst or Grubbs third-generation catalyst.

[0014] Preferably, the polymerization temperature is 60-80℃ and the polymerization time is 18-20h.

[0015] Beneficial effects: This invention provides a monomer A for improving the weather resistance of cyclic olefin polymers, wherein the molecular formula of monomer A is shown in formula (I). This invention introduces a fluorinated heterocycle into monomer A, thereby altering the electron distribution and spatial structure of monomer A, effectively improving the protection and flexibility of the corresponding material against damp heat aging, which is beneficial for subsequent improvement of the polymer's weather resistance.

[0016] Based on the aforementioned technical advantages, this invention also provides the application of monomer A in improving the weather resistance of products. By preparing cyclic olefin polymers or optical products containing cyclic olefin polymers using the monomers provided by this invention, it is beneficial to improve the tensile strength and tear strength of the products and reduce the degree of damp heat aging. Therefore, the technical solution provided by this invention is beneficial to improving the weather resistance of cyclic olefin polymers and provides a new approach to solving technical problems in this field. Detailed Implementation

[0017] To further illustrate the present invention, the solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0018] The monomers involved in the embodiments of the present invention are not subject to any special restrictions on their source and are obtained using preparation techniques well known to those skilled in the art.

[0019] In a specific embodiment of the present invention, the CAS number of the Grubbs catalyst is 246047-72-3.

[0020] Unless otherwise specified, all substances used in the embodiments of this invention are conventional commercially available products.

[0021] Example 1 After adding monomer A as shown in formula (II) to the reactor, add toluene solution (ensuring the final concentration of monomer A in the toluene solution is 0.4M) to the reactor and mix evenly to obtain a mixture. Add Grubbs catalyst to the mixture to construct a polymerization reaction system and react at 80℃ for 20h. Add a termination reaction solution and then mix the obtained product with a ruthenium catalyst (the amount of ruthenium catalyst is 0.1% of the monomer mass) and send it to a hydrogenation reactor for hydrogenation reaction (introduce hydrogen gas to the reaction pressure to 10MPa and react at 100℃ for 6h). After the reaction is completed, wash, filter and dry the material in sequence to obtain a cyclic olefin polymer.

[0022] Example 2 After adding monomer A as shown in formula (III) to the reactor, add toluene solution (ensuring the final concentration of monomer A in the toluene solution is 0.4M) to the reactor and mix evenly to obtain a mixture. Add Grubbs catalyst to the mixture to construct a polymerization reaction system and react at 80℃ for 20h. Add a termination reaction solution and then mix the obtained product with a ruthenium catalyst (the amount of ruthenium catalyst is 0.1% of the monomer mass) and send it to a hydrogenation reactor for hydrogenation reaction (introduce hydrogen gas to the reaction pressure to 10MPa and react at 100℃ for 6h). After the reaction is completed, wash, filter and dry the material in sequence to obtain a cyclic olefin polymer.

[0023] Example 3 Monomer A, as shown in formula (II), was added to the reactor, followed by the addition of toluene solution (ensuring a final concentration of 0.8 M for the mixed monomers in the toluene solution) and mixed thoroughly to obtain a mixture. Grubbs catalyst was added to the mixture to construct a polymerization reaction system, and the reaction was carried out at 80 °C for 18 h. A termination reaction solution was added, and the resulting product and a ruthenium catalyst (0.1% of the monomer mass) were mixed and sent to a hydrogenation reactor for hydrogenation reaction (hydrogen gas was introduced until the reaction pressure reached 10 MPa, and the reaction was carried out at 100 °C for 6 h). After the reaction was completed, the materials were washed, filtered, and dried sequentially to obtain a cyclic olefin polymer.

[0024] Example 4 After adding monomer A as shown in formula (III) to the reactor, add toluene solution (ensuring the final concentration of monomer A in the toluene solution is 0.8M) to the reactor and mix evenly to obtain a mixture. Add Grubbs catalyst to the mixture to construct a polymerization reaction system and react at 80℃ for 18h. Add a termination reaction solution and then mix the obtained product with a ruthenium catalyst (the amount of ruthenium catalyst is 0.1% of the monomer mass) and send it to a hydrogenation reactor for hydrogenation reaction (introduce hydrogen gas to the reaction pressure to 10MPa and react at 100℃ for 6h). After the reaction is completed, wash, filter and dry the material in sequence to obtain a cyclic olefin polymer.

[0025] Comparative Example 1 The only difference from Example 1 is that the structure of the monomer in Comparative Example 1 is as shown in Formula (IV): Formula (IV):

[0026] After adding the monomer shown in formula (IV) to the reactor, an organic solvent toluene solution was added to the reactor (ensuring that the final concentration of monomer A in the toluene solution was 0.4M) and mixed evenly to obtain a mixture. Grubbs catalyst was added to the mixture to construct a polymerization reaction system, and the reaction was carried out at 80°C for 20 h. A termination reaction solution was added, and then the obtained product and a ruthenium-based catalyst (the amount of ruthenium-based catalyst was 0.1% of the monomer mass) were mixed and sent to a hydrogenation reactor for hydrogenation reaction (hydrogen gas was introduced to the reaction pressure to 10 MPa, and the reaction was carried out at 100°C for 6 h). After the reaction was completed, the materials were washed, filtered and dried in sequence to obtain a cyclic olefin polymer.

