Diluted resin glue solution with long-term storage stability as well as preparation method and packaging process of diluted resin glue solution

Abstract

The invention discloses a diluted resin glue solution with long-term storage stability as well as a preparation method and a packaging process thereof, and relates to the technical field of resin glue solution preparation. Which comprises the following raw materials: acrylate resin, a chemical stabilizer, a physical stabilizer, a diluting solvent, 1-methoxy-2-propyl acetate, dipropylene glycol dimethyl ether, modified dipropylene glycol methyl ether and triethanolamine. The low-temperature fluidity of the dipropylene glycol monomethyl ether is obviously superior to that of unmodified dipropylene glycol monomethyl ether, so that the viscosity change rate is low after the glue solution is stored for 1 month at 3 DEG C; the anchoring auxiliary function is achieved, hydroxyl in molecules can form weak interaction with hydroxyl on the surface of fumed silica, and stabilization of a three-dimensional network is assisted; the adhesive is completely compatible with bio-based components, resin and other solvents, has no low-temperature precipitation risk, can improve the anti-freezing performance of a composite system, and avoids glue solution failure caused by solvent freezing at extremely low temperature.

Description

Technical Field

[0001] This invention relates to the field of resin preparation technology, and in particular to a diluted resin solution with long-term storage stability, its preparation method and packaging process. Background Technology

[0002] Resin adhesives typically refer to liquid mixtures composed primarily of synthetic resins, with the addition of curing agents, diluents, or modifiers. When uncured, they are viscous liquids that can be chemically cured into strong, durable solid materials, widely used in bonding, potting, coating, composite materials, and crafts manufacturing.

[0003] Traditional diluted resin solutions suffer from poor environmental performance, high VOC content, and difficulty in biodegradation. Furthermore, the original solvent in the pre-assembled slurry is prone to freezing at extremely low temperatures, failing to stably anchor fumed silica and leading to particle agglomeration and sedimentation. Traditional systems also lack chemical stability, easily undergoing oxidation, UV degradation, and metal ion catalytic failure during long-term storage, and exhibiting poor compatibility between different components, resulting in stratification and precipitation. Therefore, this invention provides a diluted resin solution with long-term storage stability, its preparation method, and packaging process. Summary of the Invention

[0004] The main objective of this invention is to provide a diluted resin solution with strong weather resistance, high biodegradability, and long-term storage stability, which is applied in a diluted resin solution with long-term storage stability, its preparation method, and packaging process.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows: This invention provides a diluted resin solution with long-term storage stability, comprising the following raw materials: 58-62 parts acrylate resin, 2.24-2.3 parts chemical stabilizer, 5.85-7.15 parts physical stabilizer, 23-26 parts diluent, 9.6-10.4 parts 1-methoxy-2-propyl acetate, 0.8-1.6 parts dipropylene glycol dimethyl ether, 1.6-2.4 parts modified dipropylene glycol methyl ether, and 0.01-0.1 parts triethanolamine.

[0006] The purity of triethanolamine is ≥99%, and the moisture content is <0.03%.

[0007] The acrylate resin has a solids content of 50% and a molecular weight distribution PDI ≤ 2.0. It is the main film-forming and bonding core material of the adhesive, possessing excellent film-forming continuity and mechanical toughness. After curing, it can form a dense and flexible adhesive film, ensuring the core bonding performance of the adhesive. It has excellent compatibility with ultra-low temperature composite solvents, bio-based components and stabilizers. After mixing, there is no stratification or precipitation, and it can be adapted to mild preparation processes with low shear stirring.

[0008] The purity of 1-methoxy-2-propyl acetate is ≥99%, and the moisture content is <0.03%.

[0009] The purity of dipropylene glycol dimethyl ether is ≥99%, the moisture content is <0.03%, and the freezing point is ≤-95℃.

[0010] Furthermore, the diluent is one of butyl acetate and limonene.

