Photovoltaic high-ultraviolet-aging-resistant light-cured resin and preparation method thereof

Abstract

The invention provides photovoltaic high-ultraviolet-aging-resistant light-cured resin. The photovoltaic high-ultraviolet-aging-resistant light-cured resin is prepared from diisocyanate, an end-capping reagent, a macromolecular chain extender, a micromolecular chain extender, a catalyst, an ultraviolet absorbent, a light stabilizer, hyperbranched polyester and a polymerization inhibitor. The ultraviolet absorbent is prepared from graphene, 2-hydroxybenzaldehyde, n-caprylic alcohol and p-toluenesulfonic acid; the light stabilizer comprises a silicon dioxide nanotube and p-phenylenediamine; the hyperbranched polyester is prepared from 2, 2-dimethylolpropionic acid and 5 to 7 parts of trimethylolpropane. According to the invention, through chain extension, the ultraviolet absorbent and the light stabilizer are added in a matched manner, so that the prepared light-cured resin has good anti-aging and anti-ultraviolet functions.

Description

Technical Field

[0001] The invention belongs to the technical field of photocurable resin preparation, and specifically relates to a photovoltaic high-ultraviolet aging-resistant photocurable resin and a preparation method thereof. Background Art

[0002] Photocurable resin, also known as photosensitive resin, is a type of oligomer that can undergo physical and chemical changes rapidly in a short period of time after being exposed to light, and then cross-link and solidify. Photocurable resin is widely used in the photovoltaic industry. It can be used as an adhesive to achieve interconnection between high-efficiency solar cells, reduce series resistance and improve battery efficiency; it can also be used to encapsulate solar cells to isolate the external environment and protect the battery from mechanical damage, thereby extending battery life; it can also be used as an electron transport layer material to effectively improve the photoelectric conversion efficiency.

[0003] Patent CN102070767B provides a method for preparing an aging-resistant UV-curable fluorinated acrylic polyurethane resin, which uses polyisocyanate, double-bond monohydroxy acrylate and polyhydroxy fluorinated acrylate resin as raw materials to improve the resistance to moisture and heat, low temperature, mildew, salt spray and oil of the photocurable resin. Patent CN107141424B provides a photocurable resin material, which uses rigid alicyclic epoxy resin, flexible alicyclic epoxy resin, acrylate monomer or prepolymer, oxetane active diluent, initiator and the like as main components to obtain a photocurable resin material with excellent mechanical properties; Patent CN112831278B provides a photocurable resin composition, including acrylic resin, multifunctional urethane (meth) acrylate with more than 3 functional groups in one molecule, acrylic monomer and photoinitiator, which can also be cured under low light intensity, and has excellent physical properties such as adhesion and weather resistance. However, the existing technology for photovoltaic photocurable resins is relatively lacking in terms of UV resistance and aging resistance. Summary of the invention

[0004] The purpose of the present invention is to provide a photovoltaic resistant high-ultraviolet aging photocurable resin and a preparation method thereof. A photocurable resin with good aging resistance is prepared by using diisocyanate, a macromolecular chain extender, a small molecule chain extender and a capping agent, in the presence of a catalyst and an inhibitor, an ultraviolet absorber and a light stabilizer.

[0005] In order to achieve the above object, the present invention provides the following technical solutions: A photovoltaic resistant high-ultraviolet aging photocurable resin comprises, by weight, 40-60 parts of diisocyanate, 10-20 parts of end-capping agent, 10-20 parts of macromolecular chain extender, 3-7 parts of small molecule chain extender, 0.04-0.08 parts of catalyst, 5-10 parts of ultraviolet absorber, 3-6 parts of light stabilizer, 3-6 parts of hyperbranched polyester and 0.05-0.1 parts of polymerization inhibitor.

[0006] Furthermore, the ultraviolet absorber includes 4-8 parts of graphene, 20-40 parts of 2-hydroxybenzaldehyde, 60-80 parts of n-octanol and 1-3 parts of p-toluenesulfonic acid.

[0007] Furthermore, the light stabilizer includes 3-5 parts of silica nanotubes and 15-25 parts of p-phenylenediamine.

