A method for improving the adhesion of HMMM resin using methylal.

Abstract

The present invention discloses a method for improving the adhesiveness of HMMM resin with methylal, and this method includes the following steps: S1, Preparation of raw materials: 9.36 - 12.48 mol of methanol, 0.408 - 4.08 mol of catalyst additive and 0.408 - 0.816 mol of hexahydroxymethylmelamine are prepared; S2, Preparation of HMMM resin: S2 - 1, Methanol, catalyst additive and hexahydroxymethylmelamine are sequentially added into a 1000 mL reaction kettle equipped with a stirrer and a reflux condenser, and the remaining methylal, methanol and water are heated up and evaporated under alkaline conditions, and distilled under reduced pressure to obtain HMMM resin. The present invention plays a role in promoting the reaction between methylal and water to generate hexamethoxymethylmelamine due to the combined effect of catalyst additive A and catalyst additive B, enhances the water absorption effect of the methylal solution, and at the same time, when the magnetic cobalt oxide is a magnetic cation exchange resin, it is fully mixed with methanol, further promotes the etherification reaction, enhances the etherification effect, and can effectively improve the adhesiveness of HMMM resin.

Description

Technical Field

[0001] The present invention relates to the technical field of resin preparation, specifically to a method for improving the adhesion of HMMM resin with methylal.

Background Art

[0002] HMMM resin is an abbreviation for hexamethoxymethylmelamine formaldehyde resin, and is also called 5 60 resin. HMMM resin has the appearance of a colorless or light yellow transparent viscous liquid, and has characteristics such as excellent heat resistance, water resistance, and good compatibility with resins. HMMM resin has low toxicity and can be used as a crosslinking agent for water-based acrylate and water-based epoxy resin adhesives, and can improve the performance of adhesives such as water resistance and heat resistance. Furthermore, HMMM resin can also be used in the preparation of coatings, gelling agents, amino resins, etc. As the main adhesive for rubber, it is used together with a methylene acceptor, and plays a role in adhering rubber to steel wire yarn and other skeletal materials. In the etherification reaction of methanol and hexahydroxymethylmelamine for preparing the etherification reaction of HMMM resin, methylal (Methylal is a compound produced by the dehydration of formaldehyde and methanol, and can "absorb" the water generated in the etherification reaction, and has no other effect on the etherification reaction itself), through the equilibrium reaction of the added methylal with methanol, formaldehyde, and water, the free water generated in the etherification reaction system can be reduced, and the etherification reaction can proceed in a direction favorable for the formation of etherification products. The reduction of water can also reduce intermolecular condensation, and the HMMM resin prepared by the above method can improve the adhesion of HMMM resin to a certain extent. ​​​​It is possible, but the improvement effect is limited. [Overview of the Initiative]

