A method for manufacturing a convenient dual-purpose microporous foaming mold

Abstract

The present invention relates to the field of microporous foaming molds, and specifically to a method for manufacturing a convenient dual-purpose microporous foaming mold, which is used to solve the problem of poor anti-sticking and anti-corrosion performance of existing dual-purpose microporous foaming molds. The manufacturing method uses epoxy resin as the main raw material, so that the mold-reinforcing coating can be well adhered to the microporous foaming mold substrate. Adding modified polysilazane and modified nano-magnesium oxide thereto can give the mold-reinforcing coating excellent anti-sticking performance, effectively avoid the problem of mold sticking, improve demolding efficiency and product qualification rate, and significantly improve the corrosion resistance and mechanical properties of the mold-reinforcing coating, giving the mold-reinforcing coating excellent stability, thereby effectively protecting the microporous foaming mold substrate, ensuring the long-term reliable operation of the microporous foaming mold substrate, and extending the service life of the microporous foaming mold substrate.

Description

Technical Field

[0001] The invention relates to the field of microporous foaming molds, and in particular to a method for manufacturing a convenient dual-purpose microporous foaming mold. Background Art

[0002] Microcellular foaming technology is widely used in the plastics industry due to its advantages of lightweight products, low cost, and excellent performance. Physical foaming and chemical foaming are two common microcellular foaming processes. Physical foaming forms bubbles by injecting inert gas, while chemical foaming relies on the thermal decomposition of the foaming agent to generate gas. Dual-use microcellular foaming molds enable flexible switching between physical and chemical foaming processes, significantly improving production efficiency and mold utilization.

[0003] However, such molds face many challenges in actual use:

[0004] The mold sticking problem is serious: during the physical foaming process, the high-temperature and high-pressure plastic melt is in close contact with the mold surface, which is prone to adhesion; during chemical foaming, the by-products produced by the decomposition of the foaming agent will also aggravate the adhesion between the melt and the mold, resulting in difficulty in demolding the product and defects such as surface damage and deformation.

[0005] High corrosion risk: Acidic or alkaline gases produced by the decomposition of chemical foaming agents, as well as auxiliary chemical reagents used in physical foaming, can cause chemical corrosion to the mold surface. At the same time, the frequent use of chemicals such as release agents and cleaning agents further accelerates the mold corrosion process.

[0006] Therefore, it is of great practical significance to develop a method for manufacturing a convenient dual-use microporous foaming mold that can meet the requirements of both physical foaming and chemical foaming processes and has excellent anti-sticking and anti-corrosion properties. Summary of the Invention

[0007] In order to overcome the above technical problems, the purpose of the present invention is to provide a convenient method for manufacturing a dual-purpose microporous foaming mold, which solves the problem of poor anti-sticking and anti-corrosion performance of the existing dual-purpose microporous foaming mold.

[0008] The purpose of the present invention can be achieved through the following technical solutions:

[0009] A method for manufacturing a convenient dual-purpose microporous foaming mold comprises the following steps:

[0010] Step 1: Weigh 40-45 parts of epoxy resin, 9-23 parts of modified polysilazane, 2-14 parts of modified nano-magnesium oxide, 3-5 parts of talc, 0.8-1.4 parts of wetting and dispersing agent, 0.3-0.5 parts of defoaming agent, 22-28 parts of curing agent, 5-9 parts of propylene glycol methyl ether acetate, 12-16 parts of acetone and 15-21 parts of xylene according to weight parts, and set aside;

[0011] Step 2: Add epoxy resin, modified polysilazane, modified nano magnesium oxide, talc, wetting dispersant, defoamer, curing agent, propylene glycol methyl ether acetate, acetone and xylene to a mixer, stir and mix at a temperature of 25-30° C. and a stirring rate of 600-800 r / min for 10-15 minutes, then adjust the stirring rate to 2000-2500 r / min and continue stirring and mixing for 30-40 minutes to obtain a mold reinforcement coating;

[0012] Step 3: After polishing and washing the microporous foaming mold base with ethanol, spray the mold reinforcement coating, drain it naturally, and then place it in a vacuum drying oven. Dry it at a temperature of 70-75°C for 2-3 hours, then heat it to 100-110°C and dry it for 30-50 minutes. After curing, cool it to room temperature to form a mold reinforcement coating with a coating thickness of 20-50μm, and obtain a convenient dual-use microporous foaming mold.

[0013] As a further solution of the present invention: the epoxy resin is E-51.

[0014] As a further solution of the present invention: the wetting and dispersing agent is TRITON CF-10.

[0015] As a further solution of the present invention: the defoaming agent is BYK-028.

[0016] As a further solution of the present invention: the curing agent is polyamide 650 curing agent.

[0017] As a further solution of the present invention: the modified polysilazane is prepared by the following steps:

[0018] Polysilazane and xylene are added to a three-necked flask equipped with a stirrer, a thermometer and an air guide tube, and nitrogen protection is introduced. The reaction is stirred at a temperature of 25-30°C and a stirring rate of 200-300 r / min for 20-30 minutes. Then, a fluorine-containing olefinic modifier and a catalyst solution are added and the temperature is raised to 70-75°C and the stirring reaction is continued for 5-7 hours. After the reaction is completed, the reaction product is cooled to room temperature, and then the solvent is removed by rotary evaporation. Then, it is placed in a vacuum drying oven and dried at a temperature of 50-55°C for 3-4 hours to obtain a modified polysilazane.

[0019] As a further solution of the present invention: the polysilazane, xylene, fluorine-containing alkenyl modifier and catalyst solution 10g: 70-80mL: 0.5-2.1g: 0.5-0.9mL.

[0020] As a further embodiment of the present invention: the polysilazane is the organopolysilazane IOTA 9150.

