Processing technology of high-transmittance composite material, high-transmittance composite material and application of high-transmittance composite material

Abstract

The invention relates to the field of high-transmittance materials, and provides a processing technology of a high-transmittance composite material, the high-transmittance composite material and application of the high-transmittance composite material in order to solve the problem that an existing cycloolefin copolymer and polycarbonate resin are low in compatibility, and the processing technology comprises the steps that S100, after cycloolefin is dissolved in a solvent, ethylene gas is introduced, and polymerization is conducted under the action of a catalyst to obtain a first pre-product solution; the polymerization time is 40-100 min, the polymerization temperature is 50-70 DEG C, and the polymerization pressure is 2-4 Mpa; s200, by weight, after pressure relief, 30-40 parts of triethanolamine, 50-70 parts of 1, 1, 1-trimethylolpropane and 300-500 parts of MMA-TC are added into the first pre-product solution, and a second pre-product solution is prepared after a reaction; the reaction time is 5-8 hours, and the reaction temperature is 70-100 DEG C; and S300, filtering, washing and drying the second pre-product solution to obtain the high-transmittance composite material. The polycarbonate chain segment is inserted into the cycloolefin polymer structure, and the ratio of the polycarbonate chain segment to the cycloolefin polymer and the reaction conditions are controlled, so that the hardness of the composite material is improved as much as possible under the condition of preferentially ensuring the combination degree and the light transmittance.

Description

Technical Field

[0001] The present invention relates to the field of high-transparency materials, and more particularly, to a processing technology of a high-transparency composite material, the high-transparency composite material and its application. Background Art

[0002] At present, most optical lenses adopt a structure of all-glass or glass + resin. Optical glass performs excellently in optical properties and hardness properties, etc., but has a high cost and a relatively heavy weight. Resin has a low cost and a light weight, but it is difficult to match optical glass in terms of optical properties and hardness. Cycloolefin polymer is an amorphous and highly pure transparent resin, which has excellent optical properties, low specific gravity, high heat resistance and chemical stability, etc., but its production cost is very high, even exceeding that of optical glass. There is an urgent need for a modified cycloolefin polymer that can be used in combination with low-cost resin lenses, so as to add a cycloolefin polymer layer on the basis of low-cost resin lenses to achieve effective cost control while improving the optical effect of the product. Summary of the Invention

[0003] The purpose of the present invention is to provide a processing technology of a high-transparency composite material to solve the problem of low compatibility between existing cycloolefin copolymers and polycarbonate resins.

[0004] Another purpose of the present invention is to provide a high-transparency composite material, which has good optical properties, hardness, processability and high compatibility with polycarbonate resin.

[0005] The purpose of the present invention is also to provide an application of a high-transparency composite material. After being applied to lenses, it can improve the optical properties of the lenses, etc. on the basis of cost control.

[0006] The embodiments of the present invention are achieved by the following technical solutions:

[0007] A processing technology of a high-transparency composite material includes:

[0008] S100. After dissolving cycloolefin in a solvent, introducing ethylene gas, and polymerizing under the action of a catalyst to obtain a first pre-product solution; the polymerization time is 40 - 100 min, the polymerization temperature is 50 - 70 °C, and the polymerization pressure is 2 - 4 Mpa;

[0009] S200. By weight, after depressurizing, adding 30 - 40 parts of triethanolamine, 50 - 70 parts of 1,1,1-trimethylolpropane and 300 - 500 parts of MMA-TC to the first pre-product solution, and reacting to obtain a second pre-product solution; the molar ratio of the cycloolefin to the MMA-TC is (30 - 50):(7 - 10), the reaction time is 5 - 8 h, and the reaction temperature is 70 - 100 °C;

[0010] The S300, the second prepolymer solution is filtered, washed, and dried to obtain a high-transparency composite material.

[0011] COC is a high-performance thermoplastic with very high transparency, almost approaching that of optical glass. Secondly, it has good biocompatibility, drug compatibility, heat resistance, high Abbe number, and low birefringence. Therefore, it has good applicability in the pharmaceutical industry and optical products. However, its production cost is relatively high. If used as the main material, it will lead to too high product cost and is difficult to be applicable in the mid- to low-end market. The common materials for optical lenses are optical glass and resin. However, the costs of optical glass and COC are relatively high. Especially for mid- to low-end optical lenses, generally glass + resin lenses or all-resin lenses are used, and resin lenses generally use PC or PMMA. Due to the poor optical performance of the materials used for the lenses, most resin lenses will also use an anti-reflection film, etc. to improve their imaging effect. The applicant hopes to reduce the cost and improve the imaging effect by covering PC with COC. However, the processing window of COC is relatively narrow, and it has a relatively high glass transition temperature, so the processing temperature is relatively high. In addition, COC has poor flexibility and is difficult to be applicable to the method of roller pasting and covering. Using optical glue to bond two resin materials will also have problems such as the compatibility between the substrate and the optical glue, the durability of the optical glue, and the high precision requirements for the bonding operation of aspherical lenses. Therefore, the applicant hopes to combine COC with PC by injection molding, hot pressing, or co-extrusion. However, if COC is directly combined with PC, the compatibility between the two is relatively poor. Therefore, one of the purposes of the present invention is to provide a high-transparency composite material with good compatibility with PC. However, during the experiment, one of the difficulties in this case is how to modify COC in the original reaction system of COC.

