Synthetic method and application of modified hydrogenated bisphenol A type epoxy acrylate high-weather-resistance resin

Abstract

The invention belongs to the technical field of resin, and particularly relates to a synthetic method and application of modified hydrogenated bisphenol A type epoxy acrylate high-weather-resistance resin. Hydrogenated bisphenol A epoxy resin, acrylic acid, p-hydroxyanisole, 2, 6-butylated hydroxytoluene and triethylamine are put into a reaction kettle, stirring is started, the temperature is slowly increased, timing is started when the temperature reaches, reaction heat release, temperature control reaction and sampling are carried out to test the acid value, after the acid value is qualified, cooling is carried out, a reagent is added, uniform stirring is carried out, cooling, discharging, filtering and packaging are carried out, and the synthetic resin is obtained. The synthetic resin can be applied to a product, and the preparation method of the product comprises the following steps: mixing the synthetic resin, an initiator, glass fiber cloth, a flatting agent and a light stabilizer to obtain a mixture, and performing hot-pressing curing to obtain the product. According to the invention, the technical problem that the epoxy resin is easy to yellow and age in outdoor application is fundamentally solved.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of resins, and particularly relates to a synthesis method and application of modified hydrogenated bisphenol A type epoxy acrylate high weather-resistant resin. BACKGROUND

[0002] The epoxy resin has excellent mechanical properties, forms a dense crosslinking network after curing, has good adhesion to various substrates, high volume resistivity, good chemical resistance and dimensional stability, and strong controllability, but due to the presence of aromatic structure, it is easy to absorb ultraviolet light, thereby causing the main chain or side chain to break, resulting in yellowing, powdering and loss of mechanical strength of the material. When an amine curing agent is used to polymerize with the epoxy resin, the free amine component can cause local temperature rise, thereby accelerating the yellowing of the resin. In addition, the amine curing agent is easy to oxidize under high temperature conditions to form a quinone structure, which is one of the main reasons for the yellowing of the resin. Therefore, the present application selects hydrogenated bisphenol A type epoxy resin as the main body, and modifies it with acrylic acid, so that it has double bond curing performance and excellent weather resistance, to solve the problem of weather resistance. SUMMARY

[0003] The present application provides a synthesis method and application of modified hydrogenated bisphenol A type epoxy acrylate high weather-resistant resin to overcome the shortcomings of the prior art.

[0004] The technical scheme of the present application is as follows: One of the technical schemes is a synthesis method of modified hydrogenated bisphenol A type epoxy acrylate high weather-resistant resin, comprising the following steps: Put hydrogenated bisphenol A type epoxy resin, acrylic acid, p-hydroxyanisole, 2,6-di-tert-butyl-p-cresol and triethylamine into a reaction kettle, start stirring, slowly heat, when the temperature reaches, start timing, the reaction is exothermic, control temperature reaction, take sample test acid value, after the acid value is qualified, cool down, add reagent, stir uniformly, cool down, discharge, filter, package, and obtain the synthesized resin.

[0005] Further, the slow heating, when the temperature reaches, the start timing comprises the following steps: Slowly heat to 65-75 DEG C, when the temperature reaches 75-85 DEG C, start timing.

[0006] Further, the temperature control reaction comprises the following steps: React for 1-2 hours at a temperature range of 80-90 DEG C, react for 1-2 hours at a temperature range of 90-100 DEG C, the reaction is exothermic itself, react for 0.5-1 hour at a temperature range of 100-105 DEG C, reach 105 DEG C and keep warm for 1-2 hours, gradually heat to a temperature range of 105-115 DEG C and react for 1-2 hours, when the temperature reaches 115 DEG C, keep warm for 1-2 hours, and take sample test acid value.

[0007] Further, the sampling test acid value includes the following steps: When the acid value is less than 2mg KOH / g, the reaction is ended, but when the acid value is close to 3mg KOH / g, the sampling is monitored every 15min, and nitrogen is needed to be introduced during the sampling process.

[0008] Further, the cooling and adding reagent includes the following steps: Cooling to below 100℃, and then adding trimethylolpropane triacrylate.