[0021] As a further solution of the present invention: the modified nano magnesium oxide is prepared by the following steps:

[0022] Step a1: Add a fluorinated olefinic modifier and toluene to a three-necked flask equipped with a stirrer, a thermometer, and an air guide tube, introduce nitrogen protection, and stir the reaction at a temperature of 25-30°C and a stirring rate of 200-300 r / min for 20-30 minutes. Then, add the catalyst solution and continue stirring the reaction at 50-55°C for 40-60 minutes. Then, add triethoxysilane and continue stirring the reaction at 70-75°C for 10-15 hours. After the reaction, cool the reaction product to room temperature, vacuum filter, and rotary evaporate the filtrate to remove the solvent to obtain a particle modifier.

[0023] Step a2: Add nano-magnesium oxide and anhydrous ethanol to a three-necked flask equipped with a stirrer, a thermometer and an air guide tube, and perform ultrasonic treatment for 30-40 minutes at an ultrasonic frequency of 40-50kHz. Then, adjust the pH to 4 with hydrochloric acid solution, and then introduce nitrogen protection. Stir and react for 10-15 minutes at a temperature of 25-30°C and a stirring rate of 200-300r / min. Then, add a particle modifier and continue stirring and reacting for 7-8 hours under the condition of raising the temperature to 70-75°C. After the reaction is completed, cool the reaction product to room temperature and then centrifuge it. Wash the precipitate with distilled water 3-5 times, and then place it in a vacuum drying oven and dry it at a temperature of 40-45°C for 8-10 hours to obtain modified nano-magnesium oxide.

[0024] As a further embodiment of the present invention: the usage ratio of the fluorine-containing alkenyl modifier, toluene, catalyst solution and triethoxysilane in step a1 is 10 mmol:60-70 mL:0.1-0.2 mL:10 mmol.

[0025] As a further solution of the present invention: the usage ratio of the nano-magnesium oxide, anhydrous ethanol and particle modifier in step a2 is 10g:100-120mL:2-7g.

[0026] As a further solution of the present invention: the average particle size of the nano-magnesium oxide in step a2 is 50 nm; and the mass fraction of the hydrochloric acid solution is 10-12%.

[0027] As a further embodiment of the present invention, the fluorine-containing alkenyl modifier is prepared by the following steps:

[0028] Perfluoro-1-heptanol, sodium hydride and anhydrous ether are added to a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, and the mixture is stirred for 20-30 minutes at a temperature of 25-30° C. and a stirring rate of 200-300 r / min. The mixture is then heated to reflux and the stirring reaction is continued for 1-2 hours. The 3-bromo-1-propylene solution is then added dropwise while stirring, and the dropping rate is controlled to 1-3 drops / s. After the addition is completed, the stirring reaction is continued for 3-5 hours. After the reaction is completed, the reaction product is cooled to room temperature and then added to ice water. The mixture is then allowed to stand for stratification, and the organic phase is rotary evaporated to remove the solvent. The mixture is then distilled at atmospheric pressure, and the fraction with a temperature of 80-85° C. is collected to obtain a fluorine-containing olefinic modifier.

[0029] As a further embodiment of the present invention, the usage ratio of the perfluoro-1-heptanol, sodium hydride, anhydrous ether and 3-bromo-1-propylene solution is 10 mmol: 20-25 mmol: 30-40 mL: 11-15 mL.

[0030] As a further embodiment of the present invention, the 3-bromo-1-propene solution is a solution formed by dissolving 3-bromo-1-propene in anhydrous ether at a ratio of 10 mmol:10 mL.

[0031] As a further embodiment of the present invention, the catalyst solution is prepared by the following steps:

[0032] Chloroplatinic acid hexahydrate and isopropanol were added to a three-necked flask equipped with a stirrer, a thermometer and a gas guide tube, and nitrogen was introduced for protection. The mixture was stirred at a temperature of 25-30°C and a stirring rate of 200-300 r / min for 3-5 minutes, and then the temperature was raised to 40-45°C and the stirring reaction was continued for 20-30 minutes. After the reaction was completed, the reaction product was cooled to room temperature to obtain a catalyst solution.

[0033] As a further solution of the present invention: the usage ratio of the chloroplatinic acid hexahydrate and isopropyl alcohol is 1-1.5 g:50 mL.

[0034] Beneficial effects of the present invention:

[0035] The present invention provides a method for preparing a convenient dual-purpose microporous foaming mold, which comprises the following steps: stirring and mixing epoxy resin, modified polysilazane, modified nano-magnesium oxide, talcum powder, a wetting dispersant, a defoaming agent, a curing agent, propylene glycol methyl ether acetate, acetone and xylene to obtain a mold reinforcement coating; polishing and washing the microporous foaming mold substrate with ethanol, spraying the mold reinforcement coating on the microporous foaming mold substrate, then naturally draining and drying, and cooling to room temperature after curing to form a mold reinforcement coating, thereby obtaining a convenient dual-purpose microporous foaming mold; using epoxy resin as the main raw material, the mold reinforcement coating can be well adhered to the microporous foaming mold substrate, and adding modified polysilazane and modified nano-magnesium oxide thereto can give the mold reinforcement coating excellent anti-sticking properties, effectively avoid mold sticking problems, improve demolding efficiency and product qualification rate, and significantly improve the corrosion resistance and mechanical properties of the mold reinforcement coating, giving the mold reinforcement coating excellent stability, thereby effectively protecting the microporous foaming mold substrate, ensuring the long-term reliable operation of the microporous foaming mold substrate, and extending the service life of the microporous foaming mold substrate.