[0027] Comparative Example 2 The only difference from Example 1 is the composition of the mixed monomers: After adding norbornene to the reactor, a toluene solution (ensuring the final concentration of the mixed monomers in the toluene solution is 0.4M) is added and mixed thoroughly to obtain a mixture. Grubbs catalyst is added to the mixture to construct a polymerization reaction system, and the reaction is carried out at 80℃ for 20h. A termination reaction solution is added, and then the obtained product and a ruthenium-based catalyst (the amount of ruthenium-based catalyst is 0.1% of the monomer mass) are mixed and sent to a hydrogenation reactor for hydrogenation reaction (hydrogen gas is introduced to the reaction pressure to 10MPa, and the reaction is carried out at 100℃ for 6h). After the reaction is completed, the materials are washed, filtered and dried sequentially to obtain a cyclic olefin polymer.

[0028] Application Example 1 The cyclic olefin polymers prepared in Examples 1-4 and Comparative Examples 1-2 were used as samples (three parallel replicates were set up for each sample when measuring each index). The refractive index and Abbe number of each sample were measured at a wavelength of 589 nm when the samples were injection molded into plates with a size of 100 mm × 50 mm × 3 mm. The haze of each sample at a 0° angle was statistically analyzed when the samples were injection molded into plates with a size of 100 mm × 10 mm × 1 mm. The results are shown in Table 1.

[0029] Table 1 Optical properties of cyclic olefin copolymers

[0030] As shown in Table 1, regardless of the examples or comparative examples, the cyclic olefin polymers have a refractive index of 1.525-1.537, an Abbe number of 52-58, and a haze of <0.1%, exhibiting good optical properties.

[0031] Application Example 2 The temperature was increased at a rate of 10°C / min using a DSC testing device. When the temperature reached 250°C, a gas with an O2 / N2 ratio of 25 / 75 was introduced. The time from the introduction of the mixed gas until the sample (the cyclic olefin polymers prepared in Examples 1-4 and Comparative Examples 1-2, ground into 500-mesh powder) began to degrade was defined as the change in oxidation-inducible period (OIT). Each sample was tested in triplicate. The results are shown in Table 2.

[0032] Table 2 OIT Variation under Different Treatments

[0033] As can be seen from the data in Table 2, compared with Comparative Example 1, the solutions in Examples 1-4 and Comparative Example 2 are more conducive to prolonging the oxidation induction period of each material. In other words, the technical solutions in Examples 1-4 and Comparative Example 2 are more conducive to improving the stability of the corresponding materials and have strong anti-aging properties.

[0034] Application Example 3 Equal amounts of cyclic olefin polymers (prepared in Examples 1-4 and Comparative Examples 1-2) were placed in a humid and hot environment (temperature 150°C, humidity 80%, 200h). Tensile strength (tensile strength refers to the stress at which a material undergoes maximum uniform plastic deformation. In a tensile test, the maximum tensile stress experienced by the specimen until fracture is the tensile strength. Higher tensile strength indicates a stronger resistance to breakage) and elongation at break (elongation at break refers to the elongation before and after stretching, compared to the original length before stretching) were measured using a tensile testing machine (A&D Company, Limited, TENSILON RTM-100 universal testing machine) at 23°C, chuck spacing 50mm, and tensile speed 50mm / min. The results are shown in Table 3.

[0035] Table 3 Performance of samples under different treatments

[0036] As shown in Table 3, compared with the comparative examples, the cyclic olefin polymers prepared in Examples 1-4 still maintain good mechanical properties after wet heat treatment.

[0037] In summary, the technical solution provided by this invention is beneficial for improving the tensile strength and tear strength of the corresponding products; reducing the degree of damp heat aging of the corresponding products; and providing a new solution for improving the weather resistance of cyclic olefin polymers.

[0038] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. People can obtain other embodiments based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A monomer A for improving the weather resistance of cyclic olefin polymers, characterized in that, The molecular formula of monomer A is shown in formula (Ⅰ): Equation (I); ； R1 and R2 are independently selected from fluorine atoms or perfluoroalkyl groups; m is 0-2.

2. The monomer A according to claim 1, characterized in that, The molecular formula of monomer A is any one of formulas (II)-(III): Formula (II): ； Formula (III): 。 3. The application of monomer A as described in claim 1 or 2 in improving the weather resistance of cycloolefin products.

4. The application according to claim 3, characterized in that, The cyclic olefin products include: cyclic olefin polymers or optical products containing cyclic olefin polymers.

5. The application according to claim 4, characterized in that, The structure of the cyclic olefin polymer is shown in formula (V): Formula (V): ； n represents the degree of aggregation, with a value of 1000≤n≤5000; m is 0-2.

6. The application according to claim 3, characterized in that, The indicators for improving the weather resistance include one or more of the following (1)-(3): (1) Improve tensile strength; (2) Improve tear strength; (3) Reduce the degree of damp heat aging.

7. A method for improving the weather resistance of cyclic olefin polymers, characterized in that, Includes the following steps: A polymerization reaction system is constructed using monomer A as described in claim 1 or 2, and after hydrogenation, a cyclic olefin polymer is obtained to improve the weather resistance of the cyclic olefin polymer.

8. The method according to claim 7, characterized in that, In the polymerization reaction system, the concentration of monomer A is 0.4~0.8M.

9. The method according to claim 6, characterized in that, The polymerization reaction system also includes: Grubbs catalyst and organic solvent; The Grubbs catalyst includes: Grubbs second-generation catalyst or Grubbs third-generation catalyst.

10. The method according to claim 6, characterized in that, The polymerization reaction temperature is 60-80℃; the polymerization reaction time is 18-20h.

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