[0009] Further, the cooling and adding reagent includes the following steps: Cooling to below 100℃, and then adding trimethylolpropane triacrylate.

[0010] It should be noted that, in the process of stirring uniformly after adding the POSS solution, there is still a small amount of triethylamine in the system. The basic characteristics of triethylamine slightly activate the silicon hydroxyl group on the surface of the POSS siloxane cage, and improve the compatibility of the POSS organic shell layer and the polymer matrix through hydrogen bonding and other interactions. Although it is not a strong chemical reaction, this microenvironment helps the POSS to be dispersed in the resin in a more uniform and stable state, and is more conducive to the formation of a composite structure during subsequent curing.

[0011] Further, the preparation method of the POSS solution includes the following steps: A three-necked flask provided with a mechanical stirrer and a nitrogen protection port is used to add acrylic functionalized POSS powder and trimethylolpropane triacrylate; the mixture is stirred and pre-mixed to obtain a mixed liquid, and then the mixed liquid is ultrasonically treated; a surfactant is added and stirred; and finally, the POSS solution is obtained by filtration.

[0012] Further, the acrylic functionalized POSS powder includes MA-POSS.

[0013] Further, according to the weight parts, the hydrogenated bisphenol A type epoxy resin is 50-60 parts, the acrylic acid is 20-25 parts, the p-hydroxyanisole is 0.1-2 parts, the 2,6-di-tert-butyl-p-cresol is 0.1-1 part, the triethylamine is 2-5 parts, and the trimethylolpropane triacrylate is 20-50 parts.

[0014] Technical solution two: a product, the preparation method of the product includes the following steps: The synthetic resin, the initiator, the glass fiber cloth, the leveling agent and the light stabilizer are mixed to obtain a mixture, and the mixture is hot-pressed and cured to obtain the product, wherein the synthetic resin is prepared according to the synthesis method of the modified hydrogenated bisphenol A type epoxy acrylate high-weather-resistant resin.

[0015] Compared with the prior art, the present application has the following advantages: The present application provides a modified epoxy acrylate resin which can be used in outdoor applications, has excellent weather resistance, adopts a double bond curing method, solves the yellowing problem of the resin, and has the excellent performance of both epoxy resin and acrylic resin, and can be applied to photovoltaic tiles and other scenarios.

[0016] The present application selects hydrogenated bisphenol A type epoxy resin as the main material for modification and synthesis, selects acrylic acid to give the resin carbon-carbon double bond functional group, changes the curing method, and adds a multi-functional active diluent to improve the crosslinking density of the resin and enhance the mechanical properties.

[0017] More specifically, the present application fundamentally solves the technical problems of yellowing and aging of epoxy-based resins in outdoor applications. By using hydrogenated bisphenol A type epoxy resin as the main skeleton, the benzene ring in the molecule is saturated into a stable alicyclic structure, reducing the absorption rate of the material to ultraviolet light and inhibiting the yellowing phenomenon caused by photo-oxidation. Further, by introducing acrylic functionalized POSS, an organic-inorganic hybrid synergistic protection network is constructed. The rigid inorganic cage structure of POSS not only effectively scatters and blocks ultraviolet light, but also acts as an energy quencher to consume light energy, thereby achieving multiple protection of the resin matrix. DETAILED DESCRIPTION

[0018] In order to make the purpose, technical scheme and advantages of the present application clearer, the present application will be further described in detail below with examples. It should be understood that the specific examples described herein are only used to explain the present application and do not limit the present application. Unless otherwise specified, the experimental methods used below are conventional methods, and the materials, reagents, etc. used are commercially available unless otherwise specified.

[0019] Special notes: Hydrogenated bisphenol A type epoxy resin: epoxy equivalent weight 200-230 g / eq, hydrogenation degree > 99.5%, viscosity (25℃): 5000-15000 mPa·s.