[0036] In the process of preparing a convenient dual-use microporous foaming mold, a modified polysilazane is first prepared, and perfluoro-1-heptanol and 3-bromo-1-propylene are reacted. The hydroxyl group on the perfluoro-1-heptanol reacts with the bromine atom on the 3-bromo-1-propylene to obtain a fluorine-containing alkenyl modifier. Then, the polysilazane is modified with the fluorine-containing alkenyl modifier. The Si-H on the polysilazane reacts with the alkenyl group on the fluorine-containing alkenyl modifier to undergo a silylation reaction, thereby introducing a large number of fluorine atoms into the polysilazane to obtain a modified polysilazane. Due to the presence of polar chemical bonds in its structure, polysilazane can improve the adhesion between the mold reinforcement coating and the microporous foaming mold substrate. The bonding strength of the body is improved, and the Si-N chemical bond in its main chain is used to give it excellent mechanical strength and heat resistance, thereby improving the stability of the mold reinforcement coating. After introducing a large number of fluorine atoms into it, it can not only give the mold reinforcement coating an extremely low surface energy, significantly reducing the adhesion between the surface of the microporous foaming mold substrate and the plastic melt, but also further improve the stability of the mold reinforcement coating, so that it can stably exist under high temperature and high pressure conditions, and effectively resist the erosion of acidic gases, release agents, cleaning agents and other chemicals generated by the decomposition of the plastic melt, effectively protecting the microporous foaming mold substrate and extending the service life of the microporous foaming mold substrate.

[0037] In the process of preparing a convenient dual-use microporous foaming mold, a modified nano-magnesium oxide is also prepared. A fluorine-containing alkenyl modifier and triethoxysilane are reacted, and the alkenyl group on the fluorine-containing alkenyl modifier undergoes a silylation reaction with the Si-H on the triethoxysilane to obtain a particle modifier. The nano-magnesium oxide is then modified using the particle modifier. The siloxane on the particle modifier is hydrolyzed to form silanol, which can be grafted onto the particle surface of the nano-magnesium oxide. At the same time, a large number of fluorine atoms are introduced into the particle surface of the nano-magnesium oxide to obtain modified nano-magnesium oxide. Nano-magnesium oxide has high strength, high hardness and high temperature resistance. After modification, the dispersibility of nano-magnesium oxide can be significantly improved, so that it can be uniformly compatible with the mold-enhancing coating, and the mechanical properties and wear resistance of the mold-enhancing coating can be significantly improved, effectively resisting the friction and wear during the opening and closing of the microporous foaming mold substrate and the demolding of the product, avoiding damage to the mold-enhancing coating, and the introduced fluorine atoms can further improve the anti-sticking performance and chemical stability of the mold-enhancing coating. DETAILED DESCRIPTION

[0038] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0039] Example 1:

[0040] This embodiment is a method for making a convenient dual-purpose microporous foaming mold, comprising the following steps:

[0041] Step S1: 10 mmol perfluoro-1-heptanol, 20 mmol sodium hydride and 30 mL anhydrous ether were added to a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, and the mixture was stirred at a temperature of 25 ° C. and a stirring rate of 200 r / min for 20 minutes, and then the temperature was raised to reflux and the stirring reaction was continued for 1 hour. Then, 11 mL of 3-bromo-1-propene was added dropwise while stirring. The 3-bromo-1-propene solution formed by dissolving 10 mmol:10 mL in anhydrous ether was added at a rate of 1 drop / s. After the addition was completed, the stirring reaction was continued for 3 hours. After the reaction was completed, the reaction product was cooled to room temperature and then added to ice water. After standing and stratification, the organic phase was rotary evaporated to remove the solvent, and then distilled at atmospheric pressure. The fraction with a temperature of 80 ° C was collected to obtain a fluorine-containing alkenyl modifier;

[0042] Step S2: 1 g of chloroplatinic acid hexahydrate and 50 mL of isopropanol were added to a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube, and nitrogen was introduced. The mixture was stirred at 25° C. and a stirring rate of 200 r / min for 3 minutes, and then the temperature was raised to 40° C. and the stirring was continued for 20 minutes. After the reaction was completed, the reaction product was cooled to room temperature to obtain a catalyst solution;

[0043] Step S3: 10 g of organopolysilazane IOTA 9150 and 70 mL of xylene were added to a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube, and nitrogen was introduced for protection. The mixture was stirred at a temperature of 25 ° C and a stirring rate of 200 r / min for 20 minutes. Then, 0.5 g of a fluorinated alkenyl modifier and 0.5 mL of a catalyst solution were added and the temperature was raised to 70 ° C. The stirring reaction was continued for 5 hours. After the reaction was completed, the reaction product was cooled to room temperature, and then the solvent was removed by rotary evaporation. It was then placed in a vacuum drying oven and dried at a temperature of 50 ° C for 3 hours to obtain a modified polysilazane;

[0044] Step S4: 10 mmol of a fluorinated alkenyl modifier and 60 mL of toluene were added to a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube, and nitrogen was introduced for protection. The mixture was stirred at 25° C. and a stirring rate of 200 r / min for 20 minutes. Subsequently, 0.1 mL of a catalyst solution was added and the temperature was raised to 50° C. and the stirring reaction was continued for 40 minutes. Subsequently, 10 mmol of triethoxysilane was added and the temperature was raised to 70° C. and the stirring reaction was continued for 10 hours. After the reaction was completed, the reaction product was cooled to room temperature, and then vacuum filtered. The filtrate was rotary evaporated to remove the solvent to obtain a particle modifier.

[0045] Step S5: 10 g of nano-magnesium oxide with an average particle size of 50 nm and 100 mL of anhydrous ethanol were added to a three-necked flask equipped with a stirrer, a thermometer, and an air guide tube, and ultrasonically treated for 30 min at an ultrasonic frequency of 40 kHz. The pH was then adjusted to 4 with a 10% hydrochloric acid solution, and nitrogen was introduced for protection. The mixture was stirred at a temperature of 25° C. and a stirring rate of 200 r / min for 10 min. After that, 2 g of a particle modifier was added and the temperature was raised to 70° C. and the stirring reaction was continued for 7 h. After the reaction was completed, the reaction product was cooled to room temperature and then centrifuged. The precipitate was washed with distilled water 3 times, and then placed in a vacuum drying oven and dried at a temperature of 40° C. for 8 h to obtain modified nano-magnesium oxide;