[0011] Butyl acetate has a purity of ≥99%, moisture content of <0.03%, and a viscosity of 0.7 mPa・s ± 0.05 mPa・s at 25℃. As the main diluent component of the ultra-low temperature solvent, it has excellent dilution ability and can quickly reduce the viscosity of acrylic resin to meet the flow and application requirements of the adhesive. It has moderate volatility, so it is not easy to cause a sudden change in the viscosity of the adhesive due to excessive evaporation during the preparation process. It can also evaporate slowly during the curing stage to avoid the formation of bubbles or pinholes in the adhesive film.

[0012] Limonene is extracted from natural biomass such as citrus peel and turpentine; its biodegradability under composting conditions is >95% (60 days); it has no volatile toxic byproducts; its purity is ≥98%; and its moisture content is ≤0.03%. Its high biodegradability significantly increases the overall bio-based content of the adhesive and further reduces VOC content, perfectly meeting the needs of high-end environmental protection scenarios. It has no side reactions with other materials and will not damage the chemical stability and physical three-dimensional network structure of the system. Its extremely low freezing point fully adapts to the ultra-low temperature storage requirements of the adhesive, synergistically enhancing the low-temperature fluidity of the solvent system. Furthermore, its chemical properties are stable, with no oxidation or discoloration issues during long-term storage, ensuring the stability of the adhesive storage.

[0013] Further, the preparation of the physical stabilizer includes the following steps: mixing and stirring methyl isopentyl glycol ether and triethyl citrate at 220 rpm for 8 minutes, adding 3A molecular sieve and letting stand for 2 hours, filtering with a 0.45 μm polytetrafluoroethylene filter membrane to remove particles, collecting the liquid, adding silica and stirring at 220 rpm for 16 minutes to obtain the physical stabilizer.

[0014] The silica is fumed silica with a specific surface area of ​​200±25 m². 2 / g, hydrophobic, hydrophobicity ≥90%, moisture <0.03%.

[0015] Methyl isopentyl glycol ether is derived from bio-based corn starch, with a biodegradability rate >90%, purity ≥98%, moisture content <0.03%, and freezing point ≤-88℃. It has both environmental friendliness and functional synergy. The biodegradability rate >90% can reduce the VOC content of the adhesive to ≤24g / L, meeting the requirements of high-end environmental protection scenarios.

[0016] Triethyl citrate is derived from bio-based citrus peel, with a biodegradability rate >90%, purity ≥98%, moisture content <0.03%, and polyester content ≥97%. It possesses the dual advantages of environmental friendliness and solvation shell construction, exhibiting excellent biodegradability and further enhancing the environmental protection level of the adhesive. At the same time, its low volatility can reduce VOC emissions from the adhesive. The polyester structure in the molecule can form a thick solvation shell on the surface of fumed silica particles, effectively preventing particle aggregation and improving dispersion uniformity.

[0017] Furthermore, the mass ratio of the methyl isopentyl glycol ether, triethyl citrate, and silicon dioxide is 4:8:1.

[0018] Further, the preparation of the modified dipropylene glycol methyl ether includes the following steps: adding dipropylene glycol methyl ether, isopentylcyclohexane oxide and N,N-bis(2-hydroxyethyl)acrylamide to a three-necked flask and mixing with nitrogen gas at a flow rate of 0.5 L / min, stirring at 200 rpm for 5 minutes, adding boron trifluoride diethyl ether complex and stirring with the stirring speed set to 200 rpm for 15 minutes, adding anhydrous ethanol and stirring for 5 minutes, adding 3A molecular sieve for dehydration, and filtering with a 0.45 μm polytetrafluoroethylene filter membrane to obtain the modified dipropylene glycol methyl ether.

[0019] Isopentyl cyclohexane has an epoxy value of 0.48–0.50 eq / 100g and a purity of ≥98%. It introduces cyclic branches, reduces intermolecular forces, improves the extremely low temperature fluidity of modified dipropylene glycol methyl ether, and optimizes the low temperature storage performance of the adhesive.

[0020] N,N-bis(2-hydroxyethyl)acrylamide has a purity of ≥98% and a dihydroxy content of ≥97%, providing multiple hydrogen bond sites to anchor fumed silica, enhance the stability of the three-dimensional network, and avoid low-temperature aggregation.

[0021] The concentration of the boron trifluoride diethyl ether complex was 46.7%, and the moisture content was <0.01%.