[0020] Method 1 A method for synthesizing a modified hydrogenated bisphenol A type epoxy acrylate high-weather-resistant resin, comprising the following steps: Prepare the raw materials by weight parts: Hydrogenated bisphenol A type epoxy resin 50-60 parts Acrylic acid 20-25 parts p-Hydroxyanisole 0.1-2 parts 0.1-1 part of 2,6-di-tert-butyl-p-cresol 2-5 parts of triethylamine 20-50 parts of trimethylolpropane triacrylate The preparation process using raw materials is as follows: Hydrogenated bisphenol A epoxy resin, acrylic acid, p-hydroxyanisole, 2,6-di-tert-butyl-p-cresol, and triethylamine were sequentially placed into a reaction vessel. Stirring was started, and the temperature was slowly increased to 75°C. When the temperature reached 80°C, timing was started. The reaction was exothermic, so temperature control was important. The reaction was carried out for 1 hour in the 80-90°C range, and then for 1 hour in the 90-100°C range. The reaction was self-exothermic, and the reaction was carried out for 0.5 hours in the 100-105°C range. The temperature was then maintained at 105°C for 1 hour. The temperature was then gradually increased to the 105-115°C range for 1 hour. When the temperature reached 115°C, the temperature was maintained for 2 hours. Samples were taken to test the acid value. The reaction ended when the acid value was less than 2 mg KOH / g. However, when the acid value was close to 3 mg KOH / g, samples were taken every 15 minutes for monitoring. Nitrogen gas was required for protection during the sampling process. After the acid value is qualified, the temperature is lowered to below 100℃, trimethylolpropane triacrylate is added, stirred evenly, cooled, discharged, filtered, and packaged to obtain the synthetic resin.

[0021] Referring to the above method, Examples 1-3 were implemented. The specific weight parts of Examples 1-3 are shown in Table 1.

[0022] Table 1

[0023] Comparative Example 1 According to the weight proportions, 55 parts of unhydrogenated bisphenol A type epoxy resin, 25 parts of acrylic acid, 0.5 parts of p-hydroxyanisole, 0.5 parts of 2,6-di-tert-butyl-p-cresol, and 3 parts of triethylamine are placed into a reaction vessel. Stirring is started, and the temperature is slowly increased to 75°C. When the temperature reaches 80°C, timing begins. The reaction is exothermic, so temperature control is important. The reaction is carried out for 1 hour in the temperature range of 80-90°C, and then for 1 hour in the temperature range of 90-100°C. The reaction is self-exothermic, so the reaction is carried out for 0.5 hours in the temperature range of 100-105°C. When the temperature reaches 105°C, it is held for 1 hour. The temperature is then gradually increased to the temperature range of 105-115°C and reacted for 1 hour. When the temperature reaches 115°C, it is held for 2 hours. Samples are taken to test the acid value. The reaction ends when the acid value is less than 2 mg KOH / g, but when the acid value is close to 3 mg KOH / g, samples are taken every 15 minutes for monitoring. Nitrogen gas protection is required during the sampling process. After the acid value is qualified, the temperature is lowered to below 100℃, trimethylolpropane triacrylate is added, stirred evenly, cooled, discharged, filtered, and packaged to obtain the synthetic resin.

[0024] Detection: Product preparation: By weight, 94 parts of synthetic resin, 1 part of initiator BPO, 2 parts of glass fiber cloth, 1 part of leveling agent (BYK-306), 1 part of leveling agent (BYK-331), and 0.8 parts of light stabilizer (Chimassorb® 944) are mixed to obtain a mixture.

[0025] The synthetic resin used is the synthetic resin prepared in Examples 1-3 or Comparative Example 1.

[0026] The mixture is hot-pressed and cured with the following parameters: pressure 0.3-0.8 MPa, temperature 90-110℃, and time 10 minutes to obtain the product.

[0027] The basic performance and weather resistance of the product were tested, and the results are shown in Tables 2 and 3.

[0028] Detection method: 1. Thickness: GB / T 6672-2001 2. Light transmittance: GB / T 2410-2008 3. Tensile strength: GB / T 1040.2-2006 4. Elastic modulus: GB / T 1040.2-2006 5. Elongation at break: GB / T 1040.2-2006 6. Volume shrinkage rate: GB / T 13477.19-2017 7. Yellowing resistance: The test was conducted using a QUV accelerated aging tester. The total aging time of the samples in the QUV equipment was 1000 hours, and the change in yellowing index (ΔYI) was recorded 500 hours after the end of aging.