[0046] Step S6: Weigh 40 parts of epoxy resin, 9 parts of modified polysilazane, 2 parts of modified nano-magnesium oxide, 3 parts of talc, 0.8 parts of wetting and dispersing agent, 0.3 parts of defoaming agent, 22 parts of curing agent, 5 parts of propylene glycol methyl ether acetate, 12 parts of acetone, and 15 parts of xylene according to weight and set aside; the epoxy resin is E-51; the wetting and dispersing agent is TRITON CF-10; the defoaming agent is BYK-028; and the curing agent is polyamide 650 curing agent;

[0047] Step S7: adding epoxy resin, modified polysilazane, modified nano-magnesium oxide, talc, wetting and dispersing agent, defoaming agent, curing agent, propylene glycol methyl ether acetate, acetone, and xylene to a mixer, stirring and mixing at a temperature of 25° C. and a stirring rate of 600 r / min for 10 minutes, then adjusting the stirring rate to 2000 r / min and continuing to stir and mix for 30 minutes to obtain a mold reinforcement coating;

[0048] Step S8: The microporous foaming mold base is polished, washed with ethanol, and then sprayed with mold-enhancing coating. It is then naturally drained and placed in a vacuum drying oven. It is dried at 70°C for 2 hours, then heated to 100°C and dried for 30 minutes. After curing, it is cooled to room temperature to form a mold-enhancing coating with a coating thickness of 50 μm, thereby obtaining a convenient dual-use microporous foaming mold.

[0049] Example 2:

[0050] This embodiment is a method for making a convenient dual-purpose microporous foaming mold, comprising the following steps:

[0051] Step S1: 10 mmol perfluoro-1-heptanol, 22 mmol sodium hydride and 35 mL anhydrous ether were added to a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, and the mixture was stirred at a temperature of 28 ° C. and a stirring rate of 250 r / min for 25 minutes, and then the mixture was heated to reflux and the stirring reaction was continued for 1.5 hours. Then, 13 mL of 3-bromo-1-propene was added dropwise while stirring. The 3-bromo-1-propene solution formed by dissolving 10 mmol:10 mL of 3-bromo-1-propene in anhydrous ether was dissolved, and the dropping rate was controlled to 2 drops / s. After the addition was completed, the stirring reaction was continued for 4 hours. After the reaction was completed, the reaction product was cooled to room temperature and then added to ice water. After standing and stratification, the organic phase was rotary evaporated to remove the solvent, and then distilled at atmospheric pressure. The fraction with a temperature of 82 ° C was collected to obtain a fluorine-containing alkenyl modifier;

[0052] Step S2: 1.2 g of chloroplatinic acid hexahydrate and 50 mL of isopropanol were added to a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube, and nitrogen was introduced for protection. The mixture was stirred at 28° C. and a stirring rate of 250 r / min for 4 minutes, and then the temperature was raised to 42° C. and the stirring was continued for 25 minutes. After the reaction was completed, the reaction product was cooled to room temperature to obtain a catalyst solution;

[0053] Step S3: 10 g of organopolysilazane IOTA 9150 and 75 mL of xylene were added to a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube, and nitrogen was introduced for protection. The reaction was stirred at a temperature of 25-30 ° C and a stirring rate of 250 r / min for 25 minutes. Then, 1.3 g of a fluorinated alkenyl modifier and 0.7 mL of a catalyst solution were added and the temperature was raised to 72 ° C. The stirring reaction was continued for 6 hours. After the reaction was completed, the reaction product was cooled to room temperature, and then the solvent was removed by rotary evaporation. It was then placed in a vacuum drying oven and dried at a temperature of 52 ° C for 3.5 hours to obtain a modified polysilazane;

[0054] Step S4: 10 mmol of a fluorinated alkenyl modifier and 65 mL of toluene were added to a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube, and nitrogen was introduced for protection. The mixture was stirred at 28° C. and a stirring rate of 250 r / min for 25 minutes. Subsequently, 0.15 mL of a catalyst solution was added and the mixture was heated to 52° C. and stirred for 50 minutes. Subsequently, 10 mmol of triethoxysilane was added and the mixture was heated to 72° C. and stirred for 12 hours. After the reaction, the reaction product was cooled to room temperature, and then vacuum filtered. The filtrate was rotary evaporated to remove the solvent to obtain a particle modifier.

[0055] Step S5: 10 g of nano-magnesium oxide with an average particle size of 50 nm and 110 mL of anhydrous ethanol were added to a three-necked flask equipped with a stirrer, a thermometer, and an air guide tube, and ultrasonically treated for 35 min at an ultrasonic frequency of 45 kHz. The pH was then adjusted to 4 with a hydrochloric acid solution having a mass fraction of 11%, and then nitrogen was introduced for protection. The mixture was stirred at a temperature of 28° C. and a stirring rate of 250 r / min for 12 min. After that, 4.5 g of a particle modifier was added and the mixture was heated to 72° C. and stirred for 7.5 h. After the reaction was completed, the reaction product was cooled to room temperature and then centrifuged. The precipitate was washed with distilled water 4 times, and then placed in a vacuum drying oven and dried at a temperature of 42° C. for 9 h to obtain modified nano-magnesium oxide;

[0056] Step S6: Weigh 42 parts of epoxy resin, 16 parts of modified polysilazane, 8 parts of modified nano-magnesium oxide, 4 parts of talc, 1.1 parts of wetting and dispersing agent, 0.4 parts of defoaming agent, 25 parts of curing agent, 7 parts of propylene glycol methyl ether acetate, 14 parts of acetone, and 18 parts of xylene according to weight and set aside; the epoxy resin is E-51; the wetting and dispersing agent is TRITON CF-10; the defoaming agent is BYK-028; and the curing agent is polyamide 650 curing agent;

[0057] Step S7: adding epoxy resin, modified polysilazane, modified nano-magnesium oxide, talc, wetting and dispersing agent, defoaming agent, curing agent, propylene glycol methyl ether acetate, acetone, and xylene to a mixer, stirring and mixing at a temperature of 28° C. and a stirring rate of 700 r / min for 12 minutes, then adjusting the stirring rate to 2300 r / min and continuing to stir and mix for 35 minutes to obtain a mold reinforcement coating;

[0058] Step S8: The microporous foaming mold base is polished, washed with ethanol, and then sprayed with mold-enhancing coating. It is then naturally drained and placed in a vacuum drying oven. It is dried at a temperature of 72°C for 2.5 hours, then heated to 105°C and dried for 40 minutes. After curing, it is cooled to room temperature to form a mold-enhancing coating with a coating thickness of 50 μm, thereby obtaining a convenient dual-use microporous foaming mold.

