Preparation method of a double-crosslinked acrylic emulsion for soft porcelain

Abstract

The present invention discloses a double-crosslinked acrylic emulsion for soft porcelain and a preparation method thereof. The preparation method adopts the seed emulsion polymerization method. Weigh acrylate monomers, methacrylic acid monomers, acrylic acid monomers, and acrylic functional monomers containing ketone carbonyl groups, mix and stir evenly to prepare a mixed monomer for standby; place emulsifiers, sodium bicarbonate, deionized water, and 30-50% of the initiator in a three-necked flask, and add 5-15% of the mixed monomer dropwise to the flask. After stabilizing for 5-20 minutes, a seed emulsion is obtained; the remaining mixed monomer and initiator are added dropwise within 2-4 hours, and after heating, curing, and cooling, the carboxyl-type acrylate emulsion is obtained by discharging; the above-mentioned acrylic emulsion containing ketone carbonyl groups is mixed with fillers, hydrazide crosslinking agents, and carboxyl crosslinking agents, and under the action of an acidic catalyst, double-crosslinked soft porcelain is prepared by high-temperature baking. This soft porcelain has excellent flexibility, strong adhesion to the substrate, and excellent weather resistance.

Description

Technical Field

[0001] The present invention belongs to the field of building materials, and particularly relates to a double-crosslinked acrylic emulsion for soft porcelain and a preparation method thereof. Background Art

[0002] Soft porcelain is a new type of energy-saving and low-carbon decorative material. Usually, it uses inorganic substances such as urban construction waste soil, cement waste blocks, porcelain slag, and stone powder as raw materials. After crushing, high-quality inorganic powder is screened out, and then special solution solvents such as adhesives are added. After mixing and stirring to form a flowing slurry, it is introduced into a prepared mold for plastic forming, and finally put into a drying room for high-temperature baking. After the baked soft porcelain is taken out and cooled, it is colored, polished, etc. according to different requirements. Nowadays, soft porcelain is widely used in the interior and exterior walls and floors of buildings.

[0003] With the development of modern building decoration technology, people have higher requirements for decoration effects and environmental quality. Traditional solvent-based coatings have been gradually phased out, and water-based environmentally friendly materials have gradually emerged. Soft porcelain materials made from 90% soil and 10% water solvent additives by baking have gradually been recognized by people. Its rich expressiveness and low-carbon environmental protection attributes are important factors for people's recognition. However, from the perspective of actual engineering construction effects, soft porcelain still has certain technical problems. Among them, the low bonding strength of the adhesive and poor weather resistance are important influencing factors. Therefore, developing a high-performance soft porcelain adhesive is the difficulty we face, enabling it to meet good mechanical properties and weather resistance, and being able to better promote this low-carbon environmental protection new green material.

[0004] Chinese Patent CN112029453A discloses a preparation technology of an adhesive with polyurethane as the main material. Through the chemical reaction between polyurethane, epoxy resin, and acrylate, an interpenetrating network structure polymer is formed, greatly improving its mechanical properties. However, the problem that the adhesive material is easily decomposed at high temperatures and has poor weather resistance has not been solved yet. Moreover, according to actual industrial production investigations, the price of polyurethane is high and it does not meet the development needs of the soft porcelain industry. Chinese Patent CN110642553A discloses a two-component polyurethane adhesive. The main materials include polyurethane, fatty acid triglyceride, and diphenylmethane diisocyanate. The polyurethane is modified by a hydroxyl-containing prepolymer and an isocyanate-containing prepolymer, greatly improving its bonding strength. However, according to actual industrial investigations, the mixing ratio of the two components changes with the change of temperature environment, bringing great challenges to construction workers and manufacturers. At the same time, a large amount of modified materials are added to the two-component polyurethane material, increasing the cost of the product.

[0005] Acrylic emulsion has become the mainstream matrix material of current soft porcelain materials due to its flexibility and excellent chemical resistance. However, as a block-type linear polymer, the acrylic emulsion has the characteristics of being hot sticky and cold brittle, resulting in the need to adjust the soft porcelain formula according to local climate and seasons at any time. At the same time, the free movement of the low glass transition segments leads to a sharp decline in performance with temperature changes. Therefore, developing a crosslinked acrylic emulsion to increase the cohesion of polymers has become the development direction for developing high-performance soft porcelain. Chinese Patent CN201811383937.6 discloses an aqueous self-crosslinking acrylic self-drying coating and its preparation method. By introducing ethyl acetoacetate methacrylate (AAEM) self-crosslinking monomer and utilizing the crosslinking and curing characteristics of this monomer, the crosslinking density of the acrylic emulsion is improved. However, the crosslinking of ketone-hydrazine crosslinking is regulated by many factors such as temperature and pH, and the crosslinking rate and degree of crosslinking are limited, with little room for improving the performance of soft porcelain.