[0029] 8. Optical stability: The QUV accelerated aging tester was used for testing. The total aging time of the sample in the QUV equipment was 1000h, and the transmittance at the end of aging was recorded.

[0030] 9. Mechanical retention rate: GB / T 1040.2-2006 10. Moisture absorption rate: GB / T 1034-2008 11. Apparent Changes: GB / T 1865-2009 Table 2

[0031] Table 3

[0032] Compared with Comparative Example 1, the basic performance and weather resistance of Examples 1-3 have been improved, but the yellowing resistance ΔYI is still around 2.0, and there is still a risk of further yellowing under long-term light exposure.

[0033] Therefore, further exploration and improvement are needed, and the following method 2 is proposed.

[0034] Method 2 A method for synthesizing a modified hydrogenated bisphenol A type epoxy acrylate high weather-resistant resin, comprising the following steps: Prepare the ingredients by weight: 50-60 parts of hydrogenated bisphenol A type epoxy resin 20-25 parts acrylic acid 0.1-2 parts of p-hydroxyanisole 0.1-1 part of 2,6-di-tert-butyl-p-cresol 2-5 parts of triethylamine 20-50 parts of trimethylolpropane triacrylate 1-3 parts of POSS solution Preparation method of POSS solution: Take a three-necked flask equipped with a mechanical stirrer and a nitrogen protection port, add 2 parts by weight of acrylic acid functionalized POSS powder (methacryloyloxypropyl cage silsesquioxane, MA-POSS) and 8 parts by weight of trimethylolpropane triacrylate (TMPTA); stir and premix at room temperature to obtain a mixture, and then sonicate the mixture at room temperature for 25 minutes; add 0.2 parts by weight of surfactant (BYK-348) and stir for 10 minutes; finally filter to obtain POSS solution.

[0035] The preparation process using raw materials is as follows: Hydrogenated bisphenol A epoxy resin, acrylic acid, p-hydroxyanisole, 2,6-di-tert-butyl-p-cresol, and triethylamine were sequentially placed into a reaction vessel. Stirring was started, and the temperature was slowly increased to 75°C. When the temperature reached 80°C, timing was started. The reaction was exothermic, so temperature control was important. The reaction was carried out for 1 hour in the 80-90°C range, and then for 1 hour in the 90-100°C range. The reaction was self-exothermic, and the reaction was carried out for 0.5 hours in the 100-105°C range. The temperature was then maintained at 105°C for 1 hour. The temperature was then gradually increased to the 105-115°C range for 1 hour. When the temperature reached 115°C, the temperature was maintained for 2 hours. Samples were taken to test the acid value. The reaction ended when the acid value was less than 2 mg KOH / g. However, when the acid value was close to 3 mg KOH / g, samples were taken every 15 minutes for monitoring. Nitrogen gas was required for protection during the sampling process. After the acid value is qualified, the temperature is lowered to below 100℃. First, POSS solution is added and stirred evenly for more than 30 minutes. Then, trimethylolpropane triacrylate is added and stirred evenly. After cooling, the material is discharged, filtered, and packaged to obtain the synthetic resin.

[0036] Referring to the above method, Examples 4-6 are given, and the specific weight parts of Examples 4-6 are shown in Table 4.

[0037] Table 4

[0038] The test was conducted according to the test method in Method 1, and the test results are shown in Tables 5 and 6.

[0039] Table 5

[0040] Table 6

[0041] analyze: Comparing the data from Examples 1-3 with Comparative Example 1 in Tables 2 and 3, we find that: Basic mechanical properties: The tensile strength, elastic modulus, and elongation at break of Examples 1-3 are all superior to those of Comparative Example 1. This indicates that the acrylate molecular chains generated by the reaction of hydrogenated bisphenol A type epoxy resin have higher rigidity and strength.

[0042] Volume shrinkage: The volume shrinkage rates of Examples 1-3 were significantly lower than those of Comparative Example 1. Volume shrinkage is a critical issue in the curing process, leading to internal stress and product deformation. The lower shrinkage rates of Examples 1-3 indicate better dimensional stability of their products.