[0003] To solve the above technical problems, the present invention provides methylal for the adhesion of HMMM resin. This provides a method to improve the situation. The technical solution of the present invention is as follows: Adhesion of HMMM resin by methylal The method to improve this includes the following steps: S1, Preparation of raw materials 9.36-12.48 mol methanol, 0.408-4.08 mol catalyst additive Prepare 0.408 to 0.816 mol of hexahydroxymethylmelamine and the above-mentioned contact The catalyst additive consists of catalyst additive A and catalyst additive B, where catalyst additive A is composed of mass % Then, 5-10% ammonium trifluoromethanesulfonate, 1-3% hydrothoro It consists of toluene and the remaining mixture, the mixture being methylal solution:anhydrous ethanol or The catalyst additive B is prepared in a volume ratio of 1:1 to 2, and the catalyst additive B is prepared in a volume ratio of catalyst additive A and the catalyst additive Agent A consists of magnetic cobalt oxide in a mass ratio of 3.5-5%. Preparation of S2, HMMM resin S2-1, methanol, catalyst additive, and hexahydroxymethylmelamine were returned to a stirrer. Add sequentially to a 1000 mL reaction vessel equipped with a flow condenser. S2-2. Raise the temperature of the reaction vessel to 45-55°C and wait until the substance inside the reaction vessel becomes clear. Keep warm, continue stirring for 40-50 minutes, then add alkaline solution to adjust the pH to 8-9. Then, raise the temperature to evaporate the remaining methylal, methanol, and water until the temperature reaches 85-95°C. Once it reaches 105-115°C, start the vacuum system and continue heating, then 25-35 Stir for a minute and maintain the temperature, then cool to 85-95°C, filter, and distill under reduced pressure. MMM resin is obtained. Description: Ammonium trifluoromethanesulfonate is methylated in the etherification reaction. It plays a role in effectively promoting the reaction between the substance and water to produce hexamethoxymethylmelamine. Furthermore, it improves the water absorption effect of the methylal solution and does not affect the water absorption efficiency of methylal. It can reduce the impact on the etherification reaction of hydrolomethanesulfonic acid, Toluene has a certain degree of solubility and stability, and promotes the reaction of methylal with water to form hexa It can generate methoxymethylmelamine, improving the water absorption effect of methylal solution. The magnetic cobalt oxide contained in catalyst additive B is methanol when used in magnetic cation exchange resins. Mix thoroughly with the etherification reaction and other organic substances to further promote the etherification effect. This can increase the viscosity, and consequently improve the viscosity of the HMMM resin. Furthermore, in step S2-1, methanol, catalyst additive and hexahydrox The steps for adding methylmelamine are as follows: S2-1-1, in a reaction vessel, combine 1 / 4 to 3 / 4 methanol and hexahydroxymethylmelamine. Adding hexahydroxymethylmelamine in a mass ratio of 5-5.5% catalyst additive A, S2-1-2, raise the temperature of the reaction vessel to 35-40°C, and continue adding 1 / 4-3 / 4 of the methanol. Add the remaining amount of catalyst additive A, keep warm for 25-30 minutes, and stir to mix uniformly. Then, the temperature is raised to 60-70°C, and the remaining methanol and the entire amount of catalyst additive B are added. Next, keep it warm for 35-50 minutes, then stir to mix evenly. Explanation: First, add catalyst additive A in the above proportions, then raise the temperature and add methanol and catalyst additive B. By adding this, the magnetic cobalt oxide can be dispersed more effectively in methylal. , further improving the etherification effect and the effect of methylal on improving the viscosity of HMMM resin It can be improved. Furthermore, in step S1, the method for preparing the catalyst additive A is as follows: 1) Remove hydrothrosotoluene and ammonium trifluoromethanesulfonate and stir in a stirring vessel. In addition, the mixture is vacuum dispersed at 95-105°C for 2-2.5 hours to obtain a premix, and then prepared. 2) Purify the methylal solution to a purity of 99.1-99.9% for 2-3 hours, and then adjust the proportions accordingly. Therefore, prepare a mixture by mixing methylal solution with anhydrous ethanol. 3) First, add the mixture obtained in step 2) to the reaction vessel and use an atomizer to step 1) The premix obtained in step 1) is processed to a particle size of 2-3 μm, and then heated at 55-60°C. The premix is ​​passed through the reaction vessel at a rate of 30-50 mL / min at a given temperature, with a passing time of 50 minutes. The process takes 60 minutes, during which the temperature is raised to 75-80°C, followed by a continuous 30-40 minutes. Stir at a speed of 120-150 r / min throughout the process to ensure uniform mixing, and finally stir for 20-25 Cool to °C to obtain catalyst additive A. Explanation: First, hydrotrosotoluene and ammonium trifluoromethanesulfonate are added under vacuum. By dispersing and then atomizing, the uniform dispersion of the premix is ​​effectively promoted. To improve its quality and stability, atomization increases the surface area of ​​the material, and the reaction rate and It can improve adsorption performance, and at the same time promote uniform dispersion and stability of materials, methylal After purifying the solution, catalyst additive A is prepared to facilitate the etherification reaction of methylal. It promotes the action, and at the same time, ammonium trifluoromethanesulfonate is trifluoromethane While having the acidity of p-toluenesulfonic acid, it also has a small inhibitory effect on the etherification reaction, and HMM can provide an acidic environment during the preparation process of M resin, reduce the additional addition of acid solution, and reduce the preparation cost can be achieved. Furthermore, in step 2), the method of the purification treatment is as follows: Mix the methylal solution and the decontaminant according to a mass ratio of 7 - 10:25 - 35, stir at 55 - 60 °C for 25 - 35 m in, then let it stand for 1 - 1.5 h, use an adsorbent to perform ultrasonic adsorption treatment on the upper layer of the standing liquid under the conditions of an ultrasonic frequency of 35 - 40 kHz and an ultrasonic output of 7 00 - 800 W, then cool the standing liquid to 20 - 25 °C, continue to separate and remove the upper layer impurities, use a distillation column to distill the bottom mixture at normal temperature and normal pressure to obtain a purified methylal solution, the ultrasonic adsorption time is 15 - 20 min, the operating pressure of the distillation column is 100 - 110 kPa, and the adsorbent is selected from any one of molecular sieves and activated carbon, Explanation: The above steps can efficiently purify the methylal solution, effectively improve the performance of methylal itself, and further improve the promoting effect of methylal on the adhesiveness of HMMM resin. Furthermore, the decontaminant consists of 20 - 25% oxalic acid, 5 - 10% composite gel and the remaining amount of ammonium oxalate in mass%, Explanation: The decontaminant adopting the above composition can effectively remove the impurities in the methylal solution while having little impact on the performance of methylal. Furthermore, the composite gel is a modified composite gel obtained after modification treatment, and the preparation method of the modified composite gel is as follows: Adjust the pH to 2 - 3 using hydrochloric acid with a mass concentration of 10%, and with a molar ratio of 1:1.5 - 3 of methyl silane Explanation: The decontaminant adopting the above composition can effectively remove the impurities in the methylal solution while having little impact on the performance of methylal. Furthermore, the composite gel is a modified composite gel obtained after modification treatment, and the preparation method of the modified composite gel is as follows: Adjust the pH to 2 - 3 using hydrochloric acid with a mass concentration of 10%, and with a molar ratio of 1:1.5 - 3 of methyl silane Sodium licate and hydrogel are mixed in a reaction vessel to undergo polymerization and obtain a precursor solution. The mass ratio of the precursor solution:ethanol:deionized water is 2.5-4.5:5-7:5-7. Then, ethanol and deionized water are added sequentially to the reaction vessel, and heated to 85-90°C, and 25-35 Maintain a constant temperature and stir, then allow the maturation reaction to proceed at a temperature of 20-25°C for 2-3 days. And finally, the mixture prepared above is subjected to vacuum drying to obtain a modified composite gel, and here, Drying temperature: 50-60°C, drying time: 1-2 hours. Description: Hydrogels are highly hydrophilic three-dimensional network gels that swell rapidly in water. Because it can retain a large amount of water without dissolving in this swollen state, it has strong water absorption capabilities. The silicate molecule is polymerized with the hydrogel, and the silicate chain segment and hydrogel It produces copolymers containing both chain segments, and has the effect of removing impurities, Since the gel can be given water-absorbing properties, the water absorption effect can be further enhanced, H This is to improve the adhesion of MMM resin. Furthermore, the ammonium trifluoromethanesulfonate is modified, and modified trifluoromethanesulfonate We obtained ammonium tansulfonate, The aforementioned modified ammonium trifluoromethanesulfonate is a benzenesulfonic acid crystal: plasticizer. Agent: Ammonium trifluoromethanesulfonate:Polyvinyl alcohol in a mass ratio of 1~ It is prepared by mixing in a ratio of 1.2:0.4~0.6:2~3:3-5. The method for preparing the modified ammonium trifluoromethanesulfonate is as follows: First, dry the benzenesulfonic acid crystals in an oven at a temperature of 40-45°C, and then dry them. The dried benzenesulfonic acid crystals and plasticizer are uniformly mixed and heated until molten, resulting in the mixed liquid M. Obtain the ammonium trifluoromethanesulfonate and polyvinyl alcohol in proportion to the obtained ammonium trifluoromethanesulfonate and polyvinyl alcohol. Prepare a mixture and mix it to obtain a mixed solution N. The mixture M is extruded in an extruder into particles with a particle size of 1 to 3 μm, and the particles are heated to -5°C. The mixture is cooled in a 5°C cooling device, molded, and finally the mixed liquid N is sprayed onto the surface of the particulate matter. Stir evenly, then dry in a room temperature dryer to prepare. Explanation: The above method first plasticizes benzenesulfonic acid crystals, and then trifluoromethane By spraying ammonium sulfonate onto the surface of benzenesulfonic acid particulate matter, modification occurs. It plays a role in increasing the specific surface area of ​​ammonium trifluoromethanesulfonate, Promoting action of ammonium denatured trifluoromethanesulfonate during the etherification process of lar. To further improve this, thereby increasing the water absorption capacity produced by the etherification reaction, By reducing the amount of free water generated in the tellucation reaction system, the performance of HMMM resin is significantly improved. It can be done. Furthermore, the plasticizer is epoxidized vegetable oil, trimethoxysilane, polyethylene glyco It is one of the following: Description: The above plasticizer can promote the melting of benzenesulfonic acid crystals. Therefore, the efficiency of preparing particulate matter can be improved. Furthermore, the alkaline solution is a sodium hydroxide solution with a mass fraction of 10-15%, This is one of the following 10-15% potassium hydroxide solutions. Description: The above alkaline solution does not generate harmful substances during use, does not cause environmental pollution, and efficiently adjusts pH. This can be changed to further improve the processing effect. [Effects of the Invention]