[0012] Common production processes of polycarbonate include phosgene interfacial polycondensation, melt transesterification polycondensation, and non-phosgene melt transesterification polycondensation. Among them, the phosgene interfacial polycondensation method has a relatively high poisoning risk and is rarely used. The reaction media of melt transesterification polycondensation and non-phosgene melt transesterification polycondensation are molten bodies. Therefore, the above three production processes are difficult to be directly applied to the COC synthesis system. Therefore, the applicant referred to the patent with the application number 2020800341688 and the patent name "Method for Synthesizing Polycarbonate from Cyclic Monothiocarbonate". Its advantage is that the synthesis of PC can be achieved through a liquid-phase reaction, and the reaction conditions do not need to be controlled as anhydrous and anaerobic. However, after inserting the corresponding PC chain segments into COC, although the binding degree with the PC layer has increased, the hardness of the composite material has significantly decreased. Therefore, the inventor tried to increase the PC polymerization degree by changing the reaction parameters, thereby increasing the hardness of the composite material. However, it was found that when the PC polymerization degree increased to a certain extent, the binding degree between the composite material and the PC layer would decrease significantly again. Therefore, the reaction parameters were adjusted again to obtain the reaction time and temperature of the present invention, and the hardness of the composite was increased as much as possible while preferentially ensuring the binding degree and light transmittance.

[0013] MMA-TC is methyl 2-methyl-2-oxo-1,3-oxathiolan-5-yl acrylate, and its structural formula can be specifically referred to the patent with the above application number 2020800341688.

[0014] Preferably, a small amount of a capping agent is added to the S200 when the reaction time is 2 - 4 h, and the capping agent includes phenolic compounds or carboxylic acid compounds.

[0015] By adding a small amount of the capping agent, the addition time, and the reaction conditions, the chain length distribution of the PC chains in the composite is regulated. The addition amount of the capping agent can ensure that a part of the chain segments in the system terminate the reaction, and a part of the chain segments can continue to grow. The regulation of the addition time of the capping agent and the reaction conditions can control the average polymerization degree of each group of short and long chain segments. Since the short chain segments are more easily dispersed in the PC layer structure, the binding degree between the composite material and the PC layer can be ensured. On the basis of the short chain segments, the long chain segments can further improve the binding degree between the composite material and the PC layer and also improve the hardness of the composite material. The phenolic compounds can be phenol and p-diphenol, etc., and the carboxylic acid compounds can be acetic acid and benzoic acid, etc.

[0016] Preferably, the dosage of the capping agent is 0.5 wt% - 1.5 wt% of MMA-TC.

[0017] Preferably, the cycloolefin includes norbornene or norbornene derivatives, the catalyst includes: metallocene catalysts or zirconium-based catalysts, the molar concentration of the cycloolefin in the mixed solution obtained by dissolving it in a solvent is 2 - 3 mol / L, and the molar ratio of the cycloolefin to ethylene is (5 - 7):(3 - 4).

[0018] The norbornene derivatives can be ethyl norbornene, butyl norbornene, dicyclopentadiene, etc.

[0019] Preferably, the solvent includes benzene or homologues of benzene.

[0020] The solvent needs to be applicable to both the S100 and S200 reaction systems simultaneously.

[0021] Preferably, in S200, after pressure relief, MMA-TC is first added to the first pre-product solution, and then triethanolamine and 1,1,1-trimethylolpropane are gradually added.

[0022] The applicant found in the experiment that after directly adding triethanolamine and 1,1,1-trimethylolpropane to the first pre-product solution, during the reaction process, especially in the initial stage of the reaction, polymer clusters would appear, and even precipitation would occur. Finally, the performance of the obtained composite material would deteriorate and be difficult to unify. At the same time, the compatibility between the composite material and the PC layer would also be affected. The applicant conjectured that the reason was that the appearance of precipitation affected the interpenetration and uniform interpenetration of the polycarbonate chain segments in the COC structure.