[0006] The present invention mainly uses a carboxyl-type acrylic resin containing a ketone carbonyl group as the main material, combining the dual crosslinking characteristics of ketone-hydrazine crosslinking and the hydrolysis crosslinking of carboxyl groups and methylated melamine resin, significantly enhancing the cohesion between acrylic molecules, solving the technical problem of the current acrylic emulsion being hot sticky and cold brittle, and endowing soft porcelain with high hardness, flexibility, weather resistance, and chemical resistance. Summary of the Invention

[0007] The purpose of the present invention is to overcome the problems existing in the prior art, and provides a dual-crosslinked acrylic emulsion that enables intermolecular crosslinking to form an interpenetrating network structure with fillers, improving the comprehensive properties such as hardness, flexibility, weather resistance, and chemical resistance of soft porcelain.

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

[0009] A dual-crosslinked acrylic emulsion for soft porcelain and its preparation method, including the following steps:

[0010] (1) Weigh 15-25 parts of acrylate monomer, 15-25 parts of methacrylate monomer, 0.5-5 parts of acrylic monomer, 0.5-5 parts of acrylic functional monomer containing a ketone carbonyl group, and 0.5-5 parts of silane coupling agent containing organic functional groups by mass fraction, mix and stir evenly to prepare a mixed monomer for standby;

[0011] (2) Add 0.5-3 parts of emulsifier, 0.05-0.3 parts of sodium bicarbonate, 15-50% of initiator, and 50-90 parts of deionized water to the reaction kettle by mass fraction, heat up to 70-85 °C, dropwise add 5-15% of the mixed monomer within 10-30 minutes, stabilize for 5-20 minutes, dropwise add the remaining mixed monomer and initiator within 2-4 hours, heat up to 80-90 °C and cure for 1-2 hours, and cool down and discharge to obtain a carboxyl-type acrylic emulsion.

[0012] To further achieve the object of the present invention, preferably, the acrylate monomer is one or more of methyl acrylate, ethyl acrylate, and butyl acrylate.

[0013] Preferably, the methacrylate monomer is one or more of methyl methacrylate, propyl methacrylate, and butyl methacrylate.

[0014] Preferably, the acrylic monomer is acrylic acid or methacrylic acid.

[0015] Preferably, the acrylic functional monomer containing a ketone carbonyl group is diacetone acrylamide or ethyl acetoacetate methacrylate.

[0016] Preferably, the initiator is one or more of sodium persulfate, potassium persulfate, and ammonium persulfate.

[0017] A preparation method for soft porcelain includes the following steps: by mass fraction, adding 5 - 20 parts of aqueous acrylic emulsion, 20 - 40 parts of calcium powder, 40 - 60 parts of quartz sand, 0.5 - 5 parts of coarse fiber, 10 - 30 parts of water, 1 - 5 parts of hydrazide crosslinking agent, 1 - 5 parts of carboxyl crosslinking agent, and 0.1 - 0.5 parts of acidic catalyst into a stirring kettle, dispersing for 5 - 10 minutes, filtering and discharging, and preparing soft porcelain by high-temperature baking.

[0018] The carboxyl-type acrylic emulsion has a solid content of 45 - 65%, a viscosity of 500 - 4000 cP, an emulsion particle size of 50 - 200 nm, and a glass transition temperature of -20 - 10°C. This type of carboxyl-type acrylic resin can introduce the dual crosslinking characteristics of ketone-hydrazide crosslinking and hydrolysis crosslinking of carboxyl and methylated melamine resin, significantly improving the cohesive force between acrylic molecules, solving the current technical problems of heat stickiness and cold brittleness of acrylic emulsion, preparing a dual crosslinked acrylic emulsion, and endowing soft porcelain with high hardness, flexibility, weather resistance, and chemical resistance.

[0019] Preferably, the coarse fiber is one or more of polypropylene fiber and acrylic fiber.