[0004] The present invention has the following beneficial effects. (1) The present invention promotes the reaction between methylal and water using catalyst additive A and catalyst additive B. It plays a role in generating xamethoxymethylmelamine, which enhances the water absorption effect of methylal solution. Furthermore, when the magnetic cobalt oxide is a magnetic cation exchange resin, it is thoroughly mixed with methanol. This further promotes the etherification reaction, enhances the etherification effect, and improves the adhesion of HMMM resin. It can be effectively improved. (2) The present invention prepares a modified composite gel using a polymerization reaction between silicate molecules and hydrogels. Therefore, the modified composite gel has the effect of removing impurities from the methylal solution, and at the same time , utilizing the three-dimensional network structure of the hydrogel, it swells rapidly in water, and in this swollen state It also has strong water absorption properties, further enhancing the effect of promoting the etherification reaction and improving the adhesion of HMMM resin. It can be improved. (3) The present invention involves plasticizing benzenesulfonic acid crystals and then the surface of benzenesulfonic acid particles. By spraying ammonium trifluoromethanesulfonate onto the surface, modified trifluoro The specific surface area of ​​ammonium romethanesulfonate can be effectively increased, and by this, Furthermore, in the etherification process, modified ammonium trifluoromethanesulfonate This can further enhance the etherification-promoting effect of methylal, and also benzenesulfonic acid By using crystals as a support, a strongly acidic environment can be provided, and polyvinyl It enhances the activity of ammonium trifluoromethanesulfonate and promotes the diffusion of H This can significantly improve the adhesive performance of MM resin. [Modes for carrying out the invention]