[0008] Furthermore, the number average molecular weight of the hyperbranched polyester is 5000-10000 g / mol, and the degree of branching is 0.4-0.5.

[0009] Furthermore, the diisocyanate is one or a mixture of XDI diisocyanate and HDI diisocyanate; the capping agent is one or a mixture of hydroxyethyl methacrylate and hydroxypropyl methacrylate; the catalyst is one of tetraisooctyl titanate, N,N-dimethylcyclohexylamine, N,N-dimethylbenzylamine or dibutyltin dilaurate; the inhibitor is one or more of p-hydroxyanisole, 2,6-di-tert-butyl-p-cresol, triphenylphosphine and hydroquinone.

[0010] Furthermore, the molecular weight of the macromolecular chain extender is 1000-2000, and it is one of polycaprolactone diol, polyhexanediol adipate, and polybutylene adipate; the molecular weight of the small molecule chain extender is 100-300, and it is one or two of diethylene glycol, 1,3-propylene glycol, and 1,4-cyclohexanedimethanol.

[0011] A method for preparing a photovoltaic resistant high ultraviolet aging photocurable resin comprises the following steps: S1: Add 40-60 parts of diisocyanate, 10-20 parts of macromolecular chain extender and 0.04-0.08 parts of catalyst into a reactor, and stir to react at room temperature; start sampling to detect isocyanate value after 0.5h of reaction, and then sample once every 0.5h; S2: When the isocyanate value is detected to be 14-16% NCO, 1-3 parts of hyperbranched polyester and 3-6 parts of light stabilizer are added to step S1, the temperature is raised to 85-95° C., and the mixture is stirred and reacted at the temperature; S3: When the isocyanate value is detected to be 4-7% NCO, 3-7 parts of a small molecule chain extender and 5-10 parts of a UV absorber are added to step S2, the temperature is lowered to 70-80°C, and the temperature is kept to continue the reaction; S4: When the isocyanate value is detected to be 0.2-0.4% NCO, add 10-20 parts of a blocking agent, cool to 30-40°C and keep warm for 25-35 minutes to obtain a high-ultraviolet aging resistant photocurable resin.

[0012] Furthermore, the preparation process of the hyperbranched polyester in step S2 is: take 25-35 parts of 2,2-dihydroxymethylpropionic acid and 5-7 parts of trimethylolpropane, mix them, add 0.3-0.5 parts of p-toluenesulfonic acid at a temperature of 130-140°C under nitrogen protection, keep warm for 1-3 hours and then turn off the nitrogen, continue to stir and react at a rate of 600r / min for 1-1.5 hours to obtain a hyperbranched polyester.

[0013] Furthermore, the preparation process of the light stabilizer in step S2 is: take 15-25 parts of p-phenylenediamine and add it to 20-30 parts of acetone solvent, stir at a temperature of 40-60°C for 10-20 minutes; under the protection of a nitrogen atmosphere, add 3-5 parts of silica nanotubes, and ultrasonically disperse for 1-2 hours to obtain a light stabilizer.

[0014] Furthermore, the preparation process of the ultraviolet absorber in step S3 is: take 20-40 parts of 2-hydroxybenzaldehyde, 60-80 parts of n-octanol and 1-3 parts of p-toluenesulfonic acid and add them into a reactor, react at a temperature of 80-100°C for 20 minutes, then add 4-8 parts of graphene, and continue to react for 2-3 hours to obtain the ultraviolet absorber.

[0015] Diisocyanates are an important class of organic compounds that contain two isocyanate groups (-N=C=O) in their molecules. These compounds are key raw materials for the synthesis of polyurethane (PU) and are widely used in coatings, adhesives, foams, elastomers, fibers and other fields; the general structural formula of diisocyanates is R(NCO)2, where R is an organic group. Depending on the R group, diisocyanates can be divided into many types, including toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) and lysine diisocyanate (LDI).

[0016] Chain extenders extend the length of polymer chains by reacting with active end groups on polymer chains (such as isocyanate groups, carboxyl groups, hydroxyl groups, etc.). For example, in polyurethane synthesis, diamines or diols can react with isocyanate groups to form new urethane or ester bonds, thereby extending the polymer chain; this process can significantly increase the molecular weight of the polymer and improve its physical and mechanical properties.