[0022] The modified dipropylene glycol methyl ether has a moisture content of <0.03%, a viscosity of 10–12 mPa·s at 25°C, a viscosity change rate of ≤2.0% after 1 month of storage at 3°C, and no low-temperature precipitation.

[0023] Furthermore, the mass ratio of dipropylene glycol methyl ether, isopentyl cyclohexane oxide, N,N-bis(2-hydroxyethyl)acrylamide, boron trifluoride diethyl ether complex, and anhydrous ethanol is 100:3.8:2.2:0.07:5.

[0024] Further, the preparation of the chemical stabilizer includes the following steps: pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris(2,4-di-tert-butylphenyl) phosphite, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole and benzotriazine derivative are added to benzaldehyde and mixed and stirred at 200 rpm for 10 minutes to obtain the chemical stabilizer.

[0025] Pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] has a purity of ≥98% and is free of impurities.

[0026] The purity of tris(2,4-di-tert-butylphenyl) phosphite is ≥97%, with no hydrolysis products.

[0027] The purity of 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole is ≥98%.

[0028] Further, the mass ratio of the tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] pentaerythritol ester, tris(2,4-di-tert-butylphenyl) phosphite, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, benzotriazine derivative and benzaldehyde is 4:3:1.5:1:74.07.

[0029] The benzotriazine derivative is one of 5-methylbenzotriazine, 1-hydroxybenzotriazine, and 4-chlorobenzotriazine, with a purity ≥96%.

[0030] Secondly, the present invention provides a method for preparing a diluted resin solution with long-term storage stability, the preparation method comprising the following steps: S1. Vacuum dry the acrylic resin, set the temperature to 55℃, the vacuum degree to -0.095MPa, and dry for 2 hours to obtain dried acrylic resin; S2. Mix and stir the diluent, 1-methoxy-2-propyl acetate, chemical stabilizer, modified dipropylene glycol methyl ether and dipropylene glycol dimethyl ether at a speed of 250-280 rpm for 10-12 minutes. Add 3A molecular sieve and let stand for 1-2 hours. Filter using a 0.45μm polytetrafluoroethylene filter membrane to remove the 3A molecular sieve and obtain the mixture. S3. Add the dried acrylate resin to the mixture and stir. Set the speed to 300 rpm and stir for 10 minutes. Increase the speed to 400 rpm and stir for 15 minutes. Add the physical stabilizer and stir. Set the reaction temperature to 30℃ and adjust the speed to 350 rpm. Stir for 30 minutes. Add triethanolamine to adjust the pH to 7-7.5. Reduce the temperature to 12℃ at a rate of 2℃ / min and reduce the speed to 180 rpm. Keep the temperature and stir for 10 minutes to obtain material A. Degas material A under vacuum. Set the vacuum degree to -0.09 MPa and degas for 15 minutes. Filter using a 0.45 μm polytetrafluoroethylene filter membrane to remove particles and obtain a diluted resin solution with long-term storage stability.

[0031] Thirdly, this invention provides a packaging process for a diluted resin solution with long-term storage stability. The packaging process uses a brown multi-layer PET / HDPE bottle with an oxygen permeability ≤0.1 cm⁻¹. 3 / (m 2 (24h·atm), bottle cap with PTFE liner, headspace oxygen concentration ≤1%.

[0032] The present invention has the following beneficial effects: 1. In this invention, a physical stabilizer is added. The hydroxyl groups of methyl isopentyl glycol ether form stable hydrogen bonds with the hydroxyl groups on the surface of silica, while triethyl citrate forms a thick solvation shell to encapsulate the particles. The uniform, semi-transparent pre-assembled slurry constructed by the two can maintain the integrity of the three-dimensional network of fumed silica during long-term storage, effectively preventing the slurry from separating, the particles from settling, or the local freezing, and ensuring that the viscosity change rate is controlled within the qualified range for a long time. On the other hand, its excellent biocompatibility and chemical stability can be compatible with the resin, composite solvent and other components in the slurry for a long time without side reactions. At the same time, its low volatility can avoid the imbalance of component ratio during storage, further enhancing the stability of long-term storage. Moreover, the environmental protection attributes do not sacrifice the stability performance, making it suitable for the long-term use requirements of high-end scenarios.

