阅读说明：本技术 一种建筑墙面抗渗透固化防水剂及其制备方法 (Anti-penetration curing waterproof agent for building wall and preparation method thereof ) 是由 不公告发明人 于 2021-08-17 设计创作，主要内容包括：本发明公开一种建筑墙面抗渗透固化防水剂,包括如下重量份原料：四甲基氯化铵0.6-1份、聚四氢呋喃二醇80-90份、六亚甲基二异氰酸酯30-40份、三甲基硅醇3-5份、甲乙酮16-20份、阻燃成分7-10份、4-羧基硼酸3-5份、辅助添加剂2-4份、4,8-二羟基喹啉-2-甲酸2-4份和去离子水100-110份；该建筑墙面抗渗透固化防水剂通过如下步骤制备：第一步、按重量份称取原料；第二步、制备预聚体；第三步、向预聚体中加入三甲基硅醇和甲乙酮,然后加入阻燃成分、4-羧基硼酸和辅助添加剂,加入三乙胺,最后加入4,8-二羟基喹啉-2-甲酸和去离子水,按照设定的条件反应,制得该防水剂。(The invention discloses a penetration-resistant curing waterproof agent for building walls, which comprises the following raw materials in parts by weight: 0.6-1 part of tetramethylammonium chloride, 80-90 parts of polytetrahydrofuran glycol, 30-40 parts of hexamethylene diisocyanate, 3-5 parts of trimethylsilanol, 16-20 parts of methyl ethyl ketone, 7-10 parts of flame retardant components, 3-5 parts of 4-carboxyl boric acid, 2-4 parts of auxiliary additives, 2-4 parts of 4, 8-dihydroxy quinoline-2-formic acid and 110 parts of deionized water; the penetration-resistant curing waterproof agent for the building wall surface is prepared by the following steps: firstly, weighing raw materials in parts by weight; secondly, preparing a prepolymer; and thirdly, adding trimethyl silanol and methyl ethyl ketone into the prepolymer, then adding the flame retardant component, 4-carboxyl boric acid and an auxiliary additive, adding triethylamine, finally adding 4, 8-dihydroxy quinoline-2-formic acid and deionized water, and reacting according to set conditions to obtain the waterproof agent.)

1. The building wall penetration-resistant curing waterproof agent is characterized by comprising the following raw materials in parts by weight:

0.6-1 part of tetramethylammonium chloride, 80-90 parts of polytetrahydrofuran glycol, 30-40 parts of hexamethylene diisocyanate, 3-5 parts of trimethylsilanol, 16-20 parts of methyl ethyl ketone, 7-10 parts of flame retardant components, 3-5 parts of 4-carboxyl boric acid, 2-4 parts of auxiliary additives, 2-4 parts of 4, 8-dihydroxy quinoline-2-formic acid and 110 parts of deionized water;

the penetration-resistant curing waterproof agent for the building wall surface is prepared by the following steps:

firstly, weighing raw materials in parts by weight;

secondly, adding tetramethylammonium chloride, polytetrahydrofuran diol and hexamethylene diisocyanate into a reaction kettle, and stirring and reacting for 4-5 hours under the conditions that the temperature is 80 ℃ and the rotating speed is 400r/min to obtain a prepolymer;

and thirdly, adding trimethylsilanol and methyl ethyl ketone into the prepolymer obtained in the second step, stirring and reacting for 3-4h at the temperature of 75 ℃ and the rotating speed of 300r/min, then adding the flame retardant component, 4-carboxyl boric acid and the auxiliary additive, raising the temperature to 85 ℃, reacting for 50min, adding triethylamine, continuing to react for 60min, then adding 4, 8-dihydroxy quinoline-2-formic acid and deionized water, and stirring for 50min to obtain the anti-penetration curing waterproof agent for the building wall surface.

2. The building wall penetration-resistant curing waterproof agent as claimed in claim 1, wherein the molecular weight of the polytetrahydrofuran diol is 1000; the auxiliary additive is diphenyl dihydroxy silane and kaempferol according to the mass ratio of 3: 1.2-1.6.

3. The building wall penetration-resistant curing waterproof agent as claimed in claim 1, wherein the flame-retardant component is prepared by the following steps:

step A1, adding ammonium polyphosphate into methanol, setting the temperature to be 60 ℃ and the rotating speed to be 100r/min, adding basic components, setting the heating rate to be 5 ℃/min, heating to 85 ℃, keeping the temperature and the rotating speed unchanged after the heating is finished, continuously stirring for reaction for 2 hours, filtering while hot after the reaction is finished, drying the obtained filter cake to constant weight at 60 ℃, and obtaining the flame-retardant component.

4. The building wall penetration-resistant curing waterproof agent as claimed in claim 3, wherein the amount ratio of the ammonium polyphosphate, the methanol and the base component in step A1 is 100 g: 300 mL: 15-20 g.