[0023] Preferably, by weight, 10-20 parts of triethanolamine and 20-35 parts of 1,1,1-trimethylolpropane are gradually added within the time period of 0h to (3-5)h, and then the remaining triethanolamine and 1,1,1-trimethylolpropane are added at one time.

[0024] In order to further improve the polymer cluster phenomenon in the initial stage of the reaction, the applicant improved the feeding process again, which can ensure the uniformity of the final product performance and its compatibility with the PC layer. The applicant conjectured that the reason was that during the process of gradually adding triethanolamine and 1,1,1-trimethylolpropane, the polarity of the polymer in the reaction system gradually increased and there was a hindrance of the carbonate chain segments, thereby improving the cluster phenomenon. Based on this, the applicant further considered whether, after the reaction system in S200 reached a certain level, the cluster phenomenon would no longer appear or almost no longer appear due to the reduction of the polarity difference of the substances in the system and the hindrance of the carbonate chain segments. After the experiment, it was found that even if the remaining raw materials were added at one time after 3-5h, it had almost no impact on the performance of the final product. Therefore, in order to shorten the process time, in this invention, stepwise feeding is adopted for the first-stage feeding and one-time feeding is adopted for the second-stage feeding. The experimental results show that the process time of the two-stage feeding can be shortened by about 17% compared with only adopting stepwise feeding.

[0025] A high-transparency composite material prepared by the processing technology described above.

[0026] An application of the high-transparency composite material described above in lens manufacturing.

[0027] Preferably, the application method includes:

[0028] A100. Melt the high-transparency composite material and benzotriazole in the first extruder, and melt the polycarbonate resin in the second extruder. Then merge the melts from the two extruders into a multi-layer co-extrusion die head. The outlet temperature of the first extruder is 120 - 180 °C, and the outlet temperature of the second extruder is 240 - 300 °C. Benzotriazole accounts for 1% - 1.5% of the high-transparency composite material.

[0029] A200. After curing and forming through a two-stage cooling and forming process, take out the lens. The temperature of the first-stage cooling is 5 - 10 °C, and the cooling time is 10 - 15 s. The temperature of the second-stage cooling is 15 - 30 °C, and the cooling time is 20 - 40 s.

[0030] The anti-aging performance of the high-transparency composite material provided by the present invention is not good. The applicant conjectures that it is caused by the use of MMA-TC. Therefore, benzotriazole is added to the first extruder in the present invention. The cooling process will affect the crystallization behavior of the polymer, stress release, and the final transparency of the lens. The first-stage rapid cooling can reduce the formation of crystal nuclei, inhibit crystallization, and improve the transparency of the product. The second-stage slow cooling can improve the bonding degree between the high-transparency composite material layer and the PC layer, and improve the dimensional stability difference between the two resin layers, especially for the dimensional stability difference when the structure layer is of a special shape.

[0031] The present invention has at least the following beneficial effects:

[0032] By interspersing polycarbonate chain segments in the cycloolefin polymer structure and controlling their proportions and reaction conditions, the present invention can improve the hardness of the composite material as much as possible while ensuring the bonding degree and light transmittance. The present invention reasonably regulates the chain segment length distribution to further improve the product hardness while ensuring the bonding degree between the composite material and the PC layer. After improving the feeding order of the polycarbonate raw material, the present invention improves the product performance, improves the performance uniformity of the product, and also shortens the process time. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following will briefly introduce the drawings required in the embodiments. It should be understood that the following drawings only show some embodiments of the present invention, so they should not be regarded as limiting the scope. For those of ordinary skill in the art, other related drawings can be obtained based on these drawings without creative efforts.

[0034] Figure 1 It is the transmittance curve in the ultraviolet-visible spectral region of the high-transparency composite material prepared according to the processing techniques of Examples 1 - 3;

[0035] Figure 2 It is the transmittance curve in the ultraviolet-visible spectral region of the high-transparency composite material prepared according to the processing techniques of Examples 4 - 6;

[0036] Figure 3 The transmittance curve in the ultraviolet-visible spectral region of the high-transparency composite material prepared by the processing technology of Examples 7-10;

[0037] Figure 4 The transmittance curve in the ultraviolet-visible spectral region of the high-transparency composite material prepared by the processing technology of Example 10 and Comparative Examples 1-2. Detailed implementation manners

[0038] To make the objectives, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described. Obviously, the described embodiments are some, but not all, of the embodiments of the present invention.