[0033] 2. In this invention, a chemical stabilizer is added, which is the core carrier ensuring the chemical stability of the adhesive during long-term storage. Benzyl alcohol has moderate viscosity and excellent solubility, which can completely dissolve the quaternary chemical stabilizer into a transparent solution, ensuring that the stabilizer is uniformly dispersed in the subsequent adhesive system. This avoids failure problems such as local oxidation and ultraviolet degradation caused by local enrichment or absence of stabilizer, and can comprehensively inhibit chemical degradation reactions during long-term storage of the adhesive, thus extending the adhesive's lifespan. At the same time, benzyl alcohol has excellent long-term compatibility with bio-based materials, silica, and acrylate resins, and will not produce phenomena such as interface separation or precipitation during storage, ensuring the uniformity and stability of the adhesive system. Its extremely low volatility means that it is almost not lost during long-term storage, which can stably maintain the proportion of adhesive components and avoid stabilizer failure or abnormal adhesive viscosity due to carrier solvent evaporation. Combined with nitrogen protection throughout the process, this further strengthens the chemical stability defense line for long-term storage of the adhesive.

[0034] 3. In this invention, modified dipropylene glycol methyl ether is added. It is the core solvent component that improves the low-temperature fluidity of the adhesive. After modification, cyclic branches and chelated multi-point hydrogen bond structures are introduced, resulting in significantly better low-temperature fluidity than unmodified dipropylene glycol methyl ether. This allows the adhesive to maintain a low viscosity change rate after one month of storage at 3°C. It also has an anchoring function, as the hydroxyl groups in its molecules can form weak interactions with the hydroxyl groups on the surface of fumed silica, thus aiding in the stability of the three-dimensional network. It is fully compatible with bio-based components, resins, and other solvents, with no risk of low-temperature precipitation or degradation. At the same time, it can improve the antifreeze performance of the composite system and avoid adhesive failure caused by solvent freezing at extremely low temperatures. Detailed Implementation

[0035] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0036] It should be noted that all raw materials used in the following experiments are commercially available.

[0037] Example 1: A diluent resin solution with long-term storage stability, comprising the following raw materials: 58 parts acrylate resin, 2.24 parts chemical stabilizer, 5.85 parts physical stabilizer, 23 parts diluent, 9.6 parts 1-methoxy-2-propyl acetate, 0.8 parts dipropylene glycol dimethyl ether, 1.6 parts modified dipropylene glycol methyl ether, and 0.01 parts triethanolamine.

[0038] The diluent is either butyl acetate or limonene.

[0039] The preparation of the physical stabilizer includes the following steps: methyl isopentyl glycol ether and triethyl citrate are mixed and stirred at 220 rpm for 8 minutes, 3A molecular sieve is added and allowed to stand for 2 hours, filtered using a 0.45 μm polytetrafluoroethylene filter membrane to remove particles, the liquid is collected, silica is added and stirred at 220 rpm for 16 minutes to obtain the physical stabilizer.

[0040] The mass ratio of methyl isopentyl glycol ether, triethyl citrate, and silicon dioxide is 4:8:1.

[0041] The preparation of modified dipropylene glycol methyl ether includes the following steps: dipropylene glycol methyl ether, isopentylepoxycyclohexane and N,N-bis(2-hydroxyethyl)acrylamide are added to a three-necked flask and mixed and stirred. Nitrogen gas is introduced at a flow rate of 0.5 L / min and the stirring speed is 200 rpm for 5 minutes. Boron trifluoride diethyl ether complex is added and stirred. The stirring speed is set to 200 rpm and stirred for 15 minutes. Anhydrous ethanol is added and stirred for 5 minutes. 3A molecular sieve is added for dehydration. The mixture is filtered using a 0.45 μm polytetrafluoroethylene filter membrane to obtain modified dipropylene glycol methyl ether.

[0042] The mass ratio of dipropylene glycol methyl ether, isopentyl cyclohexane oxide, N,N-bis(2-hydroxyethyl)acrylamide, boron trifluoride diethyl ether complex, and anhydrous ethanol is 100:3.8:2.2:0.07:5.