5. The penetration-resistant curing waterproof agent for building walls as claimed in claim 3, wherein the base component is prepared by the following steps:

step S11, adding formaldehyde and melamine into a three-neck flask, adjusting the pH value to 8 by using sodium hydroxide, heating to 70 ℃, stirring at the rotation speed of 300r/min, keeping the temperature and the rotation speed unchanged after a reaction solution is clarified, and continuously stirring for 50-60min to obtain a component A;

step S12, mixing N-ethyl, N-hydroxyethyl perfluorooctyl sulfonamide and N, N-dimethylformamide to prepare a mixed solution a, mixing 1, 2-cyclopentanedicarboxylic anhydride and N, N-dimethylformamide to prepare a mixed solution b, mixing the mixed solution a and the mixed solution b, setting the temperature at 60 ℃ and the rotating speed at 200r/min, stirring for 15-20min, then increasing the temperature to 85 ℃, adding 4-dimethylaminopyridine, and stirring for reaction for 7-9 h;

step S13, after the stirring reaction is finished, mixing the obtained reaction solution and deionized water according to the volume ratio of 1: 2, mixing, precipitating, stirring for 2 hours at the room temperature at the rotating speed of 120r/min, standing after stirring, removing supernatant, adding equal-volume deionized water, stirring for 15 minutes, standing, removing supernatant, performing vacuum filtration, and drying the obtained filter cake to constant weight at 25 ℃ under vacuum conditions to obtain a solid b;

and step S14, adding the solid b and toluene into a three-neck flask, then adding a toluene solution of the component A, stirring for 5-10min at the temperature of 60 ℃, then adding sodium bisulfite and sodium borohydride, stirring for 5-10min, raising the temperature to 80 ℃, adding 4-dimethylpyridine and N, N-dicyclohexyldiimine, stirring for reaction for 7h, filtering while hot after the reaction is finished, retaining the filtrate, mixing the filtrate with anhydrous ethanol with the same volume, distilling under reduced pressure, removing the ethanol, repeating for three times, and then drying under vacuum at the temperature of 25 ℃ to constant weight to obtain the basic component.

6. The penetration-resistant curing waterproof agent for building walls as claimed in claim 5, wherein the amount by mass ratio of formaldehyde to melamine in step S11 is 9: 3; in the step S12, the dosage ratio of the N-ethyl, N-hydroxyethyl perfluorooctyl sulfonamide to the N, N-dimethylformamide in the mixed solution a is 0.02 mol: 100mL, the dosage ratio of the 1, 2-cyclopentanedioic anhydride to the N, N-dimethylformamide in the mixed solution b is 0.08 moL: 100 mL; wherein the mixed solution a and the mixed solution b are mixed in equal volume, and the dosage of the 4-dimethylamino pyridine is 4 percent of the total mass of the N-ethyl, N-ethoxyl perfluorooctyl sulfonamide and the 1, 2-cyclopentanedioic anhydride.

7. The building wall penetration-resistant curing waterproof agent as claimed in claim 5, wherein the toluene solution of component A in step S14 is prepared by mixing component A and toluene in a ratio of 1 g: 15-20mL of the additive, toluene, a toluene solution of the component A, sodium bisulfite, sodium borohydride, 4-dimethylpyridine and N, N-dicyclohexyldiimine, wherein the dosage ratio of the additive to the toluene solution of the component A is 4-5 g: 20-30 mL: 45-50 mL: 1 g: 0.24 g: 0.12 g: 1.24 g.

8. The preparation method of the penetration-resistant curing waterproof agent for the building wall surface as claimed in claim 1, which is characterized by comprising the following steps:

firstly, weighing raw materials in parts by weight;

secondly, adding tetramethylammonium chloride, polytetrahydrofuran diol and hexamethylene diisocyanate into a reaction kettle, and stirring and reacting for 4-5 hours under the conditions that the temperature is 80 ℃ and the rotating speed is 400r/min to obtain a prepolymer;

and thirdly, adding trimethylsilanol and methyl ethyl ketone into the prepolymer obtained in the second step, stirring and reacting for 3-4h at the temperature of 75 ℃ and the rotating speed of 300r/min, then adding the flame retardant component, 4-carboxyl boric acid and the auxiliary additive, raising the temperature to 85 ℃, reacting for 50min, adding triethylamine, continuing to react for 60min, then adding 4, 8-dihydroxy quinoline-2-formic acid and deionized water, and stirring for 50min to obtain the anti-penetration curing waterproof agent for the building wall surface.

Technical Field

The invention belongs to the technical field of waterproof agent preparation, and particularly relates to a building wall surface anti-penetration curing waterproof agent and a preparation method thereof.