[0039] Example 1: A processing technology for a high-transparency composite material, comprising:

[0040] S100. After dissolving norbornene in toluene, introducing ethylene gas, and polymerizing under the action of a metallocene catalyst to obtain a first pre-product solution; the polymerization time is 40 min, the polymerization temperature is 50 °C, and the polymerization pressure is 2 Mpa; the molar concentration of the mixed solution obtained after the cycloolefin is dissolved in toluene is 2 mol / L;

[0041] S200. By weight, after depressurizing to atmospheric pressure, adding 30 parts of triethanolamine, 50 parts of 1,1,1-trimethylolpropane, and 300 parts of MMA-TC to the first pre-product solution, and reacting to obtain a second pre-product solution; the molar ratio of the cycloolefin to the MMA-TC is 30:7, the reaction time is 5 h, and the reaction temperature is 70 °C;

[0042] S300. Filter, wash, and dry the second pre-product solution to obtain a high-transparency composite material.

[0043] Example 2: A processing technology for a high-transparency composite material, comprising:

[0044] S100. After dissolving norbornene in toluene, introducing ethylene gas, and polymerizing under the action of a metallocene catalyst to obtain a first pre-product solution; the polymerization time is 100 min, the polymerization temperature is 70 °C, and the polymerization pressure is 4 Mpa; the molar concentration of the mixed solution obtained after the cycloolefin is dissolved in toluene is 3 mol / L;

[0045] S200. By weight, after depressurizing to atmospheric pressure, adding 40 parts of triethanolamine, 70 parts of 1,1,1-trimethylolpropane, and 500 parts of MMA-TC to the first pre-product solution, and reacting to obtain a second pre-product solution; the molar ratio of the cycloolefin to the MMA-TC is 50:10, the reaction time is 8 h, and the reaction temperature is 100 °C;

[0046] Filter, wash, and dry the second pre-product solution to obtain a high-transparency composite material.

[0047] Example 3: A processing process for a high-transparency composite material, including:

[0048] S100: Dissolve norbornene in toluene, then introduce ethylene gas, and polymerize under the action of a metallocene catalyst to obtain a first pre-product solution; the polymerization time is 80 min, the polymerization temperature is 60 °C, and the polymerization pressure is 3 Mpa; the molar concentration of the mixed solution obtained after dissolving the cycloolefin in toluene is 2.6 mol / L.

[0049] S200: By weight, after depressurizing to atmospheric pressure, add 34 parts of triethanolamine, 63 parts of 1,1,1-trimethylolpropane, and 412 parts of MMA-TC to the first pre-product solution, and react to obtain a second pre-product solution; the molar ratio of the cycloolefin to the MMA-TC is 42:8.4, the reaction time is 7.2 h, and the reaction temperature is 85 °C.

[0050] S300: Filter, wash, and dry the second pre-product solution to obtain a high-transparency composite material.

[0051] Example 4: A processing process for a high-transparency composite material, including:

[0052] S100: Dissolve norbornene in toluene, then introduce ethylene gas, and polymerize under the action of a metallocene catalyst to obtain a first pre-product solution; the polymerization time is 80 min, the polymerization temperature is 60 °C, and the polymerization pressure is 3 Mpa; the molar concentration of the mixed solution obtained after dissolving the cycloolefin in toluene is 2.6 mol / L.

[0053] S200: By weight, after depressurizing to atmospheric pressure, add 34 parts of triethanolamine, 63 parts of 1,1,1-trimethylolpropane, and 412 parts of MMA-TC to the first pre-product solution, and react to obtain a second pre-product solution; the molar ratio of the cycloolefin to the MMA-TC is 42:8.4, the reaction time is 7.2 h, and the reaction temperature is 85 °C; in S200, p-diphenol is added at a reaction time of 2 h, and the dosage of p-diphenol is 0.5 wt% of the MMA-TC.

[0054] S300: Filter, wash, and dry the second pre-product solution to obtain a high-transparency composite material.

[0055] Example 5: A processing process for a high-transparency composite material, including:

[0056] S100. Dissolve norbornene in toluene, then introduce ethylene gas, and polymerize under the action of a metallocene catalyst to obtain a first pre-product solution; the polymerization time is 80 min, the polymerization temperature is 60 °C, and the polymerization pressure is 3 Mpa; the molar concentration of the mixed solution obtained after the cycloolefin is dissolved in toluene is 2.6 mol / L.

[0057] S200. By weight, after depressurizing to atmospheric pressure, add 34 parts of triethanolamine, 63 parts of 1,1,1-trimethylolpropane, and 412 parts of MMA-TC to the first pre-product solution, and react to obtain a second pre-product solution; the molar ratio of the cycloolefin to the MMA-TC is 42:8.4, the reaction time is 7.2 h, and the reaction temperature is 85 °C; in S200, p-diphenol is added at a reaction time of 4 h, and the dosage of p-diphenol is 1.5 wt% of the MMA-TC.