[0059] Example 3:

[0060] This embodiment is a method for making a convenient dual-purpose microporous foaming mold, comprising the following steps:

[0061] Step S1: 10 mmol perfluoro-1-heptanol, 25 mmol sodium hydride and 40 mL anhydrous ether were added to a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, and the mixture was stirred at a temperature of 30 ° C. and a stirring rate of 300 r / min for 30 minutes, and then the temperature was raised to reflux and the stirring reaction was continued for 2 hours. Then, 15 mL of 3-bromo-1-propene was added dropwise while stirring. The 3-bromo-1-propene solution formed by dissolving 10 mmol:10 mL of 3-bromo-1-propene in anhydrous ether was dissolved, and the dropping rate was controlled to 3 drops / s. After the addition was completed, the stirring reaction was continued for 5 hours. After the reaction was completed, the reaction product was cooled to room temperature and then added to ice water. After standing and stratification, the organic phase was rotary evaporated to remove the solvent, and then distilled at atmospheric pressure. The fraction with a temperature of 85 ° C was collected to obtain a fluorine-containing alkenyl modifier;

[0062] Step S2: 1.5 g of chloroplatinic acid hexahydrate and 50 mL of isopropanol were added to a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube, and nitrogen was introduced for protection. The mixture was stirred at 30° C. and a stirring rate of 300 r / min for 5 minutes, and then the temperature was raised to 45° C. and the stirring was continued for 30 minutes. After the reaction was completed, the reaction product was cooled to room temperature to obtain a catalyst solution;

[0063] Step S3: 10 g of organopolysilazane IOTA 9150 and 80 mL of xylene were added to a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube, and nitrogen was introduced for protection. The mixture was stirred at a temperature of 30 ° C and a stirring rate of 300 r / min for 30 minutes. Then, 2.1 g of a fluorinated alkenyl modifier and 0.9 mL of a catalyst solution were added and the temperature was raised to 75 ° C. The stirring reaction was continued for 7 hours. After the reaction was completed, the reaction product was cooled to room temperature, and then the solvent was removed by rotary evaporation. It was then placed in a vacuum drying oven and dried at a temperature of 55 ° C for 4 hours to obtain a modified polysilazane;

[0064] Step S4: 10 mmol of a fluorinated alkenyl modifier and 70 mL of toluene were added to a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube, and nitrogen was introduced for protection. The mixture was stirred at 30° C. and a stirring rate of 300 r / min for 30 minutes. Subsequently, 0.2 mL of a catalyst solution was added and the temperature was raised to 55° C. and the stirring reaction was continued for 60 minutes. Subsequently, 10 mmol of triethoxysilane was added and the temperature was raised to 75° C. and the stirring reaction was continued for 15 hours. After the reaction was completed, the reaction product was cooled to room temperature, and then vacuum filtered. The filtrate was rotary evaporated to remove the solvent to obtain a particle modifier.

[0065] Step S5: 10 g of nano-magnesium oxide with an average particle size of 50 nm and 120 mL of anhydrous ethanol were added to a three-necked flask equipped with a stirrer, a thermometer, and an air guide tube, and ultrasonically treated for 40 min at an ultrasonic frequency of 50 kHz. The pH was then adjusted to 4 with a 12% mass fraction hydrochloric acid solution, and then nitrogen was introduced for protection. The mixture was stirred at a temperature of 30° C. and a stirring rate of 300 r / min for 15 min. After that, 7 g of a particle modifier was added and the temperature was raised to 75° C. and the stirring reaction was continued for 8 h. After the reaction was completed, the reaction product was cooled to room temperature and then centrifuged. The precipitate was washed with distilled water 5 times, and then placed in a vacuum drying oven and dried at a temperature of 45° C. for 10 h to obtain modified nano-magnesium oxide;

[0066] Step S6: Weigh 45 parts of epoxy resin, 23 parts of modified polysilazane, 14 parts of modified nano-magnesium oxide, 5 parts of talc, 1.4 parts of wetting and dispersing agent, 0.5 parts of defoaming agent, 28 parts of curing agent, 9 parts of propylene glycol methyl ether acetate, 16 parts of acetone, and 21 parts of xylene according to weight and set aside; the epoxy resin is E-51; the wetting and dispersing agent is TRITON CF-10; the defoaming agent is BYK-028; and the curing agent is polyamide 650 curing agent;

[0067] Step S7: adding epoxy resin, modified polysilazane, modified nano-magnesium oxide, talc, wetting and dispersing agent, defoaming agent, curing agent, propylene glycol methyl ether acetate, acetone, and xylene to a mixer, stirring and mixing at a temperature of 30° C. and a stirring rate of 800 r / min for 15 minutes, then adjusting the stirring rate to 2500 r / min and continuing to stir and mix for 40 minutes to obtain a mold reinforcement coating;

[0068] Step S8: After polishing and washing the microporous foaming mold base with ethanol, the mold-enhancing coating is sprayed on it, and then it is naturally drained. Then it is placed in a vacuum drying oven and dried at a temperature of 75°C for 3 hours. Then it is heated to 110°C and dried for 50 minutes. After curing, it is cooled to room temperature to form a mold-enhancing coating with a coating thickness of 50 μm, thereby obtaining a convenient dual-use microporous foaming mold.