[0017] Compared with the prior art, the advantages and beneficial effects of the present invention are: The invention uses XDI diisocyanate and HDI diisocyanate as raw materials, controls the NCO content in the reaction system to adjust the reaction process under the action of a catalyst and a polymerization inhibitor, and adds components such as a hyperbranched polyester, a macromolecular chain extender, a small molecular chain extender, etc. in steps, and simultaneously adds an ultraviolet absorber and a light stabilizer to absorb ultraviolet rays and inhibit photooxidation reactions, thereby delaying the aging process of the resin and improving its anti-ultraviolet and anti-aging properties. DETAILED DESCRIPTION

[0018] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0019] The raw materials used in the present invention are as follows: XDI diisocyanate and HDI diisocyanate were purchased from Guangzhou Haoyi New Materials Technology Co., Ltd. 50; hydroxyethyl methacrylate was purchased from Shanghai Yuanye Biotechnology Co., Ltd. S24381; hydroxypropyl methacrylate was purchased from Shanghai Yuanye Biotechnology Co., Ltd. Y33039; polycaprolactone diol, polyhexanediol adipate, and polybutylene adipate were purchased from Beijing Jiehui Bogao Biotechnology Co., Ltd.; diethylene glycol was purchased from Shanghai Yuanye Biotechnology Co., Ltd. S24141; 1,3-propylene glycol was purchased from Shanghai Yuanye Biotechnology Co., Ltd. S24136; 1,4-cyclohexanedimethanol was purchased from Shandong Jinyueyuan New Materials Co., Ltd. 648; tetraethylhexyl titanate was purchased from Shanghai Nuotai Chemical Co., Ltd. 5102; N,N-dimethylcyclohexylamine and N,N-dimethylbenzylamine were purchased from Shandong Jinyueyuan New Materials Co., Ltd. 1265; dibutyltin dilaurate was purchased from Jinan Shiji Tongda Chemical Co., Ltd. 1242; p-Hydroxyanisole was purchased from Weifang Luze New Materials Co., Ltd. 481; 2,6-di-tert-butyl-p-cresol was purchased from Juye Runjia Chemical Co., Ltd. 104; triphenylphosphine was purchased from Jinan Huifengda Chemical Co., Ltd. 1282; hydroquinone was purchased from Henan Yejiusheng Industrial Co., Ltd. 45; 2,2-dihydroxymethylpropionic acid was purchased from Shanghai Yuanye Biotechnology Co., Ltd. S24027; trimethylolpropane was purchased from Shanghai Yuanye Biotechnology Co., Ltd. S50717.

[0020] Example 1 This embodiment provides a method for preparing a photovoltaic resistant high ultraviolet aging photocurable resin, comprising the following steps: S1: 40g XDI diisocyanate, 10g polycaprolactone diol, 0.04g tetraisooctyl titanate and 0.05g p-hydroxyanisole were added into a reaction kettle, and stirred at a rate of 500r / min at room temperature; after 0.5h of reaction, sampling was started to detect the isocyanate value, and sampling was performed every 0.5h thereafter; S2: Mix 25g of 2,2-dimethylolpropionic acid and 5g of trimethylolpropane, add 0.3g of p-toluenesulfonic acid at 130°C under nitrogen protection, keep warm for 1h, turn off the nitrogen, continue stirring at a rate of 600r / min for 1h to obtain hyperbranched polyester; add 15g of p-phenylenediamine to 20g of acetone solvent, stir at a rate of 300r / min for 10min at a temperature of 40°C; add 3g of silica nanotubes under nitrogen protection, and disperse by ultrasonic for 1h to obtain a light stabilizer; When the isocyanate value is detected to be 14% NCO, 1 g of hyperbranched polyester and 3 g of light stabilizer are added to step S1, the temperature is raised to 85° C., and the mixture is stirred at a rate of 600 r / min to react; S3: 20 g of 2-hydroxybenzaldehyde, 60 g of n-octanol and 1 g of p-toluenesulfonic acid were added to a reaction kettle, and the mixture was reacted at 80° C. for 20 min, followed by the addition of 4 g of graphene, and the reaction was continued for 2 h to obtain a UV absorber; When the isocyanate value detected is 4% NCO, 3 g of diethylene glycol and 5 g of ultraviolet absorber are added to step S2, the temperature is lowered to 70° C., and the temperature is kept to continue the reaction; S4: When the isocyanate value is detected to be 0.2% by NCO, 10 g of hydroxyethyl methacrylate is added, the temperature is lowered to 30° C. and the reaction is carried out for 25 minutes to obtain a photocurable resin resistant to high ultraviolet aging.