[0005] In order to better reflect the advantages of the present invention, the present invention will be described below in relation to specific embodiments. I will explain in more detail. Example 1: A method for improving the adhesion of HMMM resin with methylal is as follows: Includes: S1, Preparation of raw materials 10.92 mol methanol, 2.03 mol catalyst additive and 0.627 mol Prepare hexahydroxymethylmelamine, and the catalyst additives are catalyst additive A and catalyst additive B. Therefore, here, catalyst additive A is 7% by mass of trifluoromethanesulfonic acid It consists of mononium, 2% hydrotrosotoluene, and the remainder in a mixture, and the mixture is methyl Solution: Prepared by adding anhydrous ethanol in a volume ratio of 1:1.5, and catalyst additive B is a catalyst additive It consists of magnetic cobalt oxide in a mass ratio of agent A and catalyst additive A of 4.3%. In step S1, the method for preparing catalyst additive A is as follows: 1) Remove hydrothrosotoluene and ammonium trifluoromethanesulfonate and stir in a stirring vessel. In addition, the mixture is vacuum dispersed at 100°C for 2.3 hours to obtain a premix, and then prepared. 2) Purify the methylal solution to a purity of 99.5% for 2.5 hours, and then methylal according to the proportions. Prepare a mixture by mixing the lar solution with anhydrous ethanol. 3) First, add the mixture obtained in step 2) to the reaction vessel and use an atomizer to step 1) The premix obtained in step 1) is atomized to a particle size of 2.5 μm, and then heated at a temperature of 58°C for 4 The premix was passed through the reaction vessel at a rate of 0 mL / min, and the passing time was 55 min. The temperature was raised to 8°C, and then the process continued for 35 minutes at a rate of 135 r / min during the process. Stirring to ensure uniform mixing, and finally cooling to 23°C to obtain catalyst additive A. Preparation of S2, HMMM resin S2-1, methanol, catalyst additive, and hexahydroxymethylmelamine were returned to a stirrer. Add sequentially to a 1000 mL reaction vessel equipped with a flow condenser. The steps for adding methanol, catalyst additives, and hexahydroxymethylmelamine are as follows: It is a street: S2-1-1, Add 2 / 4 methanol and hexahydroxymethylmelamine to the reaction vessel. Add catalyst additive A containing hexahydroxymethylmelamine in a mass ratio of 5.3%. S2-1-2, raise the temperature of the reaction vessel to 37°C, and continue adding 1 / 4 methanol and the remainder Add catalyst additive A in the specified amount, keep warm for 28 minutes, stir to mix uniformly, then reduce the temperature to 6 Raise the temperature to 0-70°C, add the remaining methanol and the entire amount of catalyst additive B, and keep warm for 43 minutes. Then, stir and mix uniformly. S2-2. Raise the temperature of the reaction vessel to 50°C, wait until the substance inside the reaction vessel becomes clear, and then maintain the temperature. Continue stirring for 45 minutes, then add the alkaline solution to adjust the pH to 8.5, and the remaining Methylal, methanol, and water are heated and evaporated until the temperature reaches 90°C, then vacuum is applied. Start the system and continue raising the temperature. When it reaches 110°C, stir for 30 minutes and maintain the temperature. Then, it is cooled to 90°C and filtered, and distilled under reduced pressure to obtain HMMM resin. In step 2), the purification process is as follows: Methylal solution: Decontamination agent Mix at a mass ratio of 8:30, stir at 58°C for 30 minutes, then let stand for 1.3 hours, and then use ultrasonic waves. Under conditions of a wavenumber of 37 kHz and an ultrasonic output of 750 W, the upper layer of a standing liquid is ultrasonically absorbed using an adsorbent. After the initial treatment, the standing liquid is cooled to 22°C, and then upper layer impurities are separated and removed, and the distillation column is used. The bottom mixture was distilled at room temperature and pressure to obtain a purified methylal solution, and then ultrasonic adsorption was performed. The time was 18 minutes, the operating pressure of the distillation column was 105 kPa, and activated carbon was selected as the adsorbent. The selected decontamination agent consists of 23% oxalic acid, 7% composite gel, and the remainder of oxalic acid by mass. It consists of 'mmonium', The composite gel is a modified composite gel obtained after modification treatment, and the method for preparing the modified composite gel is as follows: It is a street: The pH was adjusted to 2.5 using 10% hydrochloric acid by mass, and methyl silicate was added in a molar ratio of 1:2.2. Sodium phosphate and hydrogel are mixed in a reaction vessel to undergo polymerization, and a precursor solution is obtained. The mass ratio of the ethanol to the deionized water in the carbide solution is 3.5:6:6, according to the ratio of ethanol to deionized water. Prepare the water sequentially, add it to the reaction vessel, heat to 87°C, keep warm and stir for 30 minutes, and then The subsequent maturation reaction was carried out at a temperature of 23°C for 2.5 days, and finally the preparation described above was completed. The mixture was subjected to vacuum drying to obtain a modified composite gel, where drying temperature: 55°C, drying time: 1 It is 0.5 hours. Example 2: Unlike Example 1, in step S1, 9.36 mol methanol, 0.408 mol of catalyst additive and 0.408 mol of hexahydroxymethylmelamine Prepare the n. Example 3: Unlike Example 1, in step S1, 12.48 mol methanol , 4.08 mol of catalyst additive and 0.816 mol of hexahydroxymethylmelamine Prepare the n. Example 4: Unlike Example 1, in step S1, catalyst additive A is 5% by mass. % ammonium trifluoromethanesulfonate, 1% hydrotrosotoluene and the remainder It consists of a mixture of methylal solution and anhydrous ethanol prepared in a volume ratio of 1:1. It becomes. Example 5: Unlike Example 1, in step S1, catalyst additive A is 1 by mass%. 0% ammonium trifluoromethanesulfonate, 3% hydrotrosotoluene and The remaining mixture consists of a methylal solution and anhydrous ethanol prepared in a volume ratio of 1:2. It becomes. Example 6: Unlike Example 1, the method for preparing catalyst additive A in step S1 is as follows: As stated above: 1) Remove hydrothrosotoluene and ammonium trifluoromethanesulfonate and stir in a stirring vessel. In addition, the mixture is vacuum dispersed at 95°C for 2.5 hours to obtain a premix, and then prepared. 2) Purify the methylal solution to 99.1% purity for 2 hours, then process according to the proportions. Prepare a mixture by mixing the solution with anhydrous ethanol. 3) First, add the mixture obtained in step 2) to the reaction vessel and use an atomizer to step 1) The premix obtained in step 1) is atomized to a particle size of 2-3 μm, and then heated at a temperature of 55°C for 5 minutes. The premix was passed through the reaction vessel at a rate of 0 mL / min, and the passing time was 50 min. The temperature was raised to 5°C, and then the mixture was passed through for 40 minutes, stirring at a rate of 120 r / min during the process. The mixture is stirred to ensure uniformity, and finally cooled to 20°C to obtain catalyst additive A. Example 7: Unlike Example 1, the method for preparing catalyst additive A in step S1 is as follows: As stated above: 1) Remove hydrothrosotoluene and ammonium trifluoromethanesulfonate and stir in a stirring vessel. In addition, the mixture is vacuum dispersed at 95°C for 2.5 hours to obtain a premix, and then prepared. 