[0020] Preferably, the hydrazide crosslinking agent is one or more of adipic dihydrazide, carbonic dihydrazide, oxalic dihydrazide, and succinic dihydrazide.

[0021] Preferably, the carboxyl crosslinking agent is methylated melamine resin.

[0022] Preferably, the acidic catalyst is one or more of p-toluenesulfonic acid, acetic acid, and solid superacid.

[0023] Compared with the prior art, a dual crosslinked acrylic emulsion for soft porcelain and its preparation method of the present invention have the following advantages and beneficial effects:

[0024] (1) From the perspective of structural design, introducing the dual cross-linking characteristics of ketone-hydrazine cross-linking and the hydrolysis cross-linking of carboxyl groups with methylated melamine resin significantly enhances the intermolecular cohesion of acrylic acid, solves the technical problems of the current acrylic emulsion being hot sticky and cold brittle, prepares a dual cross-linked acrylic emulsion, and endows the soft porcelain with high hardness, flexibility, weather resistance and chemical resistance.

[0025] (2) The product synthesized by the present invention has properties such as good flexibility, high adhesion to the substrate, excellent weather resistance, and also has the characteristic of low price. Specific embodiments

[0026] The following further illustrates the present invention in conjunction with embodiments, but the scope claimed by the present invention is not limited to the scope described in the embodiments.

[0027] Example 1

[0028] (1) Preparation of acrylic emulsion, the raw material types and dosages of each component are shown in Table 1.1:

[0029] Table 1.1:

[0030]

[0031]

[0032] Preparation process: By mass, weigh 19.5 parts of butyl acrylate, 20.5 parts of methyl methacrylate, 1.2 parts of acrylic acid, 0.9 part of glycidyl methacrylate, and 1.65 parts of diacetone acrylamide, mix and stir evenly to prepare a mixed monomer for standby; Add 0.5 part of EH-9 and 0.9 part of SDS emulsifier, 0.15 part of sodium bicarbonate, 50% of KPS and 54.5 parts of deionized water to the reaction kettle, heat up to 80 °C, drop 10% of the mixed monomer within 30 minutes, stabilize for 15 minutes, drop the remaining mixed monomer and initiator within 3 hours, heat up to 85 °C and cure for 1 hour, and cool down and discharge to obtain a carboxyl-terminated acrylic emulsion.

[0033] Properties of carboxyl-terminated acrylic emulsion: Scrape and dry the acrylic emulsion, and its properties are shown in Table 1.2:

[0034] Table 1.2:

[0035]

[0036] (2) By mass, the composition of the soft porcelain is shown in Table 1.3:

[0037] Table 1.3:

[0038]

[0039]

[0040] Preparation process: By mass fraction, add 10.9 parts of modified acrylic emulsion, 29.1 parts of 400-mesh calcium powder, 41 parts of 60-mesh quartz sand, 0.4 part of p-toluenesulfonic acid, 1 part of methylated melamine resin, 1.4 parts of adipic dihydrazide, 1.5 parts of coarse fiber and 14.7 parts of water into a stirring kettle, disperse for 15 minutes, filter and discharge, and prepare soft porcelain by high-temperature baking.

[0041] Properties of soft porcelain, and its properties are shown in Table 1.4:

[0042] Table 1.4:

[0043]

[0044] As can be seen from Tables 1.2 and 1.4, the modified acrylic emulsion of the present invention and its application in the field of soft porcelain have properties such as high adhesion to the substrate, good flexibility, excellent mechanical properties and good weather resistance. The modified acrylic emulsion of the present invention introduces the dual cross-linking characteristics of ketone-hydrazide cross-linking and hydrolysis cross-linking of carboxyl group and methylated melamine resin, significantly improving the internal cohesion between acrylic molecules, solving the technical problem of the current acrylic emulsion being thermally sticky and cold brittle, preparing a dual cross-linked acrylic emulsion, and endowing soft porcelain with high hardness, flexibility, weather resistance and chemical resistance. The present invention has the advantages of energy saving, environmental protection and low cost.