[0058] S300. Filter, wash, and dry the second pre-product solution to obtain a high-transparency composite material.

[0059] Example 6: A processing technology for a high-transparency composite material, including:

[0060] S100. Dissolve norbornene in toluene, then introduce ethylene gas, and polymerize under the action of a metallocene catalyst to obtain a first pre-product solution; the polymerization time is 80 min, the polymerization temperature is 60 °C, and the polymerization pressure is 3 Mpa; the molar concentration of the mixed solution obtained after the cycloolefin is dissolved in toluene is 2.6 mol / L.

[0061] S200. By weight, after depressurizing to atmospheric pressure, add 34 parts of triethanolamine, 63 parts of 1,1,1-trimethylolpropane, and 412 parts of MMA-TC to the first pre-product solution, and react to obtain a second pre-product solution; the molar ratio of the cycloolefin to the MMA-TC is 42:8.4, the reaction time is 7.2 h, and the reaction temperature is 85 °C; in S200, p-diphenol is added at a reaction time of 3 h, and the dosage of p-diphenol is 1 wt% of the MMA-TC.

[0062] S300. Filter, wash, and dry the second pre-product solution to obtain a high-transparency composite material.

[0063] Example 7: A processing technology for a high-transparency composite material, including:

[0064] S100. Dissolve norbornene in toluene, then introduce ethylene gas, and polymerize under the action of a metallocene catalyst to obtain a first pre-product solution; the polymerization time is 80 min, the polymerization temperature is 60 °C, and the polymerization pressure is 3 Mpa; the molar concentration of the mixed solution obtained after the cycloolefin is dissolved in toluene is 2.6 mol / L.

[0065] S200. After depressurizing to atmospheric pressure, add 34 parts of triethanolamine, 63 parts of 1,1,1-trimethylolpropane, and 412 parts of MMA-TC to the first pre-product solution, and react to obtain the second pre-product solution; the molar ratio of the cycloolefin to the MMA-TC is 42:8.4, the reaction time is 7.2 h, and the reaction temperature is 85 °C; in S200, p-diphenol is added at a reaction time of 3 h, and the dosage of p-diphenol is 1 wt% of the MMA-TC. After depressurization, first add MMA-TC to the first pre-product solution, and then gradually add triethanolamine and 1,1,1-trimethylolpropane within the time period of 0 - 7.2 h, adding once every 30 min, and the addition amount each time is the same.

[0066] S300. Filter, wash, and dry the second pre-product solution to obtain a high-transparency composite material.

[0067] Example 8: A processing process for a high-transparency composite material, comprising:

[0068] S100. Dissolve norbornene in toluene, introduce ethylene gas, and polymerize under the action of a metallocene catalyst to obtain a first pre-product solution; the polymerization time is 80 min, the polymerization temperature is 60 °C, and the polymerization pressure is 3 Mpa; the molar concentration of the mixed solution obtained after the cycloolefin is dissolved in toluene is 2.6 mol / L.

[0069] S200. After depressurizing to atmospheric pressure, first add 412 parts of MMA-TC to the first pre-product solution, and then, by weight, gradually add 10 parts of triethanolamine and 20 parts of 1,1,1-trimethylolpropane to the first pre-product solution within the time period of 0 h to 3 h, adding once every 30 min, and the addition amount each time is the same, and then add 24 parts of triethanolamine and 43 parts of 1,1,1-trimethylolpropane at one time, and react to obtain the second pre-product solution; the molar ratio of the cycloolefin to the MMA-TC is 42:8.4, the reaction time is 6 h, and the reaction temperature is 85 °C; in S200, p-diphenol is added at a reaction time of 3 h, and the dosage of p-diphenol is 1 wt% of the MMA-TC.

[0070] S300. Filter, wash, and dry the second pre-product solution to obtain a high-transparency composite material.

[0071] Example 9: A processing process for a high-transparency composite material, comprising:

[0072] S100. Dissolve norbornene in toluene, introduce ethylene gas, and polymerize under the action of a metallocene catalyst to obtain a first pre-product solution; the polymerization time is 80 min, the polymerization temperature is 60 °C, and the polymerization pressure is 3 Mpa; the molar concentration of the mixed solution obtained after the cycloolefin is dissolved in toluene is 2.6 mol / L.