2) Purify the methylal solution to 99.9% purity for 2 hours, then process according to the proportions. Prepare a mixture by mixing the solution with anhydrous ethanol. 3) First, add the mixture obtained in step 2) to the reaction vessel and use an atomizer to step 1) The premix obtained in step 1) is atomized to a particle size of 2-3 μm, and then heated at a temperature of 60°C for 5 minutes. The premix was passed through the reaction vessel at a rate of 0 mL / min, and the passing time was 60 min. The temperature was raised to 0°C, and then the mixture was passed through for 30 minutes, stirring at a rate of 150 r / min during the process. The mixture is stirred to ensure uniformity, and finally cooled to 25°C to obtain catalyst additive A. Example 8: Unlike Example 1, in step 2), the purification process is as follows: Mix methylal solution and decontamination agent according to a mass ratio of 7:25 and incubate at 55°C for 35 minutes. Stirring, then letting stand for 1 hour, and then suction under ultrasonic conditions of ultrasonic frequency 35kHz and ultrasonic output 700W. The upper layer of the standing solution is subjected to ultrasonic adsorption using an adhesive, and then the standing solution is cooled to 20°C. Next, the upper layer impurities are separated and removed, and the bottom mixture is distilled using a distillation column at room temperature and atmospheric pressure to purify it. A methylal solution was obtained after preparation, the ultrasonic adsorption time was 15 min, and the operating pressure of the distillation column was 1 It is 00 kPa. Example 9: Unlike Example 1, in step 2), the purification method is as follows: Mix methylal solution and decontamination agent according to a mass ratio of 10:35 and heat at 60°C for 25 minutes. The mixture was stirred, then allowed to stand for 1.5 hours under the following conditions: ultrasonic frequency 40kHz, ultrasonic output 800W. The upper layer of the standing solution is subjected to ultrasonic adsorption using an adsorbent below, and then the standing solution is cooled to 25°C. Next, the upper layer impurities are separated and removed, and the bottom mixture is distilled at room temperature and atmospheric pressure using a distillation column. Then, a purified methylal solution was obtained, the ultrasonic adsorption time was 20 min, and the operating pressure of the distillation column was The force is 110 kPa. Example 10: Unlike Example 1, in step 2), the decontamination agent is 20% by mass. It consists of oxalic acid, 5% composite gel, and the remainder being ammonium oxalate. Example 11: Unlike Example 1, in step 2), the decontamination agent is 25% by mass. It consists of oxalic acid, 10% composite gel, and the remainder being ammonium oxalate. Example 12: Unlike Example 1, in step S2-1, methanol and catalyst additives are used. The steps for adding hexahydroxymethylmelamine are as follows: S2-1-1, Add 1 / 4 methanol and hexahydroxymethylmelamine to the reaction vessel. Add catalyst additive A containing hexahydroxymethylmelamine in a mass ratio of 5%, S2-1-2, raise the temperature of the reaction vessel to 35°C, and continue adding 2 / 4 methanol and the remainder Add catalyst additive A in the specified amount, keep warm for 25 minutes, stir to mix uniformly, then reduce the temperature to 60°C. The temperature rises to ℃, add the remaining methanol and the entire amount of catalyst additive B, maintain the temperature for 50 minutes, and stir. Then mix uniformly. Example 13: Unlike Example 1, in step S2-1, methanol and catalyst additives are used. The steps for adding hexahydroxymethylmelamine are as follows: S2-1-1, Add 2 / 4 methanol and hexahydroxymethylmelamine to the reaction vessel. Add catalyst additive A containing hexahydroxymethylmelamine in a mass ratio of 5.5%. S2-1-2, raise the temperature of the reaction vessel to 40°C, and continue adding 1 / 4 methanol and the remainder Add catalyst additive A in the specified amount, keep warm for 30 minutes, stir to mix uniformly, then reduce the temperature to 70°C. Heat to ℃, add the remaining methanol and the entire amount of catalyst additive B, maintain temperature for 35 minutes, and stir. Stir to mix uniformly. Example 14: Unlike Example 1, in step S2-2, the reaction vessel was heated to 45°C. Wait until the substance in the reaction vessel becomes clear, then maintain the temperature and continue stirring for 50 minutes. Then, add the alkaline solution to adjust the pH to 8, and add the remaining methylal, methanol, and water. Heat and evaporate, and after the temperature reaches 85°C, activate the vacuum system and continue to raise the temperature to 105°C. When it reaches ℃, stir for 35 minutes and maintain the temperature, then cool to 85℃, filter, and reduce pressure. Distillation is performed below to obtain HMMM resin. Example 15: Unlike Example 1, in step S2-2, the reaction vessel was heated to 55°C. Wait until the substance in the reaction vessel becomes clear, then maintain the temperature and continue stirring for 40 minutes. Then, add the alkaline solution to adjust the pH to 9, and add the remaining methylal, methanol, and water. Heat and evaporate, and after the temperature reaches 95°C, activate the vacuum system and continue to raise the temperature to 115°C. When it reaches ℃, stir for 25 minutes and maintain the temperature, then cool to 95℃, filter, and reduce pressure. Distillation is performed below to obtain HMMM resin. Example 16: Unlike Example 1, the method for preparing the modified composite gel is as follows: The pH was adjusted to 2 using 10% hydrochloric acid by mass, and methyl silicate was added in a molar ratio of 1:1.5. Sodium and hydrogel are mixed in a reaction vessel to undergo polymerization, and a precursor solution is obtained. Solution:Ethanol:Deionized water in a mass ratio of 2.5:5:5, according to the formula, ethanol and deionized water. Prepare the water in stages, add it to the reaction vessel, heat to 85°C, keep warm and stir for 35 minutes, then adjust the temperature. The aging reaction was carried out at 20°C for 3 days, and finally the mixture prepared above was fermented. The gel was air-dried to obtain a modified composite gel, with a drying temperature of 50°C and a drying time of 2 hours. Example 17: Unlike Example 1, the method for preparing the modified composite gel is as follows: The pH was adjusted to 3 using 10% hydrochloric acid by mass, and methyl silicate sodium was added in a molar ratio of 1:3. The lium and hydrogel are mixed in a reaction vessel to undergo polymerization, and a precursor solution is obtained. Ethanol and deionized water are mixed according to a mass ratio of 4.5:7:7. Prepare the ingredients in order, add them to the reaction vessel, heat to 90°C, keep warm and stir for 25 minutes, then the temperature will rise to 25°C. The aging reaction was carried out at °C for 2 days, and finally the mixture prepared above was vacuum dried. The gel was dried to obtain a modified composite gel, where the drying temperature was 60°C and the drying time was 1 hour. Example 18: Unlike Example 1, ammonium trifluoromethanesulfonate was modified. , obtain modified ammonium trifluoromethanesulfonate, Modified ammonium trifluoromethanesulfonate is a benzenesulfonic acid crystal: plasticizer: Ammonium trifluoromethanesulfonate:Polyvinyl alcohol in a mass ratio of 1:0.4 Prepared by mixing in a 2:3 ratio. The method for preparing modified ammonium trifluoromethanesulfonate is as follows: First, The benzoyl sulfonic acid crystals were dried in an oven at 40°C, and then the dried benzoyl sulfonic acid crystals were