Background

In the field of waterproof engineering in the building industry, waterproofing is one of important functional elements, and the waterproofing is second to structures. The waterproof materials in the market are various in various types, and can be coils, powder, emulsion and the like in form; the materials can be divided into organic, inorganic and synthetic materials; a large amount of waterproof materials play a certain positive role in the development process of building waterproofing, and the concrete surface coating is a waterproof coating which is widely used at present. The concrete is coated with a continuous film layer with a certain thickness on the surface of the concrete, so that the surface gap is completely sealed, and the concrete structure is protected from the invasion of external harmful media. The wall is corroded by moisture, and when the moisture enters and exits a crack of a cement gap, white hairs are generated after long-time accumulation, so that the appearance is influenced.

The invention patent (CN103449750B) relates to a composite waterproof agent and a preparation method thereof. The composite waterproof agent comprises the following raw materials in percentage by mass based on the total mass of the raw materials: 60-75% of alkyl triethoxysilane; 15-25% of deionized water; 1-5% of a silane coupling agent; 1-3% of aluminum sulfate; 1-3% of emulsifier; 2-5% of polyvinyl alcohol and 0.5-2% of pH regulator, when preparing, firstly stirring and dissolving the emulsifier, polyvinyl alcohol, silane coupling agent and aluminum sulfate in 50-70 ℃ deionized water accounting for 50-70% of the mass of the formula deionized water, adding alkyl triethoxysilane after complete dissolution, fully stirring until the pH value is 3-6, and finally adding the residual deionized water and stirring until emulsion is stabilized. The composite waterproof agent prepared by the method can be widely applied to concrete, bricks, mortar and the like. Good waterproof effect, long weather resistance, environmental protection, no pollution and simple preparation method.

Disclosure of Invention

The invention provides a penetration-resistant curing waterproof agent for building wall surfaces and a preparation method thereof.

The technical problems to be solved by the invention are as follows:

in the field of waterproof engineering in the building industry, water resistance is one of important functional elements, a wall is corroded by moisture, and when the moisture enters and exits a cement gap crack, white wools are generated after long-time accumulation to influence the attractiveness.

The purpose of the invention can be realized by the following technical scheme:

a penetration-resistant curing waterproof agent for building walls comprises the following raw materials in parts by weight:

0.6-1 part of tetramethylammonium chloride, 80-90 parts of polytetrahydrofuran glycol, 30-40 parts of hexamethylene diisocyanate, 3-5 parts of trimethylsilanol, 16-20 parts of methyl ethyl ketone, 7-10 parts of flame retardant components, 3-5 parts of 4-carboxyl boric acid, 2-4 parts of auxiliary additives, 2-4 parts of 4, 8-dihydroxy quinoline-2-formic acid and 110 parts of deionized water;

the penetration-resistant curing waterproof agent for the building wall surface is prepared by the following steps:

firstly, weighing raw materials in parts by weight;

secondly, adding tetramethylammonium chloride, polytetrahydrofuran diol and hexamethylene diisocyanate into a reaction kettle, and stirring and reacting for 4-5 hours under the conditions that the temperature is 80 ℃ and the rotating speed is 400r/min to obtain a prepolymer;

and thirdly, adding trimethylsilanol and methyl ethyl ketone into the prepolymer obtained in the second step, stirring and reacting for 3-4h at the temperature of 75 ℃ and the rotating speed of 300r/min, then adding the flame retardant component, 4-carboxyl boric acid and the auxiliary additive, raising the temperature to 85 ℃, reacting for 50min, adding triethylamine, continuing to react for 60min, then adding 4, 8-dihydroxy quinoline-2-formic acid and deionized water, and stirring for 50min to obtain the anti-penetration curing waterproof agent for the building wall surface.

Further, polytetrahydrofuran diol has a molecular weight of 1000; the auxiliary additive is diphenyl dihydroxy silane and kaempferol according to the mass ratio of 3: 1.2-1.6. The auxiliary additive is formed by mixing diphenyl dihydroxy silane and kaempferol, wherein the kaempferol has excellent antibacterial performance and can react with hexamethylene diisocyanate to improve the antibacterial property of the kaempferol.

Further, the flame retardant component is prepared by the following steps:

step A1, adding ammonium polyphosphate into methanol, setting the temperature to be 60 ℃ and the rotating speed to be 100r/min, adding basic components, setting the heating rate to be 5 ℃/min, heating to 85 ℃, keeping the temperature and the rotating speed unchanged after the heating is finished, continuously stirring for reaction for 2 hours, filtering while hot after the reaction is finished, drying the obtained filter cake to constant weight at 60 ℃, and obtaining the flame-retardant component. The ammonium polyphosphate is insoluble in methanol to form a suspension, and then a basic component is added to coat the suspension; the prepared basic component is coated with the ammonium polyphosphate to prepare the flame-retardant component, the flame-retardant component is dispersed in the waterproof agent without agglomeration and can be uniformly dispersed, and the flame-retardant component has high phosphorus content and high nitrogen content and has high-efficiency flame-retardant effect.

Further, in the step A1, the dosage ratio of the ammonium polyphosphate, the methanol and the basic component is 100 g: 300 mL: 15-20 g.