[0073] S200. After depressurizing to atmospheric pressure, 412 parts of MMA-TC are first added to the first pre-product solution by weight. Then, within the time period of 0 h - 5 h, 20 parts of triethanolamine and 35 parts of 1,1,1-trimethylolpropane are gradually added to the first pre-product solution by weight, with each addition every 30 min and the same addition amount each time. Then, 14 parts of triethanolamine and 28 parts of 1,1,1-trimethylolpropane are added in one go. After the reaction, a second pre-product solution is obtained. The molar ratio of the cycloolefin to the MMA-TC is 42:8.4, the reaction time is 6 h, and the reaction temperature is 85°C. At the reaction time of 3 h, p-diphenol is added to S200, and the dosage of p-diphenol is 1 wt% of the MMA-TC.

[0074] S300. The second pre-product solution is filtered, washed, and dried to obtain a high-transparency composite material.

[0075] Example 10: A processing technology for a high-transparency composite material, including:

[0076] S100. After dissolving norbornene in toluene, ethylene gas is introduced, and polymerization is carried out under the action of a metallocene catalyst to obtain a first pre-product solution. The polymerization time is 80 min, the polymerization temperature is 60°C, and the polymerization pressure is 3 Mpa. The molar concentration of the mixed solution obtained after dissolving the cycloolefin in toluene is 2.6 mol / L.

[0077] S200. After depressurizing to atmospheric pressure, 412 parts of MMA-TC are first added to the first pre-product solution by weight. Then, within the time period of 0 h - 4 h, 18 parts of triethanolamine and 30 parts of 1,1,1-trimethylolpropane are gradually added to the first pre-product solution by weight, with each addition every 30 min and the same addition amount each time. Then, 16 parts of triethanolamine and 33 parts of 1,1,1-trimethylolpropane are added in one go. After the reaction, a second pre-product solution is obtained. The molar ratio of the cycloolefin to the MMA-TC is 42:8.4, the reaction time is 6 h, and the reaction temperature is 85°C. At the reaction time of 3 h, p-diphenol is added to S200, and the dosage of p-diphenol is 1 wt% of the MMA-TC.

[0078] S300. The second pre-product solution is filtered, washed, and dried to obtain a high-transparency composite material.

[0079] Comparative Example 1: The difference from Example 10 is that the dosage of p-diphenol is 2 wt% of the MMA-TC.

[0080] Comparative Example 2: The difference from Example 10 is that the total reaction time is 10 h.

[0081] Experiment: The high-transparency composite materials prepared by the processing techniques of Examples 1-10 and Comparative Examples 1-2 were injection-molded to obtain test samples with a specification of 6 mm 10 mm 4 mm.

[0082] Experiment 1: Transmittance test

[0083] The transmittance of the high-transparency composite materials prepared by the processing techniques of Examples 1-10 and Comparative Examples 1-2 in the ultraviolet-visible spectral region was tested by a transmittance tester. The test results are shown in Figures 1 - 4 .

[0084] From Figures 1 - 3 the data, it can be seen that the high-transparency composite materials prepared by the processing technique provided by the present invention have good transmittance.

[0085] From Figure 1 the comparison between the data of Example 3 and the data in Figure 2 , it can be seen that after adding a small amount of capping agent, the transmittance of the composite material can be improved to a certain extent.

[0086] From Figure 2 the comparison between the data of Example 6 and the data in Figure 3 , it can be seen that adding raw materials in batches and gradually in S200 can improve the transmittance of the composite material to a certain extent.

[0087] From Figure 3 the comparison between the data of Example 7 and the data of Examples 8-10, it can be seen that the transmittance of the products prepared by gradually adding triethanolamine and 1,1,1-trimethylolpropane in batches and all at once is not much different from that of the products prepared by gradually adding them throughout the process, and the transmittance of the high-transparency composite material prepared in Example 10 is the lowest, but the overall process time is shortened by about 17%.

[0088] From Figure 4 the comparison between the data of Comparative Examples 1-2 and the data of Example 10, it can be seen that the addition amount of the capping agent and the reaction time in S200 both affect the transmittance of the composite material.

[0089] Experiment 2: Hardness test

[0090] The hardness of the high-transparency composite materials prepared by the processing techniques of Examples 1-10 and Comparative Examples 1-2 under the static load method was tested using a Shore D durometer. The average value was taken after 5 tests for each group. The test results are shown in Table 1.

[0091] Table 1

[0092] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Hardness (HD) 51.27 53.49 56.81 57.78 58.19 58.32 Example 7 Example 8 Example 9 Example 10 Comparative Example 1 Comparative Example 2 Hardness (HD) 67.11 66.29 66.14 67.27 64.46 67.04

[0093] From the test results of Examples 1 - 10, it can be seen that the high-transparency composite material prepared by the processing technology provided by the present invention has good hardness properties.