[0043] The preparation of the chemical stabilizer includes the following steps: pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris(2,4-di-tert-butylphenyl) phosphite, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole and 5-methylbenzotriazole hydrazine are added to benzaldehyde and mixed and stirred at 200 rpm for 10 minutes to obtain the chemical stabilizer.

[0044] The mass ratio of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris(2,4-di-tert-butylphenyl)phosphite, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 5-methylbenzotriazine, and benzaldehyde is 4:3:1.5:1:74.07.

[0045] A method for preparing a diluted resin solution with long-term storage stability, the method comprising the following steps: S1. Vacuum dry the acrylic resin, set the temperature to 55℃, the vacuum degree to -0.095MPa, and dry for 2 hours to obtain dried acrylic resin; S2. Limonene, 1-methoxy-2-propyl acetate, chemical stabilizer, modified dipropylene glycol methyl ether and dipropylene glycol dimethyl ether are mixed and stirred at 280 rpm for 12 minutes. 3A molecular sieve is added and allowed to stand for 1 hour. The mixture is then filtered using a 0.45 μm polytetrafluoroethylene filter membrane to remove the 3A molecular sieve and obtain the mixture. S3. Add the dried acrylate resin to the mixture and stir. Set the speed to 300 rpm and stir for 10 minutes. Increase the speed to 400 rpm and stir for 15 minutes. Add the physical stabilizer and stir. Set the reaction temperature to 30℃ and adjust the speed to 350 rpm. Stir for 30 minutes. Add triethanolamine to adjust the pH to 7. Reduce the temperature to 12℃ at a rate of 2℃ / min and reduce the speed to 180 rpm. Keep the temperature and stir for 10 minutes to obtain material A. Degas material A under vacuum. Set the vacuum degree to -0.09 MPa and degas for 15 minutes. Filter using a 0.45 μm polytetrafluoroethylene filter membrane to remove particles and obtain a diluted resin solution with long-term storage stability.

[0046] A packaging process for a diluted resin solution with long-term storage stability, wherein the packaging is a brown multi-layer PET bottle with an oxygen permeability ≤0.1cm. 3 / (m 2 (24h·atm), bottle cap with PTFE liner, headspace oxygen concentration ≤1%.

[0047] Example 2: A diluent resin solution with long-term storage stability, comprising the following raw materials: 60 parts acrylate resin, 2.27 parts chemical stabilizer, 6.5 parts physical stabilizer, 24.5 parts diluent, 10 parts 1-methoxy-2-propyl acetate, 1.2 parts dipropylene glycol dimethyl ether, 2 parts modified dipropylene glycol methyl ether, and 0.04 parts triethanolamine.

[0048] The diluent is either butyl acetate or limonene.

[0049] The preparation of the physical stabilizer includes the following steps: methyl isopentyl glycol ether and triethyl citrate are mixed and stirred at 220 rpm for 8 minutes, 3A molecular sieve is added and allowed to stand for 2 hours, filtered using a 0.45 μm polytetrafluoroethylene filter membrane to remove particles, the liquid is collected, silica is added and stirred at 220 rpm for 16 minutes to obtain the physical stabilizer.

[0050] The mass ratio of methyl isopentyl glycol ether, triethyl citrate, and silicon dioxide is 4:8:1.

[0051] The preparation of modified dipropylene glycol methyl ether includes the following steps: dipropylene glycol methyl ether, isopentylepoxycyclohexane and N,N-bis(2-hydroxyethyl)acrylamide are added to a three-necked flask and mixed and stirred. Nitrogen gas is introduced at a flow rate of 0.5 L / min and the stirring speed is 200 rpm for 5 minutes. Boron trifluoride diethyl ether complex is added and stirred. The stirring speed is set to 200 rpm and stirred for 15 minutes. Anhydrous ethanol is added and stirred for 5 minutes. 3A molecular sieve is added for dehydration. The mixture is filtered using a 0.45 μm polytetrafluoroethylene filter membrane to obtain modified dipropylene glycol methyl ether.

[0052] The mass ratio of dipropylene glycol methyl ether, isopentyl cyclohexane oxide, N,N-bis(2-hydroxyethyl)acrylamide, boron trifluoride diethyl ether complex, and anhydrous ethanol is 100:3.8:2.2:0.07:5.