[0069] Comparative Example 1:

[0070] This comparative example is a method for making a convenient dual-purpose microporous foaming mold, comprising the following steps:

[0071] Step S1: Weigh 45 parts of epoxy resin, 5 parts of talc, 1.4 parts of wetting and dispersing agent, 0.5 parts of defoaming agent, 28 parts of curing agent, 9 parts of propylene glycol methyl ether acetate, 16 parts of acetone, and 21 parts of xylene according to weight and set aside; the epoxy resin is E-51; the wetting and dispersing agent is TRITON CF-10; the defoaming agent is BYK-028; and the curing agent is polyamide 650 curing agent;

[0072] Step S2: adding epoxy resin, talc, wetting and dispersing agent, defoaming agent, curing agent, propylene glycol methyl ether acetate, acetone, and xylene into a mixer, stirring and mixing at a temperature of 30° C. and a stirring rate of 800 r / min for 15 minutes, then adjusting the stirring rate to 2500 r / min and continuing to stir and mix for 40 minutes to obtain a mold reinforcement coating;

[0073] Step S3: The microporous foaming mold base is polished, washed with ethanol, and then sprayed with mold-enhancing coating. It is then naturally drained and placed in a vacuum drying oven. It is dried at 75°C for 3 hours, then heated to 110°C and dried for 50 minutes. After curing, it is cooled to room temperature to form a mold-enhancing coating with a coating thickness of 50 μm, thereby obtaining a convenient dual-use microporous foaming mold.

[0074] Comparative Example 2:

[0075] This comparative example is a method for making a convenient dual-purpose microporous foaming mold, comprising the following steps:

[0076] Step S1: 10 mmol perfluoro-1-heptanol, 25 mmol sodium hydride and 40 mL anhydrous ether were added to a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, and the mixture was stirred at a temperature of 30 ° C. and a stirring rate of 300 r / min for 30 minutes, and then the temperature was raised to reflux and the stirring reaction was continued for 2 hours. Then, 15 mL of 3-bromo-1-propene was added dropwise while stirring. The 3-bromo-1-propene solution formed by dissolving 10 mmol:10 mL of 3-bromo-1-propene in anhydrous ether was dissolved, and the dropping rate was controlled to 3 drops / s. After the addition was completed, the stirring reaction was continued for 5 hours. After the reaction was completed, the reaction product was cooled to room temperature and then added to ice water. After standing and stratification, the organic phase was rotary evaporated to remove the solvent, and then distilled at atmospheric pressure. The fraction with a temperature of 85 ° C was collected to obtain a fluorine-containing alkenyl modifier;

[0077] Step S2: 1.5 g of chloroplatinic acid hexahydrate and 50 mL of isopropanol were added to a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube, and nitrogen was introduced for protection. The mixture was stirred at 30° C. and a stirring rate of 300 r / min for 5 minutes, and then the temperature was raised to 45° C. and the stirring was continued for 30 minutes. After the reaction was completed, the reaction product was cooled to room temperature to obtain a catalyst solution;

[0078] Step S3: 10 g of organopolysilazane IOTA 9150 and 80 mL of xylene were added to a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube, and nitrogen was introduced for protection. The mixture was stirred at a temperature of 30 ° C and a stirring rate of 300 r / min for 30 minutes. Then, 2.1 g of a fluorinated alkenyl modifier and 0.9 mL of a catalyst solution were added and the temperature was raised to 75 ° C. The stirring reaction was continued for 7 hours. After the reaction was completed, the reaction product was cooled to room temperature, and then the solvent was removed by rotary evaporation. It was then placed in a vacuum drying oven and dried at a temperature of 55 ° C for 4 hours to obtain a modified polysilazane;

[0079] Step S4: Weigh 45 parts of epoxy resin, 23 parts of modified polysilazane, 5 parts of talc, 1.4 parts of wetting and dispersing agent, 0.5 parts of defoaming agent, 28 parts of curing agent, 9 parts of propylene glycol methyl ether acetate, 16 parts of acetone, and 21 parts of xylene according to weight and set aside; the epoxy resin is E-51; the wetting and dispersing agent is TRITON CF-10; the defoaming agent is BYK-028; and the curing agent is polyamide 650 curing agent;

[0080] Step S5: adding epoxy resin, modified polysilazane, talc, wetting and dispersing agent, defoaming agent, curing agent, propylene glycol methyl ether acetate, acetone, and xylene to a mixer, stirring and mixing at a temperature of 30° C. and a stirring rate of 800 r / min for 15 minutes, then adjusting the stirring rate to 2500 r / min and continuing to stir and mix for 40 minutes to obtain a mold reinforcement coating;

[0081] Step S6: The microporous foaming mold base is polished, washed with ethanol, and then sprayed with mold-enhancing coating. It is then naturally drained and placed in a vacuum drying oven. It is dried at 75°C for 3 hours, then heated to 110°C and dried for 50 minutes. After curing, it is cooled to room temperature to form a mold-enhancing coating with a coating thickness of 50 μm, thereby obtaining a convenient dual-use microporous foaming mold.