[0094] From the comparative examples of Examples 4 - 6 and Example 3, it can be seen that after adding the capping agent, the hardness of the high-transparency composite material increases slightly. Although the addition of the capping agent provided by the present invention increases the number of short chains with low degree of polymerization in the material, theoretically the hardness should decrease to a certain extent, but the test result shows a slight increase. The applicant guesses that the possible reason is the improved interpenetration of PC chains in the COC structure.

[0095] From the comparison of the test results of Example 6 and Example 7, it can be seen that gradually adding triethanolamine and 1,1,1-trimethylolpropane to the first prepolymer solution can significantly improve the hardness of the high-transparency composite material.

[0096] From the comparison of the test results of Examples 7 - 10, it can be seen that there is little difference in the light transmittance of the products prepared by gradually adding triethanolamine and 1,1,1-trimethylolpropane step by step and adding them all at once throughout the process, and the hardness of the high-transparency composite material prepared in Example 10 is the highest, and the overall process time is also shortened by about 17%.

[0097] From the comparison of the test results of Comparative Examples 1 - 2 and Example 10, it can be seen that too high an addition amount of the capping agent will affect the hardness of the high-transparency composite material; after increasing the reaction time of S200, the hardness of the high-transparency composite material will increase to a certain extent, but the light transmittance will decrease relatively.

[0098] Example 11: Application of the high-transparency composite material in lens manufacturing, and the application method includes:

[0099] A100. Melting the high-transparency composite material and benzotriazole in the first extruder, melting the polycarbonate resin in the second extruder, and merging the melts in the two extruders into a multi-layer co-extrusion die head; the outlet temperature of the first extruder is 120 °C, and the outlet temperature of the second extruder is 240 °C; benzotriazole accounts for 1% of the high-transparency composite material;

[0100] A200. After curing and forming through a two-stage cooling and forming process, take out the lens; the temperature of the first-stage cooling is 5 °C, and the cooling time is 10 s; the temperature of the second-stage cooling is 15 °C, and the cooling time is 20 s.

[0101] Example 12: Application of the high-transparency composite material in lens manufacturing, and the application method includes:

[0102] A100. Melt the high-transparency composite material and benzotriazole in the first extruder, and melt the polycarbonate resin in the second extruder. Merge the melts from the two extruders into a multi-layer co-extrusion die head. The outlet temperature of the first extruder is 180 °C, and the outlet temperature of the second extruder is 300 °C. Benzotriazole accounts for 1.5% of the high-transparency composite material.

[0103] A200. After curing and forming through a two-stage cooling and forming process, take out the lens. The temperature of the first-stage cooling is 10 °C, and the cooling time is 15 s. The temperature of the second-stage cooling is 30 °C, and the cooling time is 40 s.

[0104] Example 13: Application of the high-transparency composite material in lens manufacturing. The application method includes:

[0105] A100. Melt the high-transparency composite material and benzotriazole in the first extruder, and melt the polycarbonate resin in the second extruder. Merge the melts from the two extruders into a multi-layer co-extrusion die head. The outlet temperature of the first extruder is 150 °C, and the outlet temperature of the second extruder is 260 °C. Benzotriazole accounts for 1.2% of the high-transparency composite material.

[0106] A200. After curing and forming through a two-stage cooling and forming process, take out the lens. The temperature of the first-stage cooling is 8 °C, and the cooling time is 12 s. The temperature of the second-stage cooling is 20 °C, and the cooling time is 30 s.

[0107] Comparative Example 3: The difference from Example 13 is that the cooling process is single-stage cooling, the cooling temperature is 8 °C, and the cooling time is 42 s.

[0108] Test Three: Mechanical Property Test

[0109] The polycarbonate resin is purchased from Teijin, Japan, SP-3810 optical grade.

[0110] After making the high-transparency composite materials prepared by the processing processes of Examples 1 - 10 and Comparative Examples 1 - 2 into lenses (the thickness of the composite material layer is 0.6 mm, and the thickness of the polycarbonate resin layer is 0.6 mm) through the application method of Example 13, test the tensile strength (ISO 527) and notched impact strength (ASTM D256, the specimen length is 64 mm, and the width is 12.7 mm) of the lenses. After testing 5 times for each group, take the average value. The test results are shown in Table 2. The unit of tensile strength is MPa, and the unit of impact strength is kJ / m.

[0111] Table 2

[0112] Example 1 Example 2 Example 3 Example 4 Example 5 Tensile Strength 38.74 39.14 39.42 44.34 45.10 Impact Strength 0.94 0.94 0.95 1.16 1.20 Example 6 Example 7 Example 8 Example 9 Example 10 Tensile Strength 45.18 48.18 46.95 47.37 48.16 Impact Strength 1.25 1.37 1.34 1.35 1.37 Comparative Example 1 Comparative Example 2 Comparative Example 3 Tensile Strength 41.27 45.76 40.58 Impact Strength 1.05 0.93 1.08

[0113] From the test results of Examples 1-10, it can be seen that the high-transparency composite material prepared by the processing technology provided by the present invention has good mechanical properties after being combined with the polycarbonate resin matrix, and thus the compatibility between the two is good.