[0053] The preparation of the chemical stabilizer includes the following steps: pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris(2,4-di-tert-butylphenyl) phosphite, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole and 1-hydroxybenzotriazole hydrazine are added to benzaldehyde and mixed and stirred at 200 rpm for 10 minutes to obtain the chemical stabilizer.

[0054] The mass ratio of tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] pentaerythritol ester, tris(2,4-di-tert-butylphenyl) phosphite, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 1-hydroxybenzotriazole hydrazine, and benzaldehyde is 4:3:1.5:1:74.07.

[0055] A method for preparing a diluted resin solution with long-term storage stability, the method comprising the following steps: S1. Vacuum dry the acrylic resin, set the temperature to 55℃, the vacuum degree to -0.095MPa, and dry for 2 hours to obtain dried acrylic resin; S2. Mix butyl acetate, 1-methoxy-2-propyl acetate, chemical stabilizer, modified dipropylene glycol methyl ether and dipropylene glycol dimethyl ether, set the speed to 250 rpm, stir for 10 minutes, add 3A molecular sieve and let stand for 1.5 hours, filter with 0.45 μm polytetrafluoroethylene filter membrane to remove 3A molecular sieve, and obtain the mixture; S3. Add the dried acrylate resin to the mixture and stir. Set the speed to 300 rpm and stir for 10 minutes. Increase the speed to 400 rpm and stir for 15 minutes. Add the physical stabilizer and stir. Set the reaction temperature to 30℃ and adjust the speed to 350 rpm. Stir for 30 minutes. Add triethanolamine to adjust the pH to 7-7.5. Reduce the temperature to 12℃ at a rate of 2℃ / min and reduce the speed to 180 rpm. Keep the temperature and stir for 10 minutes to obtain material A. Degas material A under vacuum. Set the vacuum degree to -0.09 MPa and degas for 15 minutes. Filter using a 0.45 μm polytetrafluoroethylene filter membrane to remove particles and obtain a diluted resin solution with long-term storage stability.

[0056] A packaging process for a diluted resin solution with long-term storage stability, wherein the packaging is a brown multi-layer PET bottle with an oxygen permeability ≤0.1cm. 3 / (m 2 (24h·atm), bottle cap with PTFE liner, headspace oxygen concentration ≤1%.

[0057] Example 3: A diluted resin solution with long-term storage stability, comprising the following raw materials: 62 parts acrylate resin, 2.3 parts chemical stabilizer, 7.15 parts physical stabilizer, 26 parts diluent, 10.4 parts 1-methoxy-2-propyl acetate, 1.6 parts dipropylene glycol dimethyl ether, 2.4 parts modified dipropylene glycol methyl ether, and 0.1 parts triethanolamine.

[0058] The diluent is either butyl acetate or limonene.

[0059] The preparation of the physical stabilizer includes the following steps: methyl isopentyl glycol ether and triethyl citrate are mixed and stirred at 220 rpm for 8 minutes, 3A molecular sieve is added and allowed to stand for 2 hours, filtered using a 0.45 μm polytetrafluoroethylene filter membrane to remove particles, the liquid is collected, silica is added and stirred at 220 rpm for 16 minutes to obtain the physical stabilizer.

[0060] The mass ratio of methyl isopentyl glycol ether, triethyl citrate, and silicon dioxide is 4:8:1.

[0061] The preparation of modified dipropylene glycol methyl ether includes the following steps: dipropylene glycol methyl ether, isopentylepoxycyclohexane and N,N-bis(2-hydroxyethyl)acrylamide are added to a three-necked flask and mixed and stirred. Nitrogen gas is introduced at a flow rate of 0.5 L / min and the stirring speed is 200 rpm for 5 minutes. Boron trifluoride diethyl ether complex is added and stirred. The stirring speed is set to 200 rpm and stirred for 15 minutes. Anhydrous ethanol is added and stirred for 5 minutes. 3A molecular sieve is added for dehydration. The mixture is filtered using a 0.45 μm polytetrafluoroethylene filter membrane to obtain modified dipropylene glycol methyl ether.