[0082] Comparative Example 3:

[0083] This comparative example is a method for making a convenient dual-purpose microporous foaming mold, comprising the following steps:

[0084] Step S1: 10 mmol perfluoro-1-heptanol, 25 mmol sodium hydride and 40 mL anhydrous ether were added to a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, and the mixture was stirred at a temperature of 30 ° C. and a stirring rate of 300 r / min for 30 minutes, and then the temperature was raised to reflux and the stirring reaction was continued for 2 hours. Then, 15 mL of 3-bromo-1-propene was added dropwise while stirring. The 3-bromo-1-propene solution formed by dissolving 10 mmol:10 mL of 3-bromo-1-propene in anhydrous ether was dissolved, and the dropping rate was controlled to 3 drops / s. After the addition was completed, the stirring reaction was continued for 5 hours. After the reaction was completed, the reaction product was cooled to room temperature and then added to ice water. After standing and stratification, the organic phase was rotary evaporated to remove the solvent, and then distilled at atmospheric pressure. The fraction with a temperature of 85 ° C was collected to obtain a fluorine-containing alkenyl modifier;

[0085] Step S2: 1.5 g of chloroplatinic acid hexahydrate and 50 mL of isopropanol were added to a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube, and nitrogen was introduced for protection. The mixture was stirred at 30° C. and a stirring rate of 300 r / min for 5 minutes, and then the temperature was raised to 45° C. and the stirring was continued for 30 minutes. After the reaction was completed, the reaction product was cooled to room temperature to obtain a catalyst solution;

[0086] Step S3: 10 mmol of a fluorinated alkenyl modifier and 70 mL of toluene were added to a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube, and nitrogen was introduced for protection. The mixture was stirred at 30° C. and a stirring rate of 300 r / min for 30 minutes. Subsequently, 0.2 mL of a catalyst solution was added and the temperature was raised to 55° C. and the stirring reaction was continued for 60 minutes. Subsequently, 10 mmol of triethoxysilane was added and the temperature was raised to 75° C. and the stirring reaction was continued for 15 hours. After the reaction was completed, the reaction product was cooled to room temperature, and then vacuum filtered. The filtrate was rotary evaporated to remove the solvent to obtain a particle modifier.

[0087] Step S4: 10 g of nano-magnesium oxide with an average particle size of 50 nm and 120 mL of anhydrous ethanol were added to a three-necked flask equipped with a stirrer, a thermometer, and an air guide tube, and ultrasonically treated for 40 min at an ultrasonic frequency of 50 kHz. The pH was then adjusted to 4 with a 12% mass fraction hydrochloric acid solution, and then nitrogen was introduced for protection. The mixture was stirred at a temperature of 30° C. and a stirring rate of 300 r / min for 15 min. After that, 7 g of a particle modifier was added and the temperature was raised to 75° C. and the stirring reaction was continued for 8 h. After the reaction was completed, the reaction product was cooled to room temperature and then centrifuged. The precipitate was washed with distilled water 5 times, and then placed in a vacuum drying oven and dried at a temperature of 45° C. for 10 h to obtain modified nano-magnesium oxide;

[0088] Step S5: Weigh 45 parts of epoxy resin, 14 parts of modified nano-magnesium oxide, 5 parts of talc, 1.4 parts of wetting and dispersing agent, 0.5 parts of defoaming agent, 28 parts of curing agent, 9 parts of propylene glycol methyl ether acetate, 16 parts of acetone, and 21 parts of xylene according to weight and set aside; the epoxy resin is E-51; the wetting and dispersing agent is TRITON CF-10; the defoaming agent is BYK-028; and the curing agent is polyamide 650 curing agent;

[0089] Step S6: adding epoxy resin, modified nano-magnesium oxide, talc, wetting and dispersing agent, defoaming agent, curing agent, propylene glycol methyl ether acetate, acetone, and xylene into a mixer, stirring and mixing at a temperature of 30° C. and a stirring rate of 800 r / min for 15 minutes, then adjusting the stirring rate to 2500 r / min and continuing to stir and mix for 40 minutes to obtain a mold reinforcement coating;

[0090] Step S7: The microporous foaming mold base is polished, washed with ethanol, and then sprayed with mold-enhancing coating. It is then naturally drained and placed in a vacuum drying oven. It is dried at 75°C for 3 hours, then heated to 110°C and dried for 50 minutes. After curing, it is cooled to room temperature to form a mold-enhancing coating with a coating thickness of 50 μm, thereby obtaining a convenient dual-use microporous foaming mold.

[0091] Comparative Example 4:

[0092] This comparative example is a method for making a convenient dual-purpose microporous foaming mold, comprising the following steps:

[0093] Step S1: 45 parts of epoxy resin, 23 parts of organopolysilazane IOTA, 14 parts of nano-magnesium oxide with an average particle size of 50 nm, 5 parts of talc, 1.4 parts of wetting and dispersing agent, 0.5 parts of defoaming agent, 28 parts of curing agent, 9 parts of propylene glycol methyl ether acetate, 16 parts of acetone, and 21 parts of xylene are weighed and set aside according to weight; the epoxy resin is E-51; the wetting and dispersing agent is TRITON CF-10; the defoaming agent is BYK-028; and the curing agent is polyamide 650 curing agent;

[0094] Step S2: adding epoxy resin, organopolysilazane IOTA, nano-magnesium oxide, talc, wetting and dispersing agent, defoaming agent, curing agent, propylene glycol methyl ether acetate, acetone, and xylene into a mixer, stirring and mixing at a temperature of 30° C. and a stirring rate of 800 r / min for 15 minutes, then adjusting the stirring rate to 2500 r / min and continuing to stir and mix for 40 minutes to obtain a mold reinforcement coating;

[0095] Step S3: The microporous foaming mold base is polished, washed with ethanol, and then sprayed with mold-enhancing coating. It is then naturally drained and placed in a vacuum drying oven. It is dried at 75°C for 3 hours, then heated to 110°C and dried for 50 minutes. After curing, it is cooled to room temperature to form a mold-enhancing coating with a coating thickness of 50 μm, thereby obtaining a convenient dual-use microporous foaming mold.

[0096] The mold reinforcement coatings of Examples 1-3 and Comparative Examples 1-4 were subjected to performance tests, and the test results are shown in the following table:

[0097]

[0098] The acid treatment is to immerse the mold reinforcement coating in a hydrochloric acid solution with a mass fraction of 10% for 24 hours.