Further, the base component is prepared by the following steps:

step S11, adding formaldehyde and melamine into a three-neck flask, adjusting the pH value to 8 by using sodium hydroxide, heating to 70 ℃, stirring at the rotation speed of 300r/min, keeping the temperature and the rotation speed unchanged after a reaction solution is clarified, and continuously stirring for 50-60min to obtain a component A;

step S12, mixing N-ethyl, N-hydroxyethyl perfluorooctyl sulfonamide and N, N-dimethylformamide to prepare a mixed solution a, mixing 1, 2-cyclopentanedicarboxylic anhydride and N, N-dimethylformamide to prepare a mixed solution b, mixing the mixed solution a and the mixed solution b, setting the temperature at 60 ℃ and the rotating speed at 200r/min, stirring for 15-20min, then increasing the temperature to 85 ℃, adding 4-dimethylaminopyridine, and stirring for reaction for 7-9 h;

step S13, after the reaction is finished, mixing the obtained reaction solution and deionized water according to the volume ratio of 1: 2, mixing, precipitating, stirring for 2 hours at the room temperature at the rotating speed of 120r/min, standing after stirring, removing supernatant, adding equal-volume deionized water, stirring for 15 minutes, standing, removing supernatant, performing vacuum filtration, and drying the obtained filter cake to constant weight at 25 ℃ under vacuum conditions to obtain a solid b;

step S14, adding the solid b and toluene into a three-neck flask, then adding a toluene solution of the component A, stirring for 5-10min at the temperature of 60 ℃, then adding sodium bisulfite and sodium borohydride, stirring for 5-10min, raising the temperature to 80 ℃, adding 4-dimethylpyridine and N, N-dicyclohexyldiimine, stirring for reaction for 7h, filtering while hot after the reaction is finished, retaining the filtrate, mixing the filtrate with anhydrous ethanol with the same volume, carrying out reduced pressure distillation, removing the ethanol, repeating for three times, removing the toluene in the system, and then carrying out vacuum drying to constant weight at the temperature of 25 ℃ to obtain the basic component.

Two amino groups on formaldehyde and melamine are firstly subjected to hydroxylamine condensation to obtain a component A, N-ethyl, N-hydroxyethyl perfluorooctyl sulfonamide and 1, 2-cyclopentanedioic anhydride, the esterification reaction is carried out under the catalytic action of 4-dimethylpyridine to obtain a solid b, the hydroxyl group on the solid b and the unreacted amino group on the component A are subjected to amidation reaction, and finally the solid b and the unreacted amino group are subjected to polycondensation to obtain melamine resin to obtain a basic component. Fluorine elements are introduced into melamine resin in the reaction process, the surface energy of fluorine carbon bonds is less than that of carbon-hydrogen bonds, the waterproof performance of the waterproof agent is further improved, after the waterproof agent is cured, the surface tension can be improved, and the antifouling effect of an interface is improved.

Further, the mass ratio of the formaldehyde to the melamine in the step S11 is 9: 3; in the step S12, the dosage ratio of the N-ethyl, N-hydroxyethyl perfluorooctyl sulfonamide to the N, N-dimethylformamide in the mixed solution a is 0.02 mol: 100mL, the dosage ratio of the 1, 2-cyclopentanedioic anhydride to the N, N-dimethylformamide in the mixed solution b is 0.08 moL: 100 mL; wherein the mixed solution a and the mixed solution b are mixed in equal volume, and the dosage of the 4-dimethylamino pyridine is 4 percent of the total mass of the N-ethyl, N-ethoxyl perfluorooctyl sulfonamide and the 1, 2-cyclopentanedioic anhydride.

Further, the toluene solution of component a in step S14 was prepared by mixing component a and toluene in an amount of 1 g: 15-20mL of the additive, toluene, a toluene solution of the component A, sodium bisulfite, sodium borohydride, 4-dimethylpyridine and N, N-dicyclohexyldiimine, wherein the dosage ratio of the additive to the toluene solution of the component A is 4-5 g: 20-30 mL: 45-50 mL: 1 g: 0.24 g: 0.12 g: 1.24 g.

Further, the preparation method of the anti-penetration curing waterproof agent for the building wall comprises the following steps:

firstly, weighing raw materials in parts by weight;

secondly, adding tetramethylammonium chloride, polytetrahydrofuran diol and hexamethylene diisocyanate into a reaction kettle, and stirring and reacting for 4-5 hours under the conditions that the temperature is 80 ℃ and the rotating speed is 400r/min to obtain a prepolymer;

and thirdly, adding trimethylsilanol and methyl ethyl ketone into the prepolymer obtained in the second step, stirring and reacting for 3-4h at the temperature of 75 ℃ and the rotating speed of 300r/min, then adding the flame retardant component, 4-carboxyl boric acid and the auxiliary additive, raising the temperature to 85 ℃, reacting for 50min, adding triethylamine, continuing to react for 60min, then adding 4, 8-dihydroxy quinoline-2-formic acid and deionized water, and stirring for 50min to obtain the anti-penetration curing waterproof agent for the building wall surface.