[0062] The mass ratio of dipropylene glycol methyl ether, isopentyl cyclohexane oxide, N,N-bis(2-hydroxyethyl)acrylamide, boron trifluoride diethyl ether complex, and anhydrous ethanol is 100:3.8:2.2:0.07:5.

[0063] The preparation of the chemical stabilizer includes the following steps: pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris(2,4-di-tert-butylphenyl) phosphite, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole and 4-chlorobenzotriazole hydrazine are added to benzaldehyde and mixed and stirred at 200 rpm for 10 minutes to obtain the chemical stabilizer.

[0064] The mass ratio of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris(2,4-di-tert-butylphenyl)phosphite, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 4-chlorobenzotriazole hydrazine, and benzaldehyde is 4:3:1.5:1:74.07.

[0065] A method for preparing a diluted resin solution with long-term storage stability, the method comprising the following steps: S1. Vacuum dry the acrylic resin, set the temperature to 55℃, the vacuum degree to -0.095MPa, and dry for 2 hours to obtain dried acrylic resin; S2. Mix butyl acetate, 1-methoxy-2-propyl acetate, chemical stabilizer, modified dipropylene glycol methyl ether and dipropylene glycol dimethyl ether, set the speed to 260 rpm, stir for 11 minutes, add 3A molecular sieve and let stand for 2 hours, filter with 0.45 μm polytetrafluoroethylene filter membrane to remove 3A molecular sieve, and obtain the mixture. S3. Add the dried acrylate resin to the mixture and stir. Set the speed to 300 rpm and stir for 10 minutes. Increase the speed to 400 rpm and stir for 15 minutes. Add the physical stabilizer and stir. Set the reaction temperature to 30℃ and adjust the speed to 350 rpm. Stir for 30 minutes. Add triethanolamine to adjust the pH to 7-7.5. Reduce the temperature to 12℃ at a rate of 2℃ / min and reduce the speed to 180 rpm. Keep the temperature and stir for 10 minutes to obtain material A. Degas material A under vacuum. Set the vacuum degree to -0.09 MPa and degas for 15 minutes. Filter using a 0.45 μm polytetrafluoroethylene filter membrane to remove particles and obtain a diluted resin solution with long-term storage stability.

[0066] A packaging process for a diluted resin solution with long-term storage stability, wherein the packaging is a brown multi-layer HDPE bottle with an oxygen permeability ≤0.1cm. 3 / (m 2(24h·atm), bottle cap with PTFE liner, headspace oxygen concentration ≤1%.

[0067] Comparative Example 1: The difference between this comparative example and Example 1 is that: Modified dipropylene glycol methyl ether was used in this comparative example.

[0068] Comparative Example 2: The difference between this comparative example and Example 1 is that: This comparative example of physical stabilizers does not contain methyl isopentyl glycol ether.

[0069] Comparative Example 3: The difference between this comparative example and Example 1 is that: No chemical stabilizers were used in this comparative example.

[0070] Performance testing: The diluted resin solutions with long-term storage stability prepared in Examples 1, 2, 3, Comparative Examples 1, 2, and 3 were tested.

[0071] Performance testing: The relevant properties of the diluted resin solutions with long-term storage stability provided in Examples 1-3 and Comparative Examples 1-3, as well as their preparation methods and packaging process samples, were tested respectively. The test data are recorded in Table 1 below:

[0072] Based on the above data, the following conclusions can be drawn: Among them, the viscosity change rate of diluted resin solutions with long-term storage stability prepared by Example 1, Example 2, Example 3, Comparative Example 1, Comparative Example 2 and Comparative Example 3 in GB / T7123.1-2015 was tested after being stored at 25°C for 6 months. Biodegradation rate of diluted resin solutions with long-term storage stability prepared under composting conditions for 60 days using the test methods in GB / T19277.1-2021 (Examples 1, 2, 3, Comparative Examples 1, 2, and 3) was tested. The weather resistance viscosity change rate of diluted resin solutions with long-term storage stability prepared according to the test methods in GB / T16422.3-2014 in Examples 1, 2, 3, Comparative Examples 1, 2, and 3 was tested after 500 hours.