[0114] From the comparison of the results of Examples 4-6 with those of Example 3, it can be seen that after using the capping agent, the compatibility between the high-transparency composite material and the polycarbonate resin is further improved.

[0115] From the comparison of the results of Example 7 with those of Example 6, it can be seen that the feeding process of triethanolamine and 1,1,1-trimethylolpropane affects the compatibility between the high-transparency composite material and the polycarbonate resin.

[0116] From the comparison of the results of Examples 8-10 with those of Example 7, it can be seen that after the present invention adopts step-by-step feeding in the first-stage feeding and one-time feeding in the second-stage feeding, the compatibility between the high-transparency composite material and the polycarbonate resin is hardly affected, but the process time can be shortened by about 17%.

[0117] From the comparison of the results of Comparative Examples 1-3 with those of Example 10, it can be seen that the addition amount of the capping agent, the reaction time of S200, and the cooling process in the application method all affect the product performance to a certain extent.

[0118] In summary, although the composite material prepared by the processing technology provided in Example 10 has a slightly lower light transmittance than the composite materials prepared by the processing technologies provided in Examples 7-9, the compatibility with the polycarbonate resin is significantly improved.

[0119] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention can have various changes and modifications. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A processing technology for a highly transparent composite material, characterized in that, Including: S100. Dissolve the cycloolefin in a solvent, introduce ethylene gas, and polymerize under the action of a catalyst to obtain a first pre-product solution; the polymerization time is 40 - 100 min, the polymerization temperature is 50 - 70 °C, and the polymerization pressure is 2 - 4 Mpa; S200. By weight, after depressurization, add 30 - 40 parts of triethanolamine, 50 - 70 parts of 1,1,1 - trimethylolpropane, and 300 - 500 parts of MMA-TC to the first pre-product solution, and react to obtain a second pre-product solution; the molar ratio of the cycloolefin to the MMA-TC is (30 - 50):(7 - 10), the reaction time is 5 - 8 h, and the reaction temperature is 70 - 100 °C; S300. Filter, wash, and dry the second pre-product solution to obtain a high-transparency composite material.

2. The processing technology according to claim 1, characterized in that, In S200, a small amount of a capping agent is added when the reaction time is 2 - 4 h, and the capping agent includes a phenol compound or a carboxylic acid compound.

3. The processing technology according to claim 2, characterized in that, The dosage of the capping agent is 0.5 wt% - 1.5 wt% of the MMA-TC.

4. The processing technology according to claim 1, characterized in that, The cycloolefin includes norbornene or a norbornene derivative, the catalyst includes a metallocene catalyst or a zirconium-based catalyst, the molar concentration of the mixture obtained after the cycloolefin is dissolved in the solvent is 2 - 3 mol / L, and the molar ratio of the cycloolefin to ethylene is (5 - 7):(3 - 4).

5. The processing technology according to claim 1, characterized in that The solvent includes benzene or a homolog of benzene.

6. The processing technology according to any one of claims 1-5, characterized in that, S200 includes: after depressurization, first add MMA-TC to the first pre-product solution, and then gradually add triethanolamine and 1,1,1 - trimethylolpropane.

7. The processing technology according to claim 6, characterized in that, By weight, gradually add 10 - 20 parts of triethanolamine and 20 - 35 parts of 1,1,1 - trimethylolpropane within the time period of 0 h to (3 - 5) h, and then add the remaining triethanolamine and 1,1,1 - trimethylolpropane at one time.

8. A high-transparency composite material prepared by the processing technology according to any one of claims 1 - 7.

9. An application of the high-transparency composite material according to claim 8 in lens manufacturing.

10. The application according to claim 9, wherein The application method includes: A100. Melt the high-transparency composite material and benzotriazole in a first extruder, melt the polycarbonate resin in a second extruder, and merge the melts in the two extruders into a multi-layer co-extrusion die head; the outlet temperature of the first extruder is 120 - 180 °C, and the outlet temperature of the second extruder is 240 - 300 °C; benzotriazole accounts for 1% - 1.5% of the high-transparency composite material; A200. After curing and forming through a two-stage cooling forming process, take out the lens; the temperature of the first-stage cooling is 5 - 10 °C, and the cooling time is 10 - 15 s; the temperature of the second-stage cooling is 15 - 30 °C, and the cooling time is 20 - 40 s.

Images