[0045] Example 2

[0046] (1) Preparation of acrylic emulsion, the raw material types and dosages of each component are shown in Table 2.1:

[0047] Table 2.1:

[0048]

[0049]

[0050] Preparation process: By mass fraction, weigh 17.5 parts of butyl acrylate, 20.5 parts of methyl methacrylate, 1.2 parts of acrylic acid, 0.9 part of glycidyl methacrylate, 2.75 parts of diacetone acrylamide, mix and stir evenly to prepare a mixed monomer for standby; add 0.5 part of EH-9 and 0.9 part of SDS emulsifier, 0.15 part of sodium bicarbonate, 50% of KPS and 54.5 parts of deionized water into a reaction kettle, heat up to 80 °C, dropwise add 10% of the mixed monomer within 30 minutes, stabilize for 15 minutes, dropwise add the remaining mixed monomer and initiator within 3 hours, heat up to 85 °C and cure for 1 hour, and cool down and discharge to obtain a carboxyl-terminated acrylic emulsion.

[0051] Properties of the carboxyl - terminated acrylic emulsion: The acrylic emulsion was spread with a scraper and dried, and its properties are shown in Table 2.2:

[0052] Table 2.2:

[0053]

[0054] (2) In parts by mass, the composition of the soft porcelain is shown in Table 2.3:

[0055] Table 2.3:

[0056]

[0057]

[0058] Preparation process: In parts by mass, 10.9 parts of the modified acrylic emulsion, 28.1 parts of 400 - mesh calcium powder, 41 parts of 60 - mesh quartz sand, 0.4 part of p - toluenesulfonic acid, 1 part of methylated melamine resin, 2.4 parts of adipic dihydrazide, 1.5 parts of coarse fiber and 14.7 parts of water were added to a stirring kettle, dispersed for 15 minutes, filtered and discharged, and then prepared into soft porcelain by high - temperature baking. The properties of the weather - resistant cross - linked soft porcelain are shown in Table 2.4:

[0059] Table 2.4:

[0060]

[0061] Example 3

[0062] (1) Preparation of the acrylic emulsion. The raw material types and dosages of each component are shown in Table 3.1:

[0063] Table 3.1:

[0064]

[0065] Preparation process: In parts by mass, 19.5 parts of butyl acrylate, 20.5 parts of methyl methacrylate, 1.2 parts of acrylic acid, 0.9 part of glycidyl methacrylate, and 1.65 parts of ethyl acetoacetate - methyl acrylate were mixed and stirred evenly to prepare the mixed monomer for standby; 0.5 part of EH - 9 and 0.9 part of SDS emulsifier, 0.15 part of sodium bicarbonate, 50% of KPS and 54.5 parts of deionized water were added to the reaction kettle, heated to 80 °C, 10% of the mixed monomer was added dropwise within 30 minutes, and after stabilizing for 15 minutes, the remaining mixed monomer and initiator were added dropwise within 3 hours, then heated to 85 °C and cured for 1 hour, and cooled and discharged to obtain the carboxyl - terminated acrylic emulsion.

[0066] Properties of the carboxyl - terminated acrylic emulsion: The acrylic emulsion was spread with a scraper and dried, and its properties are shown in Table 3.2:

[0067] Table 3.2:

[0068]

[0069] (2) In parts by mass, the composition of the soft porcelain is shown in Table 3.3:

[0070] Table 3.3:

[0071]

[0072] Preparation process: In parts by mass, add 10.9 parts of modified acrylic emulsion, 29.1 parts of 400-mesh calcium powder, 41 parts of 60-mesh quartz sand, 0.4 part of p-toluenesulfonic acid, 1 part of methylated melamine resin, 1.4 parts of adipic dihydrazide, 1.5 parts of coarse fiber and 14.7 parts of water into a stirring kettle, disperse for 15 minutes, filter and discharge, and prepare soft porcelain by high-temperature baking.

[0073] Properties of the soft porcelain, and its properties are shown in Table 3.4:

[0074] Table 3.4:

[0075]

[0076]

[0077] Example 4

[0078] (1) Preparation of acrylic emulsion, the raw material types and dosages of each component are shown in Table 4.1:

[0079] Table 4.1:

[0080]

[0081] Preparation process: In parts by mass, weigh 17.5 parts of butyl acrylate, 20.5 parts of methyl methacrylate, 1.2 parts of acrylic acid, 0.9 part of glycidyl methacrylate, 2.75 parts of ethyl acetoacetate methacrylate and mix and stir evenly to prepare a mixed monomer for standby; add 0.5 part of EH-9 and 0.9 part of SDS emulsifier, 0.15 part of sodium bicarbonate, 50% of KPS and 54.5 parts of deionized water into the reaction kettle, heat up to 80 °C, drop 10% of the mixed monomer within 30 minutes, stabilize for 15 minutes, drop the remaining mixed monomer and initiator within 3 hours, heat up to 85 °C and cure for 1 hour, and cool and discharge to obtain a carboxyl-terminated acrylic emulsion.