[0043] Optical stability: After 1000 hours of QUV aging, the light transmittance retention of Examples 1-3 was higher than that of Comparative Example 1, indicating that the materials of Examples 1-3 have stronger resistance to photodegradation.

[0044] Mechanical retention rate: The mechanical retention rates of Examples 1-3 are also slightly higher than those of Comparative Example 1.

[0045] Yellowing resistance: Examples 1-3 showed improvement compared to Comparative Example 1.

[0046] Mechanism: In the ordinary bisphenol A structure, the isopropyl linker (connecting the carbon atoms of the two benzene rings) has a hydrogen atom on the adjacent carbon atom. The CH bond energy on it is low and it is easily oxidized under ultraviolet light to form a chromophore (such as a quinone structure). This is the fundamental reason for the yellowing of the material.

[0047] Hydrogenated bisphenol A type epoxy resin: The hydrogenation process saturates the benzene ring into an alicyclic structure. The alicyclic structure has higher bond energy and chemical stability, and its absorption window for ultraviolet light shifts to a shorter wavelength, thereby reducing the photo-oxidation reaction rate of the material under natural light.

[0048] After the hydrogenated bisphenol A type epoxy resin reacts with the other components, the molecular backbone consists of a stable hydrogenated bisphenol A backbone and an acrylate double bond cross-linked network. This structure forms a denser and more stable network at the microscopic level, thus exhibiting higher modulus, strength, and lower water absorption (wet heat water absorption rate in Table 3).

[0049] Method 1 improves the light stability of the material by altering the chemical structure of the molecular chain.

[0050] Method 2 introduces a variable based on Method 1: the POSS solution.

[0051] Comparing Tables 5 and 6 with Tables 2 and 3, we find that the addition of POSS brings a second performance improvement: Yellowing resistance: ΔYI in Examples 4-6 was significantly reduced, and the effect improved with increasing POSS dosage. This indicates that POSS effectively inhibits the photo-oxidative yellowing process of the material.

[0052] Optical stability and mechanical retention: The optical stability and mechanical retention of Examples 4-6 were further improved. This demonstrates that POSS not only protects the material's color but also its structural and mechanical integrity.

[0053] Mechanical properties and dimensional stability: The elastic modulus of Examples 4-6 was further improved, and the volume shrinkage rate was further reduced. This indicates that the addition of POSS enhanced and constrained the cross-linked network of the material.

[0054] Hydrophobicity: The hygrothermal water absorption rate of Examples 4-6 was further reduced, indicating that POSS improved the material's ability to block water vapor.

[0055] Mechanism: Based on the highly stable molecular framework of Method 1, cage-like silsesquioxanes were introduced to construct an organic-inorganic hybrid synergistic enhancement network at the microscopic level.

[0056] POSS possesses a well-defined cage-like siloxane inorganic framework (Si-O-Si). When MA-POSS participates in and is cured into the crosslinked network of epoxy acrylate through acrylic functional groups, these rigid inorganic "nanocages" are uniformly dispersed within the organic polymer matrix. They can reflect and scatter ultraviolet light, blocking ultraviolet rays from penetrating deep into the material, and reducing the probability of chromophore formation (such as carbonyl groups that may form in alicyclic structures under extreme conditions).

[0057] The three-dimensional structure of POSS creates steric hindrance, restricting the mobility of molecular chain segments, especially chromophore precursors. This makes it more difficult for molecules to undergo chemical rearrangement reactions that lead to yellowing after absorbing light energy. At the same time, the inorganic framework of POSS can act as an energy quencher, dissipating the ultraviolet light energy absorbed by the polymer as harmless heat energy, preventing energy transfer to surrounding organic molecules and initiating photodegradation.

[0058] Finally, it should be noted that the above content is only used to illustrate the technical solution of the present invention, and is not intended to limit the scope of protection of the present invention. Simple modifications or equivalent substitutions made by those skilled in the art to the technical solution of the present invention do not depart from the essence and scope of the technical solution of the present invention.