The invention has the beneficial effects that:

the ammonium polyphosphate is insoluble in methanol to form a suspension, and then a basic component is added to coat the suspension; the prepared basic component is coated with the ammonium polyphosphate to prepare the flame-retardant component, the flame-retardant component is dispersed in the waterproof agent without agglomeration and can be uniformly dispersed, and the flame-retardant component has high phosphorus content and high nitrogen content and has high-efficiency flame-retardant effect.

The method comprises the steps of firstly carrying out hydroxylamine condensation on formaldehyde and two amino groups on melamine to obtain a component A, carrying out esterification reaction on N-ethyl, N-hydroxyethyl perfluorooctylsulfonamide and 1, 2-cyclopentanedioic anhydride under the catalytic action of 4-dimethylpyridine to obtain a solid b, carrying out amidation reaction on hydroxyl groups on the solid b and unreacted amino groups on the component A, and finally carrying out condensation polymerization to obtain melamine resin to obtain a basic component.

The auxiliary additive is formed by mixing diphenyl dihydroxy silane and kaempferol, wherein the kaempferol has excellent antibacterial performance and can react with hexamethylene diisocyanate to improve the antibacterial property of the kaempferol.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

A penetration-resistant curing waterproof agent for building walls comprises the following raw materials in parts by weight:

0.6 part of tetramethylammonium chloride, 80 parts of polytetrahydrofuran diol, 3 parts of hexamethylene diisocyanate, 3 parts of trimethylsilanol, 16 parts of methyl ethyl ketone, 7 parts of a flame retardant component, 3 parts of 4-carboxyl boric acid, 2 parts of an auxiliary additive, 2 parts of 4, 8-dihydroxy quinoline-2-formic acid and 100 parts of deionized water;

the penetration-resistant curing waterproof agent for the building wall surface is prepared by the following steps:

firstly, weighing raw materials in parts by weight;

secondly, adding tetramethylammonium chloride, polytetrahydrofuran diol and hexamethylene diisocyanate into a reaction kettle, and stirring and reacting for 4 hours under the conditions that the temperature is 80 ℃ and the rotating speed is 400r/min to obtain a prepolymer;

and thirdly, adding trimethylsilanol and methyl ethyl ketone into the prepolymer obtained in the second step, stirring and reacting for 3 hours at the temperature of 75 ℃ and the rotating speed of 300r/min, then adding the flame-retardant component, 4-carboxyl boric acid and the auxiliary additive, raising the temperature to 85 ℃, reacting for 50 minutes, adding triethylamine, continuing to react for 60 minutes, then adding 4, 8-dihydroxy quinoline-2-formic acid and deionized water, and stirring for 50 minutes to obtain the anti-penetration curing waterproof agent for the building wall surface.

Wherein the molecular weight of the polytetrahydrofuran diol is 1000; the auxiliary additive is diphenyl dihydroxy silane and kaempferol according to the mass ratio of 3: 1.2 mixing.

Wherein the flame retardant component is prepared by the following steps:

step A1, adding ammonium polyphosphate into methanol, setting the temperature to be 60 ℃ and the rotating speed to be 100r/min, adding basic components, setting the heating rate to be 5 ℃/min, heating to 85 ℃, keeping the temperature and the rotating speed unchanged after the heating is finished, continuously stirring for reaction for 2 hours, filtering while hot after the reaction is finished, drying the obtained filter cake to constant weight at 60 ℃, and obtaining the flame-retardant component.

Wherein the dosage ratio of the ammonium polyphosphate to the methanol to the basic components in the step A1 is 100 g: 300 mL: 15 g.

Wherein the base component is prepared by the following steps:

step S11, adding formaldehyde and melamine into a three-neck flask, adjusting the pH value to 8 by using sodium hydroxide, heating to 70 ℃, stirring at the rotation speed of 300r/min, keeping the temperature and the rotation speed unchanged after a reaction solution is clarified, and continuously stirring for 50min to obtain a component A;

step S12, mixing N-ethyl, N-hydroxyethyl perfluorooctyl sulfonamide and N, N-dimethylformamide to prepare a mixed solution a, mixing 1, 2-cyclopentanedicarboxylic anhydride and N, N-dimethylformamide to prepare a mixed solution b, mixing the mixed solution a and the mixed solution b, setting the temperature at 60 ℃ and the rotating speed at 200r/min, stirring for 15min, then heating the temperature to 85 ℃, adding 4-dimethylaminopyridine, and stirring for reaction for 7 h;

step S13, after the stirring reaction is finished, mixing the obtained reaction solution and deionized water according to the volume ratio of 1: 2, mixing, precipitating, stirring for 2 hours at the room temperature at the rotating speed of 120r/min, standing after stirring, removing supernatant, adding equal-volume deionized water, stirring for 15 minutes, standing, removing supernatant, performing vacuum filtration, and drying the obtained filter cake to constant weight at 25 ℃ under vacuum conditions to obtain a solid b;