[0099] Referring to the data in the above table, according to the comparison between Examples 1-3 and Comparative Examples 1-4, it can be seen that the addition of modified polysilazane and modified nano-magnesium oxide can significantly improve the anti-sticking and easy demoulding properties, mechanical properties and corrosion resistance of the mold reinforcement coating, thereby effectively protecting the microporous foaming mold substrate. In addition, under the synergistic effect of modified polysilazane and modified nano-magnesium oxide, the convenient dual-use microporous foaming mold is given excellent corrosion resistance, anti-sticking and wear resistance.

[0100] Throughout this specification, references to terms such as "one embodiment," "example," or "specific example" indicate that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, schematic representations of these 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 any one or more embodiments or examples.

[0101] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in similar ways. As long as they do not deviate from the invention or exceed the scope defined in this application, they should all fall within the scope of protection of the present invention.

Claims

1. A method for making a convenient dual-purpose microporous foaming mold, characterized in that: The following steps are involved: Step 1: Weigh 40-45 parts of epoxy resin, 9-23 parts of modified polysilazane, 2-14 parts of modified nano-magnesium oxide, 3-5 parts of talc, 0.8-1.4 parts of wetting and dispersing agent, 0.3-0.5 parts of defoaming agent, 22-28 parts of curing agent, 5-9 parts of propylene glycol methyl ether acetate, 12-16 parts of acetone and 15-21 parts of xylene according to weight parts, and set aside; Step 2: Add epoxy resin, modified polysilazane, modified nano magnesium oxide, talc, wetting dispersant, defoamer, curing agent, propylene glycol methyl ether acetate, acetone and xylene to a mixer, stir and mix at a temperature of 25-30° C. and a stirring rate of 600-800 r / min for 10-15 minutes, then adjust the stirring rate to 2000-2500 r / min and continue stirring and mixing for 30-40 minutes to obtain a mold reinforcement coating; Step 3: After polishing and washing the microporous foaming mold substrate with ethanol, spray the mold reinforcement coating, drain it naturally, and then place it in a vacuum drying oven. Dry it at a temperature of 70-75°C for 2-3 hours, then heat it to 100-110°C and dry it for 30-50 minutes. After curing, cool it to room temperature to form a mold reinforcement coating with a coating thickness of 20-50μm, thereby obtaining a convenient dual-use microporous foaming mold. Wherein, the modified polysilazane is prepared by the following steps: Adding polysilazane and xylene to a three-necked flask equipped with a stirrer, a thermometer, and an air guide tube to carry out stirring reaction, then adding a fluorine-containing alkenyl modifier and a catalyst solution to continue stirring reaction, and after the reaction is completed, cooling the reaction product, then rotary evaporating, and then drying to obtain modified polysilazane; The modified nano magnesium oxide is prepared by the following steps: Step a1: stirring a fluorinated alkenyl modifier and toluene to react, then adding a catalyst solution and triethoxysilane and continuing to stir and react. After the reaction is completed, the reaction product is cooled, then vacuum filtered, and the filtrate is rotary evaporated to obtain a particle modifier; Step a2: subjecting nano-magnesium oxide and anhydrous ethanol to ultrasonic treatment, adjusting the pH with hydrochloric acid solution, adding a particle modifier, and continuing to stir the reaction. After the reaction is completed, the reaction product is cooled, centrifuged, and the precipitate is washed and dried to obtain modified nano-magnesium oxide.

2. The method for making a convenient dual-purpose microporous foaming mold according to claim 1, characterized in that: The epoxy resin is E-51; The wetting and dispersing agent is TRITON CF-10; The defoamer is BYK-028; The curing agent is polyamide 650 curing agent.

3. The method for making a convenient dual-purpose microporous foaming mold according to claim 1, characterized in that: The polysilazane, xylene, fluorine-containing alkenyl modifier and catalyst solution are 10g:70-80mL:0.5-2.1g:0.5-0.9mL; the polysilazane is organic polysilazane IOTA 9150.

4. The method for making a convenient dual-purpose microporous foaming mold according to claim 1, characterized in that: The usage ratio of the fluorine-containing alkenyl modifier, toluene, catalyst solution and triethoxysilane in step a1 is 10 mmol:60-70 mL:0.1-0.2 mL:10 mmol.

5. The method for manufacturing a convenient dual-purpose microporous foaming mold according to claim 1, characterized in that: The dosage ratio of the nano-magnesium oxide, anhydrous ethanol and particle modifier in step a2 is 10g:100-120mL:2-7g; the average particle size of the nano-magnesium oxide is 50nm; and the mass fraction of the hydrochloric acid solution is 10-12%.

6. The method for manufacturing a convenient dual-purpose microporous foaming mold according to claim 1, characterized in that: The fluorine-containing alkenyl modifier is prepared by the following steps: Perfluoro-1-heptanol, sodium hydride and anhydrous ether are stirred for reaction, and then 3-bromo-1-propylene solution is added and the stirring reaction is continued. After the reaction is completed, the reaction product is cooled to room temperature and then added to ice water. After standing and stratification, the organic phase is rotary evaporated and then distilled at atmospheric pressure. The fractions are collected to obtain a fluorine-containing olefinic modifier.

7. The method for manufacturing a convenient dual-purpose microporous foaming mold according to claim 6, characterized in that: The usage ratio of the perfluoro-1-heptanol, sodium hydride, anhydrous ether and 3-bromo-1-propene solution is 10 mmol: 20-25 mmol: 30-40 mL: 11-15 mL; the 3-bromo-1-propene solution is a solution formed by dissolving 3-bromo-1-propene in anhydrous ether at a ratio of 10 mmol: 10 mL.

8. The method for manufacturing a convenient dual-purpose microporous foaming mold according to claim 1, characterized in that: The catalyst solution is prepared by the following steps: Chloroplatinic acid hexahydrate and isopropyl alcohol are stirred for reaction, and after the reaction is completed, the reaction product is cooled to obtain a catalyst solution.

9. The method for manufacturing a convenient dual-purpose microporous foaming mold according to claim 8, characterized in that: The usage ratio of the chloroplatinic acid hexahydrate and isopropyl alcohol is 1-1.5 g:50 mL.

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