Claims

1. A method for synthesizing a modified hydrogenated bisphenol A type epoxy acrylate high weather-resistant resin, characterized in that, Includes the following steps: Hydrogenated bisphenol A epoxy resin, acrylic acid, p-hydroxyanisole, 2,6-di-tert-butyl-p-cresol, and triethylamine were placed in a reaction vessel. Stirring was started, and the temperature was slowly increased. When the temperature was reached, timing was started. The reaction was exothermic, and the temperature was controlled. A sample was taken to test the acid value. After the acid value was qualified, the temperature was lowered, reagents were added, and the mixture was stirred evenly. The temperature was then lowered again, the material was discharged, filtered, and packaged to obtain the synthetic resin.

2. The method for synthesizing a modified hydrogenated bisphenol A type epoxy acrylate high weather-resistant resin according to claim 1, characterized in that, The process involves slowly increasing the temperature and starting a timer once the desired temperature is reached, including the following steps: Slowly raise the temperature to 65-75℃, and start timing when the temperature reaches 75-85℃.

3. The method for synthesizing a modified hydrogenated bisphenol A type epoxy acrylate high weather-resistant resin according to claim 1, characterized in that, The temperature-controlled reaction includes the following steps: React at 80-90℃ for 1-2 hours, at 90-100℃ for 1-2 hours (the reaction is exothermic), at 100-105℃ for 0.5-1 hours, hold at 105℃ for 1-2 hours, gradually increase the temperature to 105-115℃ for 1-2 hours, hold at 115℃ for 1-2 hours, and then take samples to test the acid value.

4. The method for synthesizing a modified hydrogenated bisphenol A type epoxy acrylate high weather-resistant resin according to claim 1, characterized in that, The sampling and testing of acid value includes the following steps: The reaction ends when the acid value is less than 2 mg KOH / g, but when the acid value is close to 3 mg KOH / g, samples are taken every 15 minutes for monitoring. Nitrogen gas is required for protection during the sampling process.

5. The method for synthesizing a modified hydrogenated bisphenol A type epoxy acrylate high weather-resistant resin according to claim 1, characterized in that, The cooling and reagent addition process includes the following steps: Cool down to below 100°C and add trimethylolpropane triacrylate.

6. The method for synthesizing a modified hydrogenated bisphenol A type epoxy acrylate high weather-resistant resin according to claim 1, characterized in that, The cooling and reagent addition process includes the following steps: Cool the temperature to below 100℃, add the POSS solution first, stir well, and then add trimethylolpropane triacrylate.

7. The method for synthesizing a modified hydrogenated bisphenol A type epoxy acrylate high weather-resistant resin according to claim 6, characterized in that, The preparation method of POSS solution includes the following steps: Take a three-necked flask equipped with a mechanical stirrer and a nitrogen protection port, add acrylic acid-functionalized POSS powder and trimethylolpropane triacrylate; stir and premix to obtain a mixture, then sonicate the mixture; add a surfactant and stir; finally filter to obtain a POSS solution.

8. The method for synthesizing a modified hydrogenated bisphenol A type epoxy acrylate high weather-resistant resin according to claim 7, characterized in that, Acrylic functionalized POSS powders include MA-POSS.

9. The method for synthesizing a modified hydrogenated bisphenol A type epoxy acrylate high weather-resistant resin according to claim 1, characterized in that, By weight, 50-60 parts of hydrogenated bisphenol A type epoxy resin, 20-25 parts of acrylic acid, 0.1-2 parts of p-hydroxyanisole, 0.1-1 parts of 2,6-di-tert-butyl-p-cresol, 2-5 parts of triethylamine, and 20-50 parts of trimethylolpropane triacrylate.

10. A product characterized in that, The preparation method of this product includes the following steps: The synthetic resin, initiator, glass fiber cloth, leveling agent, and light stabilizer are mixed to obtain a mixture, which is then hot-pressed and cured to obtain the product. The synthetic resin is prepared by the method for synthesizing a modified hydrogenated bisphenol A type epoxy acrylate high weather-resistant resin according to any one of claims 1-9.

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