processed. Zensulfonic acid crystals and a plasticizer are uniformly mixed and heated to a molten state to obtain a mixture M, and the proportion Prepare ammonium trifluoromethanesulfonate and polyvinyl alcohol accordingly. Mix to obtain mixed solution N, The mixture M is extruded into particles with a diameter of 1-3 μm using an extruder, and the particles are cooled to a temperature of -5°C. Place in a cooler, mold, and finally spray the mixed liquid N onto the surface of the above particles and stir uniformly. Then, dry them in a room-temperature drying oven to prepare them. Example 19: Unlike Example 18, modified ammonium trifluoromethanesulfonate is Benzene sulfonic acid crystals: Plasticizer: Ammonium trifluoromethanesulfonate: Poly It is prepared by mixing vinyl alcohol in a mass ratio of 1.1:0.5:2.5:4. In a method for preparing modified ammonium trifluoromethanesulfonate, first, benzenesulfonate The honic acid crystals were dried in an oven at 43°C, and the mixture M was extruded in an extruder to form particles with a particle size of 1~ The material is extruded into 3 μm particles, which are then cooled in a cooling device at 0°C to form the shape. Example 20: Unlike Example 18, modified ammonium trifluoromethanesulfonate is Benzene sulfonic acid crystals: Plasticizer: Ammonium trifluoromethanesulfonate: Poly It is prepared by mixing vinyl alcohol in a mass ratio of 1.2:0.6:3:5. In the method for preparing ammonium trifluoromethanesulfonate, first, benzenesulfon The acid crystals were dried in an oven at 45°C, and the mixture M was extruded using an extruder to produce particles with a size of 1-3 μm. The material is extruded into m-sized particles, and the particles are cooled in a cooling device at a temperature of 5°C to form the shape. Experimental example: For the HMMM resin prepared in each example, 5 samples were taken from each example. Individual samples were taken, and the viscosity and degree of etherification test results of the five samples from each example were averaged to the following values. The performance measurement results of the example were specifically explored as follows: 1. Investigation of the effect of the composition and proportion of catalyst additives on the adhesive performance of HMMM resin. Table 1 Performance of HMMM resins prepared in Examples 1-11, 16-18 and Control Examples 1-2 TIFF2026512193000001.tif110144 Control Example 1: Unlike Example 1, the premix is ​​not atomized in step 3). Control Example 2: Unlike Example 1, in step 2), the purification method directly uses the decontamination agent. The method involves using methylal solution to decontaminate the area. Conclusion: As can be seen from the data of Examples 1-3 in Table 1, the content of the catalyst additive was prepared. The effect on the adhesive performance of the HMMM resin was small, and from the data of Examples 1 and 4-5... As you can see, the ratio of ammonium trifluoromethanesulfonate to hydrothrosotoluene As the compound increases, the performance of HMMM resin tends to increase first, then decrease later. The best result was obtained with the ratio in Example 1, which suggests that in the synthesis process of methylal, an appropriate amount of Ammonium difluoromethanesulfonate can catalyze the production of methylal, It can improve the yield and purity of the product, but excessive amounts have adverse effects, and hydrotrophic Sotoluene can improve the water absorption performance of methylal, and hydrothrosotoluene is excessive In excess cases, many microstructures are formed within methylal, affecting its water absorption capacity and absorption rate. It improves the stability, but if hydrotrosotoluene is in excess, it affects the stability of methylal. It reduces the methylal-promoting effect on the methylation reaction, As can be seen from the data comparison of Example 1, Examples 6-7 and Control Example 1, in the control example, atomization treatment Catalyst additive A, prepared without processing, has a small effect on promoting the adhesion performance of HMMM resin. This first involves hydrothrosotoluene and ammonium trifluoromethanesulfonate. By atomizing the premix after air dispersion, the uniform dispersion of the premix is ​​effectively promoted. This process improves quality and stability, and atomization increases the surface area of ​​the material, improving reaction rate and adsorption. It can improve performance and simultaneously contribute to the uniform dispersion and stability of the material. This can be seen from the data comparison between Example 1, Examples 8-11, Examples 16-18 and Control Example 2. In control example 2, treating the methylal solution directly with a decontamination agent showed a certain decontamination effect. However, its effect is limited, and Examples 16-18 modify the composite gel in the decontamination agent composition. By doing so, the composite gel has a decontamination effect and water absorption properties, thereby H To achieve the objective of further improving the adhesion of MMM resin, and considering all factors, Example 17 The adhesive performance of the HMMM resin prepared using this method is optimal. 2. Investigation of the effect of the HMMM resin preparation process on the adhesive performance of HMMM resin. Table 2 Performance of HMMM resins prepared in Examples 1, 12-15 and Control Example 3 TIFF2026512193000002.tif33139 Control Example 3: Unlike Example 1, in step S2-1, catalyst additive A, catalyst additive Mix B with methanol and hexahydroxymethylmelamine by direct stirring until homogeneous. Conclusion: As can be seen from the data comparison of Example 1, Examples 12-13 and Control Example 4 in Table 2, Catalyst additive A and catalyst additive B are added to the reaction vessel in stages to further enhance the effect of catalyst additive B. This improves the process, effectively dispersing magnetic cobalt oxide with methylal and enhancing the etherification effect. To further improve this, thereby enhancing the viscosity-improving effect of methylal on HMMM resin viscosity. As can be seen from the data comparison between Example 1 and Examples 14-15, Claim 1 Preparation parameters for HMMM resin within the specified range have little effect on the adhesion properties of HMMM resin. 3. Modification of ammonium trifluoromethanesulfonate affects the adhesion performance of HMMM resin. Investigation of the impact Table 3 Performance of HMMM resins prepared in Example 17 and Examples 18-20 TIFF2026512193000003.tif46133 Conclusion: As can be seen from the data comparison of Examples 17-20 in Table 3, the preparations made in Examples 18-20 The adhesive performance of the HMMM resin was significantly improved compared to Example 17, and the adjustments made in Example 19 were made. The adhesive performance of the manufactured HMMM resin is superior, and this is because it plasticizes benzenesulfonic acid crystals. Then, ammonium trifluoromethanesulfonate is placed on the surface of benzenesulfonic acid particulate matter. By spraying it onto a surface, the specific surface area of ​​modified ammonium trifluoromethanesulfonate is increased. It effectively increases the methylal etherification process, and modifies trifluoromethylal during the etherification process. The ammonium tansulfonate enhances its promoting effect, and benzenesulfonic acid crystals act as a strong carrier. It provides an acidic environment, enhances the activity of polyvinyl alcohol, and trifluoromethanesulfonic acid The diffusion of ammonium is promoted, significantly improving the adhesive performance of HMMM resin. Therefore.