[0082] Properties of the carboxyl-terminated acrylic emulsion: Scrape and dry the acrylic emulsion, and its properties are shown in Table 4.2:

[0083] Table 4.2:

[0084]

[0085]

[0086] (2) By parts by mass, the composition of the soft porcelain is shown in Table 4.3:

[0087] Table 4.3:

[0088]

[0089] Preparation process: By parts by mass, add 10.9 parts of modified acrylic emulsion, 28.1 parts of 400-mesh calcium powder, 41 parts of 60-mesh quartz sand, 0.4 part of p-toluenesulfonic acid, 1 part of methylated melamine resin, 2.4 parts of adipic dihydrazide, 1.5 parts of coarse fiber and 14.7 parts of water into a stirring kettle, disperse for 15 minutes, filter and discharge, and prepare soft porcelain by high-temperature baking. The performance of the weather-resistant cross-linked soft porcelain is shown in Table 4.4:

[0090] Table 4.4:

[0091]

[0092] Example 5

[0093] (1) Preparation of acrylic emulsion, the raw material types and dosages of each component are shown in Table 5.1:

[0094] Table 5.1:

[0095]

[0096] Preparation process: By parts by mass, weigh 19.5 parts of butyl acrylate, 20.5 parts of methyl methacrylate, 1.2 parts of acrylic acid, 0.9 part of glycidyl methacrylate, 1.65 parts of ethyl acetoacetate methyl acrylate, mix and stir evenly to prepare a mixed monomer for standby; add 0.5 part of EH-9 and 0.9 part of SDS emulsifier, 0.15 part of sodium bicarbonate, 50% of KPS and 54.5 parts of deionized water into a reaction kettle, heat up to 80 °C, dropwise add 10% of the mixed monomer within 30 minutes, stabilize for 15 minutes, dropwise add the remaining mixed monomer and initiator within 3 hours, heat up to 85 °C and cure for 1 hour, and cool and discharge to obtain a carboxyl-terminated acrylic emulsion.

[0097] Performance of the carboxyl-terminated acrylic emulsion: Scrape and dry the acrylic emulsion, and its performance is shown in Table 5.2:

[0098] Table 5.2:

[0099]

[0100]

[0101] (2) By mass parts, the composition of the soft porcelain is shown in Table 5.3:

[0102] Table 5.3:

[0103]

[0104] Preparation process: By mass parts, add 10.9 parts of modified acrylic emulsion, 29.1 parts of 400-mesh calcium powder, 41 parts of 60-mesh quartz sand, 0.4 part of p-toluenesulfonic acid, 1 part of methylated melamine resin, 1.4 parts of carbohydrazide, 1.5 parts of coarse fiber and 14.7 parts of water into a stirring kettle, disperse for 15 minutes, filter and discharge, and prepare soft porcelain by high-temperature baking.

[0105] Properties of the soft porcelain, and its properties are shown in Table 5.4:

[0106] Table 5.4:

[0107]

[0108] Example 6

[0109] (1) Preparation of acrylic emulsion, the raw material types and dosages of each component are shown in Table 6.1:

[0110] Table 6.1:

[0111]

[0112]

[0113] Preparation process: By mass parts, weigh 17.5 parts of butyl acrylate, 20.5 parts of methyl methacrylate, 1.2 parts of acrylic acid, 0.9 part of glycidyl methacrylate, 2.75 parts of diacetone acrylamide, mix and stir evenly to prepare a mixed monomer for standby; add 0.5 part of EH-9 and 0.9 part of SDS emulsifier, 0.15 part of sodium bicarbonate, 50% of KPS and 54.5 parts of deionized water into a reaction kettle, heat up to 80 °C, dropwise add 10% of the mixed monomer within 30 minutes, stabilize for 15 minutes, dropwise add the remaining mixed monomer and initiator within 3 hours, heat up to 85 °C and cure for 1 hour, and cool and discharge to obtain a carboxyl-terminated acrylic emulsion.