and step S14, adding the solid b and toluene into a three-neck flask, then adding a toluene solution of the component A, stirring for 5min at the temperature of 60 ℃, then adding sodium bisulfite and sodium borohydride, stirring for 5min, raising the temperature to 80 ℃, adding 4-dimethylpyridine and N, N-dicyclohexyldiimine, stirring for reaction for 7h, filtering while hot after the reaction is finished, retaining the filtrate, mixing the filtrate with anhydrous ethanol with the same volume, carrying out reduced pressure distillation, removing ethanol, repeating for three times, and then carrying out vacuum drying to constant weight at the temperature of 25 ℃ to obtain the basic component.

Wherein, the mass ratio of the formaldehyde to the melamine in the step S11 is 9: 3; in the step S12, the dosage ratio of the N-ethyl, N-hydroxyethyl perfluorooctyl sulfonamide to the N, N-dimethylformamide in the mixed solution a is 0.02 mol: 100mL, the dosage ratio of the 1, 2-cyclopentanedioic anhydride to the N, N-dimethylformamide in the mixed solution b is 0.08 moL: 100 mL; wherein the mixed solution a and the mixed solution b are mixed in equal volume, and the dosage of the 4-dimethylamino pyridine is 4 percent of the total mass of the N-ethyl, N-ethoxyl perfluorooctyl sulfonamide and the 1, 2-cyclopentanedioic anhydride.

Wherein the toluene solution of the component A in the step S14 is prepared by mixing the component A and toluene according to the dosage ratio of 1 g: 15mL of the auxiliary agent, toluene, a toluene solution of the component A, sodium bisulfite, sodium borohydride, 4-dimethylpyridine and N, N-dicyclohexyldiimine, wherein the dosage ratio of the auxiliary agent to the toluene solution of the component A is 4 g: 20mL of: 45mL of: 1 g: 0.24 g: 0.12 g: 1.24 g.

Example 2

A penetration-resistant curing waterproof agent for building walls comprises the following raw materials in parts by weight:

0.8 part of tetramethylammonium chloride, 85 parts of polytetrahydrofuran glycol, 35 parts of hexamethylene diisocyanate, 4 parts of trimethylsilanol, 18 parts of methyl ethyl ketone, 8 parts of a flame retardant component, 4 parts of 4-carboxyl boric acid, 3 parts of an auxiliary additive, 3 parts of 4, 8-dihydroxy quinoline-2-formic acid and 105 parts of deionized water;

the penetration-resistant curing waterproof agent for the building wall surface is prepared by the following steps:

firstly, weighing raw materials in parts by weight;

secondly, adding tetramethylammonium chloride, polytetrahydrofuran diol and hexamethylene diisocyanate into a reaction kettle, and stirring and reacting for 4.5 hours under the conditions that the temperature is 80 ℃ and the rotating speed is 400r/min to obtain a prepolymer;

and thirdly, adding trimethylsilanol and methyl ethyl ketone into the prepolymer obtained in the second step, stirring and reacting for 3.5 hours at the temperature of 75 ℃ and the rotating speed of 300r/min, then adding the flame-retardant component, 4-carboxyl boric acid and the auxiliary additive, raising the temperature to 85 ℃, reacting for 50 minutes, adding triethylamine, continuing to react for 60 minutes, then adding 4, 8-dihydroxy quinoline-2-formic acid and deionized water, and stirring for 50 minutes to obtain the anti-penetration curing waterproof agent for the building wall surface.

Wherein the molecular weight of the polytetrahydrofuran diol is 1000; the auxiliary additive is diphenyl dihydroxy silane and kaempferol according to the mass ratio of 3: 1.4 mixing.

Wherein the flame retardant component is prepared by the following steps:

step A1, adding ammonium polyphosphate into methanol, setting the temperature to be 60 ℃ and the rotating speed to be 100r/min, adding basic components, setting the heating rate to be 5 ℃/min, heating to 85 ℃, keeping the temperature and the rotating speed unchanged after the heating is finished, continuously stirring for reaction for 2 hours, filtering while hot after the reaction is finished, drying the obtained filter cake to constant weight at 60 ℃, and obtaining the flame-retardant component.

Wherein the dosage ratio of the ammonium polyphosphate to the methanol to the basic components in the step A1 is 100 g: 300 mL: 18 g.