[0021] Example 2 This embodiment provides a method for preparing a photovoltaic resistant high ultraviolet aging photocurable resin, comprising the following steps: S1: Add 60g HDI diisocyanate, 20g polybutylene adipate, 0.08g N,N-dimethylcyclohexylamine and 0.1g 2,6-di-tert-butyl-p-cresol into a reactor, and stir at a rate of 500r / min at room temperature; start sampling to detect the isocyanate value after 0.5h of reaction, and then sample once every 0.5h; S2: 35 g of 2,2-dimethylolpropionic acid and 7 g of trimethylolpropane were mixed, and 0.5 g of p-toluenesulfonic acid was added at 140°C under nitrogen protection. After keeping the temperature for 3 hours, the nitrogen was turned off, and the reaction was continued at a stirring rate of 600 r / min for 1.5 hours to obtain a hyperbranched polyester; 25 g of p-phenylenediamine was added to 30 g of acetone solvent, and stirred at 60°C at a rate of 500 r / min for 20 min; 5 g of silica nanotubes was added under nitrogen atmosphere, and ultrasonic dispersion was performed for 2 h to obtain a light stabilizer; When the isocyanate value is detected to be 16% NCO, 3 g of hyperbranched polyester and 6 g of light stabilizer are added to step S1, the temperature is raised to 95° C., and the mixture is stirred at a rate of 600 r / min to react; S3: 40 g of 2-hydroxybenzaldehyde, 80 g of n-octanol and 3 g of p-toluenesulfonic acid were added to a reaction kettle, and the mixture was reacted at 100° C. for 20 min, followed by adding 8 g of graphene and continuing the reaction for 3 h to obtain a UV absorber; When the isocyanate value detected is 7% NCO, add 7g 1,3-propylene glycol and 10g ultraviolet absorber to step S2, cool to 80°C, and keep warm to continue the reaction; S4: When the isocyanate value is detected to be 0.4% NCO, 20 g of hydroxypropyl methacrylate is added, the temperature is lowered to 40° C. and the reaction is kept for 35 minutes to obtain a high-ultraviolet aging-resistant photocurable resin.

[0022] Example 3 This embodiment provides a method for preparing a photovoltaic resistant high ultraviolet aging photocurable resin, comprising the following steps: S1: 30g XDI diisocyanate, 20g HDI diisocyanate, 15g polyhexanediol adipate, 0.06g N,N-dimethylbenzylamine, 0.04g 2,6-di-tert-butyl-p-cresol and 0.04g triphenylphosphine were added into a reaction kettle, and stirred at a rate of 500r / min at room temperature; after 0.5h of reaction, sampling was started to detect the isocyanate value, and sampling was performed every 0.5h thereafter; S2: 30 g of 2,2-dimethylolpropionic acid and 6 g of trimethylolpropane were mixed, and 0.4 g of p-toluenesulfonic acid was added at 135°C under nitrogen protection. After keeping the temperature for 3 hours, the nitrogen was turned off, and the reaction was continued at a stirring rate of 600 r / min for 1.5 hours to obtain a hyperbranched polyester; 20 g of p-phenylenediamine was added to 25 g of acetone solvent, and stirred at 500 r / min for 15 min at a temperature of 55°C. Under the protection of a nitrogen atmosphere, 4 g of silica nanotubes was added, and ultrasonic dispersion was performed for 1.5 h to obtain a light stabilizer.