[0114] Properties of the carboxyl-terminated acrylic emulsion: Scrape and dry the acrylic emulsion, and its properties are shown in Table 6.2:

[0115] Table 6.2:

[0116]

[0117] (2) In parts by mass, the composition of the soft porcelain is shown in Table 6.3:

[0118] Table 6.3:

[0119]

[0120]

[0121] Preparation process: In parts by mass, 10.9 parts of modified acrylic emulsion, 28.1 parts of 400-mesh calcium powder, 41 parts of 60-mesh quartz sand, 0.4 part of p-toluenesulfonic acid, 2 parts of methylated melamine resin, 1.4 parts of adipic dihydrazide, 1.5 parts of coarse fiber and 14.7 parts of water are added to a stirring kettle, dispersed for 15 minutes, filtered and discharged, and then prepared into soft porcelain by high-temperature baking. The properties of the weather-resistant cross-linked soft porcelain are shown in Table 2.4:

[0122] Table 2.4:

[0123]

[0124] Comparative Example 1

[0125] Using a commercial acrylic emulsion (Shanghai Baolijia flexible acrylic emulsion BLJ-938) as the main resin, the key parameters of the product are shown in Table 7.1:

[0126] Table 7.1:

[0127]

[0128] In parts by mass, the composition of the soft porcelain is shown in Table 7.2:

[0129] Table 7.2:

[0130]

[0131] Preparation process: In parts by mass, 10.9 parts of modified acrylic emulsion, 29.1 parts of 400-mesh calcium powder, 42.3 parts of 60-mesh quartz sand, 3 parts of coarse fiber and 14.7 parts of water are added to a stirring kettle, dispersed for 15 minutes, filtered and discharged.

[0132] The properties of the weather-resistant cross-linked soft porcelain are shown in Table 7.3:

[0133] Table 7.3:

[0134]

[0135] Comparative Example 2:

[0136] Using a commercial acrylic emulsion (Shanghai Zhenzhou Paint KB-soft porcelain special A) as the main resin, the key parameters of the product are shown in Table 8.1:

[0137] Table 8.1:

[0138]

[0139] In parts by mass, the formulation composition of the weather-resistant crosslinked soft porcelain type is shown in Table 8.2:

[0140] Table 8.2:

[0141]

[0142] Preparation process: In parts by mass, 10.9 parts of modified acrylic emulsion, 29.1 parts of 400-mesh calcium powder, 42.3 parts of 60-mesh quartz sand, 3 parts of coarse fiber, and 14.7 parts of water are added to a stirring kettle, dispersed for 15 minutes, and then filtered and discharged.

[0143] The properties of the weather-resistant crosslinked soft porcelain are shown in Table 8.4:

[0144] Table 8.4:

[0145]

[0146] The embodiments of the present invention are not limited by the above embodiments. Any other modifications, changes, substitutions, combinations, and simplifications made departing from the spirit and principle of the present invention shall be equivalent replacement methods and shall all be included within the protection scope of the present invention.

Claims

1. A preparation method of a soft porcelain material, characterized in that, Weigh 19.5 parts of butyl acrylate, 20.5 parts of methyl methacrylate, 1.2 parts of acrylic acid, 0.9 parts of glycidyl methacrylate, and 1.65 parts of diacetone acrylamide by mass fraction, mix and stir evenly to prepare a mixed monomer for standby; Add 0.5 parts of EH-9 and 0.9 parts of SDS emulsifier, 0.15 parts of sodium bicarbonate, 50% of KPS, and 54.5 parts of deionized water into the reaction kettle, heat up to 80 °C, dropwise add 10% of the mixed monomer within 30 minutes, stabilize for 15 minutes, dropwise add the remaining mixed monomer and initiator KPS within 3 hours, heat up to 85 °C and cure for 1 hour, cool down and discharge to obtain a carboxyl-terminated acrylic emulsion; Weigh 10.9 parts of carboxyl-terminated acrylic emulsion, 29.1 parts of 400-mesh calcium powder, 41 parts of 60-mesh quartz sand, 0.4 parts of p-toluenesulfonic acid, 1 part of methylated melamine resin, 1.4 parts of adipic dihydrazide, 1.5 parts of coarse fiber, and 14.7 parts of water by mass fraction, add them into the stirring kettle, disperse for 15 minutes, filter and discharge, and prepare soft porcelain by high-temperature baking.

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