Claims

1. The following steps are included: Step S1: Preparation of raw materials 9.36–12.48 mol of methanol, 0.408–4.08 mol of catalyst additive Prepare hexahydroxymethylmelamine in an amount of 0.408 to 0.816 mol, and the above-mentioned chemical The catalyst additive consists of catalyst additive A and catalyst additive B, where catalyst additive A is composed of mass % Then, 5-10% ammonium trifluoromethanesulfonate, 1-3% hydrothoro It consists of toluene and the remaining mixture, the mixture being methylal solution:anhydrous ethanol or The catalyst additive B is prepared in a volume ratio of 1:1 to 2, and the catalyst additive B is prepared in a volume ratio of catalyst additive A and the catalyst additive Agent A consists of magnetic cobalt oxide in a mass ratio of 3.5 to 5%. Step S2, Preparation of HMMM resin Step S2-1, Stir methanol, catalyst additive and hexahydroxymethylmelamine. The mixture is sequentially added to a 1000 mL reaction vessel equipped with a mixer and reflux condenser. Step S2-2: Heat the reaction vessel to 45-55°C until the substance inside the vessel becomes clear. Wait, keep warm, continue stirring for 40-50 minutes, then add the alkaline solution to bring the pH to 8-9. Adjust to the desired temperature, then raise the temperature to evaporate the remaining methylal, methanol, and water until the temperature reaches 85°C. When it reaches ~95°C, start the vacuum system and continue to raise the temperature, and when it reaches 105-115°C, 2 Stir for 5-35 minutes and maintain temperature, then cool to 85-95°C, filter, and steam under reduced pressure. To obtain HMM resin, A method for improving the adhesion of HMMM resin by using methylal, characterized by the above.

2. In step S2-1, methanol, catalyst additive and hexahydroxymethyl The melamine addition steps are as follows: Step S2-1-1: Add 1 / 4 to 3 / 4 methanol and hexahydroxymethyl methyl ester to the reaction vessel. Adding melamine, catalyst additive A contains hexahydroxymethylmelamine in a mass ratio of 5-5.5%. Add, Step S2-1-2: Raise the temperature of the reaction vessel to 35-40°C and add 1 / 4 to 3 / 4 of the methanol. Add the remaining amount of catalyst additive A, keep warm for 25-30 minutes, and stir to mix uniformly. Then, the temperature is raised to 60-70°C, and the remaining methanol and the entire amount of catalyst additive B are added. The method described in paragraph 1 is characterized by keeping the mixture warm for 35 to 50 minutes and stirring to mix it uniformly. A method for improving the adhesion of HMMM resin using methylal.