[0073] Through the above demonstrations, the present invention is significantly superior to the control group in terms of viscosity change rate, biodegradation rate and weather resistance viscosity change rate after 6 months of storage at 25°C, thus verifying the advanced nature and rationality of the preparation process.

[0074] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0075] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to the specific implementations described. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A diluted resin solution with long-term storage stability, characterized in that, The diluted resin solution with long-term storage stability comprises the following raw materials: 58-62 parts acrylate resin, 2.24-2.3 parts chemical stabilizer, 5.85-7.15 parts physical stabilizer, 23-26 parts diluent, 9.6-10.4 parts 1-methoxy-2-propyl acetate, 0.8-1.6 parts dipropylene glycol dimethyl ether, 1.6-2.4 parts modified dipropylene glycol methyl ether, and 0.01-0.1 parts triethanolamine.

2. The diluted resin solution with long-term storage stability according to claim 1, characterized in that, The diluent is either butyl acetate or limonene.

3. The diluted resin solution with long-term storage stability according to claim 1, characterized in that, The preparation of the physical stabilizer includes the following steps: Methyl isopentyl glycol ether and triethyl citrate were mixed and stirred, then 3A molecular sieve was added and allowed to stand. The mixture was filtered through a filter membrane to remove particles, and the liquid was collected. Silica was added and stirred to obtain a physical stabilizer.

4. The diluted resin solution with long-term storage stability according to claim 3, characterized in that, The mass ratio of methyl isopentyl glycol ether, triethyl citrate, and silicon dioxide is 4:8:

1.

5. The diluted resin solution with long-term storage stability according to claim 1, characterized in that, The preparation of the modified dipropylene glycol methyl ether includes the following steps: Dipropylene glycol methyl ether, isopentyl cyclohexane oxide, and N,N-bis(2-hydroxyethyl)acrylamide were added to a three-necked flask and stirred. Nitrogen gas was introduced, boron trifluoride diethyl ether complex was added and stirred, anhydrous ethanol was added and stirred, and 3A molecular sieve was added and filtered through a filter membrane to obtain modified dipropylene glycol methyl ether.

6. The diluted resin solution with long-term storage stability according to claim 5, characterized in that, The mass ratio of dipropylene glycol methyl ether, isopentyl cyclohexane oxide, N,N-bis(2-hydroxyethyl)acrylamide, boron trifluoride diethyl ether complex, and anhydrous ethanol is 100:3.8:2.2:0.07:

5.

7. The diluted resin solution with long-term storage stability according to claim 1, characterized in that, The preparation of the chemical stabilizer includes the following steps: adding pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris(2,4-di-tert-butylphenyl) phosphite, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole and benzotriazole hydrazine derivative to benzaldehyde and mixing to obtain the chemical stabilizer.

8. The diluted resin solution with long-term storage stability according to claim 6, characterized in that, The mass ratio of the tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] pentaerythritol ester, tris(2,4-di-tert-butylphenyl) phosphite, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, benzotriazine derivative and benzaldehyde is 4:3:1.5:1:74.07; The benzotriazine derivative is one of 5-methylbenzotriazine, 1-hydroxybenzotriazine, and 4-chlorobenzotriazine.

9. A method for preparing a diluted resin solution with long-term storage stability according to any one of claims 1-8, characterized in that, The preparation method includes the following steps: S1. Vacuum dry the acrylate resin to obtain dried acrylate resin; S2. Mix and stir the diluent, 1-methoxy-2-propyl acetate, chemical stabilizer, modified dipropylene glycol methyl ether and dipropylene glycol dimethyl ether, add 3A molecular sieve, filter through filter membrane to obtain the mixture; S3. Add the dried acrylate resin to the mixture and stir. Add the physical stabilizer and stir. Add triethanolamine to obtain material A. Vacuum degas material A and filter it through a filter membrane to obtain a diluted resin solution with long-term storage stability.

10. A packaging process for a diluted resin solution with long-term storage stability according to any one of claims 1-9, characterized in that, The packaging process uses brown bottles with an oxygen permeability of ≤0.1cm. 3 / (m 2 (24h·atm), bottle cap with PTFE liner, headspace oxygen concentration ≤1%.

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