[0023] When the isocyanate value is detected to be 15% NCO, 2 g of hyperbranched polyester and 4 g of light stabilizer are added to step S1, the temperature is raised to 92° C., and the mixture is stirred at a rate of 600 r / min to react; S3: 30 g of 2-hydroxybenzaldehyde, 70 g of n-octanol and 2 g of p-toluenesulfonic acid were added to a reaction kettle, and the mixture was reacted at 90° C. for 20 min, followed by the addition of 6 g of graphene, and the reaction was continued for 2.5 h to obtain a UV absorber; When the isocyanate value detected is 6% NCO, 3 g of diethylene glycol, 2 g of 1,4-cyclohexanedimethanol and 7 g of ultraviolet absorber are added to step S2, the temperature is lowered to 76° C., and the temperature is kept to continue the reaction; S4: When the isocyanate value detected is NCO 0.3%, 7g of hydroxyethyl methacrylate and 8g of hydroxypropyl methacrylate are added, and the temperature is lowered to 36°C and kept for reaction for 30 minutes to obtain a high-ultraviolet aging resistant photocurable resin.

[0024] Comparative Example 1 The difference between this comparative example and Example 1 is that the hyperbranched polyester is missing in step S2, and the other steps are the same.

[0025] Comparative Example 2 The difference between this comparative example and Example 1 is that there is no light stabilizer in step S2, and the other steps are the same.

[0026] Comparative Example 3 The difference between this comparative example and Example 1 is that the ultraviolet absorber is missing in step S3, and the other steps are the same.

[0027] Comparative Example 4 The difference between this comparative example and Example 1 is that in step S2, when the isocyanate value detected is NCO 30%, 1 g of hyperbranched polyester is added to step S1, and the other steps are the same.

[0028] Comparative Example 5 The difference between this comparative example and Example 1 is that in step S3, when the isocyanate value detected is NCO 10%, 3 g of diethylene glycol is added, and the other steps are the same.

[0029] Performance Test: The photocurable resin synthesized in each embodiment and comparative example, the photocurable monomer (mixed with isobornyl acrylate and trimethylolpropane triacrylate in a mass ratio of 1:3), and the initiator (mixed with TPO and 184 in a mass ratio of 1:1.5) were reacted in a mass ratio of 65:30:3 to prepare a paint film with a thickness of 100 μm. 2 The material was cured twice with energy light. After drying, the initial yellowness b value and elongation at break were tested; According to GB / T16422.3 test, the paint film was placed in a fluorescent ultraviolet lamp (lamp model UVB-313, light intensity 40W / m, 8 320W in total; wavelength 280nm~400nm) for 240 hours, and then the yellowness b value and elongation at break were retested. The results are shown in the table below.

[0030] Table 1

[0031] It can be seen from the above performance test results that Examples 1-3 have excellent performance in terms of UV resistance and aging. In particular, the comprehensive performance of Example 3 is the most outstanding. However, since Comparative Examples 1-5 do not adopt the necessary technical solutions, their performance in the corresponding performance tests is significantly worse than that of the Examples. The above experimental results further prove the importance of the technical solutions defined in the present invention for its technical effects.

[0032] The above is a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A photovoltaic resistant high ultraviolet aging photocurable resin, characterized in that: The invention comprises, by weight, 40-60 parts of diisocyanate, 10-20 parts of end-capping agent, 10-20 parts of macromolecular chain extender, 3-7 parts of small molecular chain extender, 0.04-0.08 parts of catalyst, 5-10 parts of ultraviolet absorber, 3-6 parts of light stabilizer, 3-6 parts of hyperbranched polyester and 0.05-0.1 parts of polymerization inhibitor.

2. The photovoltaic high-ultraviolet aging resistant photocurable resin according to claim 1, characterized in that: The ultraviolet absorber comprises 4-8 parts of graphene, 20-40 parts of 2-hydroxybenzaldehyde, 60-80 parts of n-octanol and 1-3 parts of p-toluenesulfonic acid.

3. The photovoltaic resistant high ultraviolet aging photocurable resin according to claim 1, characterized in that: The light stabilizer includes 3-5 parts of silica nanotubes and 15-25 parts of p-phenylenediamine.