Wherein the base component is prepared by the following steps:

step S11, adding formaldehyde and melamine into a three-neck flask, adjusting the pH value to 8 by using sodium hydroxide, heating to 70 ℃, stirring at the rotation speed of 300r/min, keeping the temperature and the rotation speed unchanged after a reaction solution is clarified, and continuously stirring for 55min to obtain a component A;

step S12, mixing N-ethyl, N-hydroxyethyl perfluorooctyl sulfonamide and N, N-dimethylformamide to prepare a mixed solution a, mixing 1, 2-cyclopentanedicarboxylic anhydride and N, N-dimethylformamide to prepare a mixed solution b, mixing the mixed solution a and the mixed solution b, setting the temperature at 60 ℃ and the rotating speed at 200r/min, stirring for 18min, then heating the temperature to 85 ℃, adding 4-dimethylaminopyridine, and stirring for reacting for 8 h;

step S13, after the stirring reaction is finished, mixing the obtained reaction solution and deionized water according to the volume ratio of 1: 2, mixing, precipitating, stirring for 2 hours at the room temperature at the rotating speed of 120r/min, standing after stirring, removing supernatant, adding equal-volume deionized water, stirring for 15 minutes, standing, removing supernatant, performing vacuum filtration, and drying the obtained filter cake to constant weight at 25 ℃ under vacuum conditions to obtain a solid b;

and step S14, adding the solid b and toluene into a three-neck flask, then adding a toluene solution of the component A, stirring for 8min at the temperature of 60 ℃, then adding sodium bisulfite and sodium borohydride, stirring for 8min, raising the temperature to 80 ℃, adding 4-dimethylpyridine and N, N-dicyclohexyldiimine, stirring for reaction for 7h, filtering while hot after the reaction is finished, retaining the filtrate, mixing the filtrate with anhydrous ethanol with the same volume, carrying out reduced pressure distillation, removing ethanol, repeating for three times, and then carrying out vacuum drying to constant weight at the temperature of 25 ℃ to obtain the basic component.

Wherein, the mass ratio of the formaldehyde to the melamine in the step S11 is 9: 3; in the step S12, the dosage ratio of the N-ethyl, N-hydroxyethyl perfluorooctyl sulfonamide to the N, N-dimethylformamide in the mixed solution a is 0.02 mol: 100mL, the dosage ratio of the 1, 2-cyclopentanedioic anhydride to the N, N-dimethylformamide in the mixed solution b is 0.08 moL: 100 mL; wherein the mixed solution a and the mixed solution b are mixed in equal volume, and the dosage of the 4-dimethylamino pyridine is 4 percent of the total mass of the N-ethyl, N-ethoxyl perfluorooctyl sulfonamide and the 1, 2-cyclopentanedioic anhydride.

Wherein the toluene solution of the component A in the step S14 is prepared by mixing the component A and toluene according to the dosage ratio of 1 g: 18mL of the mixture is obtained by mixing, wherein the dosage ratio of the auxiliary agent, toluene solution of the component A, sodium bisulfite, sodium borohydride, 4-dimethylpyridine and N, N-dicyclohexyldiimine is 4.5 g: 25mL of: 48mL of: 1 g: 0.24 g: 0.12 g: 1.24 g.

Example 3

A penetration-resistant curing waterproof agent for building walls comprises the following raw materials in parts by weight:

1 part of tetramethylammonium chloride, 90 parts of polytetrahydrofuran diol, 40 parts of hexamethylene diisocyanate, 5 parts of trimethylsilanol, 20 parts of methyl ethyl ketone, 10 parts of flame retardant components, 5 parts of 4-carboxyl boric acid, 4 parts of auxiliary additives, 4 parts of 4, 8-dihydroxy quinoline-2-formic acid and 110 parts of deionized water;

the penetration-resistant curing waterproof agent for the building wall surface is prepared by the following steps:

firstly, weighing raw materials in parts by weight;

secondly, adding tetramethylammonium chloride, polytetrahydrofuran diol and hexamethylene diisocyanate into a reaction kettle, and stirring and reacting for 5 hours under the conditions that the temperature is 80 ℃ and the rotating speed is 400r/min to obtain a prepolymer;

and thirdly, adding trimethylsilanol and methyl ethyl ketone into the prepolymer obtained in the second step, stirring and reacting for 4 hours at the temperature of 75 ℃ and the rotating speed of 300r/min, then adding the flame-retardant component, 4-carboxyl boric acid and the auxiliary additive, raising the temperature to 85 ℃, reacting for 50 minutes, adding triethylamine, continuing to react for 60 minutes, then adding 4, 8-dihydroxy quinoline-2-formic acid and deionized water, and stirring for 50 minutes to obtain the anti-penetration curing waterproof agent for the building wall surface.

Wherein the molecular weight of the polytetrahydrofuran diol is 1000; the auxiliary additive is diphenyl dihydroxy silane and kaempferol according to the mass ratio of 3: 1.6 mixing.

Wherein the flame retardant component is prepared by the following steps:

step A1, adding ammonium polyphosphate into methanol, setting the temperature to be 60 ℃ and the rotating speed to be 100r/min, adding basic components, setting the heating rate to be 5 ℃/min, heating to 85 ℃, keeping the temperature and the rotating speed unchanged after the heating is finished, continuously stirring for reaction for 2 hours, filtering while hot after the reaction is finished, drying the obtained filter cake to constant weight at 60 ℃, and obtaining the flame-retardant component.