3. In step S1, the method for preparing the catalyst additive A is as follows: 1) Remove hydrothrosotoluene and ammonium trifluoromethanesulfonate and stir in a stirring vessel. In addition, the mixture is vacuum dispersed at 95-105°C for 2-2.5 hours to obtain a premix, and then prepared. 2) Purify the methylal solution for 2-3 hours until it reaches a purity of 99.1-99.9%, and then... Prepare the mixture by mixing the methylal solution and anhydrous ethanol according to the instructions. 3) First, add the mixture obtained in step 2) to the reaction vessel and use an atomizer to step 1) The premix obtained in step 1) is atomized to a particle size of 2-3 μm, and then 55-60 The premix is ​​passed through the reaction vessel at a rate of 30-50 mL / min at a temperature of °C, for a passing time of 5 The process is 0-60 min, then the temperature is raised to 75-80°C, and then it is continued for 30-40 min. Stir at a speed of 120-150 r / min throughout the process to ensure uniform mixing, and finally stir for 20-25 The methylal according to claim 1 is characterized by being cooled to °C to obtain catalyst additive A. This is a method to improve the adhesion of HMMM resin.

4. In step 2), the purification process is as follows: Methylal solution: Decontamination Mix the agents so that the mass ratio is 7-10:25-35, and heat at 55-60°C for 25-35 minutes. Stir, then let stand for 1 to 1.5 hours, using an ultrasonic frequency of 35 to 40 kHz and an ultrasonic output of 70 The upper layer of the standing liquid is subjected to ultrasonic adsorption treatment using an adsorbent under conditions of 0 to 800 W, and then the standing liquid is subjected to ultrasonic adsorption treatment. The solution is cooled to 20-25°C, and then upper layer impurities are separated and removed using a distillation column. The bottom mixture was distilled under normal pressure to obtain a purified methylal solution, and the ultrasonic adsorption time was 1 The duration is 5 to 20 min, and the operating pressure of the distillation column is 100 to 110 kPa, and the adsorption The agent is characterized by being selected from either molecular sieves or activated carbon. A method for improving the adhesion of HMMM resin using methylal as described in item 3.

5. The decontamination agent consists of 20-25% oxalic acid, 5-10% composite gel, and the remainder, in mass percent. The methylal according to claim 4, characterized in that it consists of ammonium oxalate. A method for improving the adhesion of HMMM resin.

6. The aforementioned composite gel is a modified composite gel obtained after modification treatment, and the method for preparing the modified composite gel The following applies: Adjust the pH to 2-3 using 10% hydrochloric acid by mass, and add methyl sulfate in a molar ratio of 1:1.5-3. Sodium licate and hydrogel are mixed in a reaction vessel to undergo polymerization and obtain a precursor solution. The mass ratio of the precursor solution:ethanol:deionized water is 2.5-4.5:5-7:5-7. Then, prepare ethanol and deionized water in sequence, add them to the reaction vessel, and heat to 85-90°C. Keep warm for 5-35 minutes and stir, then allow the maturation reaction to occur at a temperature of 20-25°C. The process takes 2-3 days, and finally, the mixture prepared above is subjected to vacuum drying to obtain a modified composite gel. The claim is characterized in that, thereafter, the drying temperature is 50 to 60°C and the drying time is 1 to 2 hours. A method for improving the adhesion of HMMM resin using methylal as described in item 5.

7. The ammonium trifluoromethanesulfonate is modified, and modified trifluoromethanesulfonate is We obtained ammonium phosphate, The aforementioned modified ammonium trifluoromethanesulfonate is a benzenesulfonic acid crystal: plasticizer Agent: Ammonium trifluoromethanesulfonate:Polyvinyl alcohol in a mass ratio of 1 to 1 It is prepared by mixing in a ratio of 2:0.4-0.6:2-3:0.5-0.

7. The method for preparing the modified ammonium trifluoromethanesulfonate is as follows: First, the benzenesulfonic acid crystals were dried in an oven at a temperature of 40-45°C, and then dried... The dried benzenesulfonic acid crystals and plasticizer are uniformly mixed and heated to a molten state, and the mixture M is Obtained, according to the ratio, ammonium trifluoromethanesulfonate and polyvinyl alcohol Prepare the ingredients and mix them to obtain a mixed solution N. The mixture M is extruded in an extruder into particles with a particle size of 1 to 3 μm, and the particles are heated to a temperature of -5 to The mixture is cooled in a 5°C cooling device, molded, and finally the mixed liquid N is sprayed onto the surface of the particulate matter. The preparation is characterized by uniform stirring and drying in a room temperature drying oven as described in paragraph 1. A method for improving the adhesion of HMMM resin using methylal.

8. The aforementioned plasticizer is epoxidized vegetable oil, trimethoxysilane, polyethylene glycol, The methylal in the HMM resin according to characteristic 7 is one of the following: Methods to improve adhesion.

9. The aforementioned alkaline solution is a sodium hydroxide solution with a mass fraction of 10-15%, and a solution with a mass fraction of 10- The claim according to claim 1, which is one of the 15% potassium hydroxide solutions. A method for improving the adhesion of HMMM resin using methylal.

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