4. The photovoltaic high-ultraviolet aging resistant photocurable resin according to claim 1, characterized in that: The hyperbranched polyester has a number average molecular weight of 5000-10000 g / mol and a branching degree of 0.4-0.

5.

5. The photovoltaic high-ultraviolet aging resistant photocurable resin according to claim 1, characterized in that: The diisocyanate is one of XDI diisocyanate and HDI diisocyanate or a mixture of the two; the end-capping agent is one of hydroxyethyl methacrylate and hydroxypropyl methacrylate or a mixture of the two; the catalyst is one of tetraisooctyl titanate, N,N-dimethylcyclohexylamine, N,N-dimethylbenzylamine or dibutyltin dilaurate; and the inhibitor is one or more of p-hydroxyanisole, 2,6-di-tert-butyl-p-cresol, triphenylphosphine and hydroquinone.

6. The photovoltaic resistant high-ultraviolet aging photocurable resin according to claim 1, characterized in that: The molecular weight of the macromolecular chain extender is 1000-2000, and it is one of polycaprolactone diol, polyhexanediol adipate, and polybutylene adipate; the molecular weight of the small molecule chain extender is 100-300, and it is one or two of diethylene glycol, 1,3-propylene glycol, and 1,4-cyclohexanedimethanol.

7. A method for preparing a photovoltaic resistant high ultraviolet aging photocurable resin, characterized in that: The following steps are involved: S1: Add 40-60 parts of diisocyanate, 10-20 parts of macromolecular chain extender and 0.04-0.08 parts of catalyst into a reactor, and stir to react at room temperature; start sampling to detect isocyanate value after 0.5h of reaction, and then sample once every 0.5h; S2: When the isocyanate value is detected to be 14-16% NCO, 1-3 parts of hyperbranched polyester and 3-6 parts of light stabilizer are added to step S1, the temperature is raised to 85-95° C., and the mixture is stirred and reacted at the temperature; S3: When the isocyanate value is detected to be 4-7% NCO, 3-7 parts of a small molecule chain extender and 5-10 parts of a UV absorber are added to step S2, the temperature is lowered to 70-80°C, and the temperature is kept to continue the reaction; S4: When the isocyanate value is detected to be 0.2-0.4% NCO, 10-20 parts of a blocking agent are added, the temperature is lowered to 30-40°C and kept to react for 25-35 minutes, thereby obtaining a high-ultraviolet aging-resistant photocurable resin.

8. The preparation method according to claim 7, a preparation method of a photovoltaic resistant high ultraviolet aging photocurable resin, characterized in that: The preparation process of the hyperbranched polyester in step S2 is as follows: 25-35 parts of 2,2-dihydroxymethylpropionic acid and 5-7 parts of trimethylolpropane are mixed, 0.3-0.5 parts of p-toluenesulfonic acid are added at a temperature of 130-140° C. under nitrogen protection, the nitrogen is turned off after keeping warm for 1-3 hours, and the reaction is continued at a rate of 600 r / min with stirring for 1-1.5 hours to obtain a hyperbranched polyester.

9. The preparation method according to claim 7, a preparation method of a photovoltaic resistant high ultraviolet aging photocurable resin, characterized in that: The preparation process of the light stabilizer in step S2 is: take 15-25 parts of p-phenylenediamine and add it to 20-30 parts of acetone solvent, stir it at a temperature of 40-60° C. for 10-20 minutes; under the protection of a nitrogen atmosphere, add 3-5 parts of silica nanotubes, and ultrasonically disperse it for 1-2 hours to obtain the light stabilizer.

10. The preparation method according to claim 7, a preparation method of a photovoltaic resistant high ultraviolet aging photocurable resin, characterized in that: The preparation process of the ultraviolet absorber in step S3 is as follows: 20-40 parts of 2-hydroxybenzaldehyde, 60-80 parts of n-octanol and 1-3 parts of p-toluenesulfonic acid are added to a reaction kettle, reacted at a temperature of 80-100° C. for 20 minutes, then 4-8 parts of graphene are added, and the reaction is continued for 2-3 hours to obtain the ultraviolet absorber.

Images