Wherein the dosage ratio of the ammonium polyphosphate to the methanol to the basic components in the step A1 is 100 g: 300 mL: 20 g.

Wherein the base component is prepared by the following steps:

step S11, adding formaldehyde and melamine into a three-neck flask, adjusting the pH value to 8 by using sodium hydroxide, heating to 70 ℃, stirring at the rotation speed of 300r/min, keeping the temperature and the rotation speed unchanged after a reaction solution is clarified, and continuously stirring for 60min to obtain a component A;

step S12, mixing N-ethyl, N-hydroxyethyl perfluorooctyl sulfonamide and N, N-dimethylformamide to prepare a mixed solution a, mixing 1, 2-cyclopentanedicarboxylic anhydride and N, N-dimethylformamide to prepare a mixed solution b, mixing the mixed solution a and the mixed solution b, setting the temperature at 60 ℃ and the rotating speed at 200r/min, stirring for 20min, then heating the temperature to 85 ℃, adding 4-dimethylaminopyridine, and stirring for reacting for 9 h;

step S13, after the stirring reaction is finished, mixing the obtained reaction solution and deionized water according to the volume ratio of 1: 2, mixing, precipitating, stirring for 2 hours at the room temperature at the rotating speed of 120r/min, standing after stirring, removing supernatant, adding equal-volume deionized water, stirring for 15 minutes, standing, removing supernatant, performing vacuum filtration, and drying the obtained filter cake to constant weight at 25 ℃ under vacuum conditions to obtain a solid b;

and step S14, adding the solid b and toluene into a three-neck flask, then adding a toluene solution of the component A, stirring for 10min at the temperature of 60 ℃, then adding sodium bisulfite and sodium borohydride, stirring for 10min, raising the temperature to 80 ℃, adding 4-dimethylpyridine and N, N-dicyclohexyldiimine, stirring for reaction for 7h, filtering while hot after the reaction is finished, retaining the filtrate, mixing the filtrate with anhydrous ethanol with the same volume, carrying out reduced pressure distillation, removing ethanol, repeating for three times, and then carrying out vacuum drying to constant weight at the temperature of 25 ℃ to obtain the basic component.

Wherein, the mass ratio of the formaldehyde to the melamine in the step S11 is 9: 3; in the step S12, the dosage ratio of the N-ethyl, N-hydroxyethyl perfluorooctyl sulfonamide to the N, N-dimethylformamide in the mixed solution a is 0.02 mol: 100mL, the dosage ratio of the 1, 2-cyclopentanedioic anhydride to the N, N-dimethylformamide in the mixed solution b is 0.08 moL: 100 mL; wherein the mixed solution a and the mixed solution b are mixed in equal volume, and the dosage of the 4-dimethylamino pyridine is 4 percent of the total mass of the N-ethyl, N-ethoxyl perfluorooctyl sulfonamide and the 1, 2-cyclopentanedioic anhydride.

Wherein the toluene solution of the component A in the step S14 is prepared by mixing the component A and toluene according to the dosage ratio of 1 g: 20mL of the mixture is obtained by mixing, wherein the dosage ratio of the auxiliary agent, the toluene solution of the component A, the sodium bisulfite, the sodium borohydride, the 4-dimethylpyridine and the N, N-dicyclohexyl diimine is 5 g: 30mL of: 50mL of: 1 g: 0.24 g: 0.12 g: 1.24 g.

Comparative example 1

The flame retardant ingredients in example 1 were replaced with ammonium polyphosphate, and the remaining raw materials and preparation process remained unchanged.

The water repellent agents obtained in examples 1 to 3 and comparative example 1 were tested by the following methods:

water resistance: uniformly coating a proper amount of waterproof agent on a cement board, and drying at a certain temperature to form a film; and measuring a contact angle with water, then putting the cement board into deionized water for soaking for 48 hours, and observing the conditions of blue, whitish, foaming, wrinkling and shedding of a coating film. Flame retardancy is measured by the smoke density method (maximum smoke density, time to reach maximum smoke density), oxygen index;

the test results are shown in table 1 below:

TABLE 1

As can be seen from the above table 1, the contact angles of the prepared waterproofing agent and water are all larger than 120 degrees, the prepared waterproofing agent belongs to a hydrophobic surface, no bubble is generated after the waterproofing agent is soaked in water, water infiltration can be effectively prevented, fluorine element is introduced into melamine resin in the reaction process, the surface energy of fluorine-carbon bonds is smaller than that of carbon-hydrogen bonds, the waterproofing performance of the waterproofing agent is further improved, the surface tension can be improved and the antifouling effect of an interface can be improved after the waterproofing agent is solidified, and the prepared waterproofing agent has a good waterproofing effect. The flame retardant effect is good, and the application prospect is good.

In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.