A highly hydrophobic, stretch-resistant fluorinated acrylic resin paper waterproofing agent and a method of making

Abstract

This invention discloses a highly hydrophobic, tensile-resistant fluorinated acrylic resin paper waterproofing agent and its preparation method, belonging to the field of waterproof material preparation. Using N,N-methylenebisacrylamide, isooctyl acrylate, styrene, hydroxyethyl methacrylate, acrylic acid, glyceryl acrylate, and hexafluorobutyl methacrylate as monomers, and deionized water as the medium, a free radical polymerization reaction is carried out under alkaline conditions at 80-90℃ in the presence of an initiator and emulsifier. The mixture is then kept at this temperature, and the resulting emulsion is adjusted to neutral to obtain a highly hydrophobic, tensile-resistant fluorinated acrylic resin paper waterproofing agent in emulsion form. The polymer emulsion can form extremely low surface energy on the paper surface, effectively preventing water molecules from entering and achieving excellent hydrophobic effects. Due to the addition of cross-linking functional monomers to the polymer emulsion, the tensile strength of the paper is further improved, resulting in high overall practicality.

Description

Technical Field

[0001] This invention belongs to the field of waterproof material preparation, specifically a highly hydrophobic, tensile-resistant fluorinated acrylic resin paper waterproofing agent and its preparation method. Background Technology

[0002] Acrylic resins are high-molecular polymers copolymerized from acrylates, methacrylates, and other olefin monomers. They possess excellent heat resistance, corrosion resistance, light resistance, weather resistance, and coating properties, and are widely used in coatings, adhesives, and leather finishing agents. Traditional single-solvent-based acrylic resins have poor thermal stability, inadequate water resistance and chemical resistance, and high surface energy, which limits their applications. With increasing emphasis on health and environmental protection, traditional solvent-based acrylic resins are being phased out, replaced by safer, greener, and low-VOC water-based acrylic resins.

[0003] Fluoropolymers possess three high properties and two repellent properties: high chemical inertness, high thermal stability, high surface activity, and hydrophobic and oleophobic properties. They can be used as finishing agents for textile fibers, leather coatings, and anti-corrosion coatings. Acrylic ester emulsions with fluorocarbon side chains form films with extremely low surface energy and high thermal stability. The addition of fluorinated functional monomers can give the polymer excellent anti-aging properties, thermal stability, low dielectric constant, low tribological properties, and a uniquely low surface free energy, resulting in resins that exhibit outstanding hydrophobic and antifouling properties. Fluorinated acrylic resins not only retain the original characteristics of ordinary polyacrylates but also exhibit strong surface properties, leading to their widespread application in many high-tech fields due to their unique and superior performance.

[0004] Paper waterproofing agents come in a variety of types, broadly categorized into two main types: natural polymers, such as carboxymethyl cellulose, chitosan, and starch, and synthetic polymers, such as alkyl ketene dimers, alkenyl succinic anhydride, and styrene-acrylate copolymers. Natural polymers have certain limitations in sizing and waterproofing performance; for example, carboxymethyl cellulose has a weak waterproofing effect and is usually used in combination with other waterproofing agents, while starch can affect other paper properties such as strength and air permeability. Synthetic polymers, such as alkyl ketene dimers and alkenyl succinic anhydride, are either too expensive or require stringent sizing conditions, placing a significant burden on papermaking. However, utilizing the low surface energy of fluoropolymers, fluorinated monomers are used to modify styrene-acrylate copolymers to synthesize fluorinated acrylic resin copolymers. Due to their highly efficient and unique waterproofing properties, these copolymers are widely used in paper waterproofing agents. Paper treated with fluorinated acrylic resin waterproofing agents has been used in printing, industrial packaging, food packaging, and daily necessities. However, its waterproof and mechanical properties no longer meet current needs, which greatly limits its further application. Summary of the Invention

[0005] To address the problems existing in the prior art, this invention provides a highly hydrophobic and tensile-resistant fluorinated acrylic resin paper waterproofing agent and its preparation method. This solves the problem that the waterproofing and mechanical properties of current fluorinated acrylic resins cannot meet current needs when treating paper. It is safe, environmentally friendly, and has a low production cost. The polymer emulsion can form an extremely low surface energy on the paper surface, thereby effectively preventing water molecules from entering and achieving excellent hydrophobic effects. Due to the addition of crosslinking functional monomers to the polymer emulsion, the tensile strength of the paper is further improved, resulting in high overall practicality.

[0006] This invention is achieved through the following technical solution:

[0007] A method for preparing a highly hydrophobic, tensile-resistant fluorinated acrylic resin paper waterproofing agent involves using N,N-methylenebisacrylamide, isooctyl acrylate, styrene, hydroxyethyl methacrylate, acrylic acid, glyceryl acrylate, and hexafluorobutyl methacrylate as reactants, and deionized water as the medium. The reaction is carried out under alkaline conditions at 80-90°C with the aid of an initiator and emulsifier, followed by heat preservation. The resulting emulsion is then adjusted to neutral to obtain the highly hydrophobic, tensile-resistant fluorinated acrylic resin paper waterproofing agent.

[0008] A further improvement of the present invention is that:

[0009] The mixture comprises hexafluorobutyl methacrylate as component I, isooctyl acrylate and styrene as component II, and hydroxyethyl methacrylate, acrylic acid, glyceryl acrylate and N,N-methylenebisacrylamide as component III. Hexafluorobutyl methacrylate accounts for 28% of the total mass M of components I, II, III, initiator and emulsifier, component II accounts for 52% of M, isooctyl acrylate and styrene have a mass ratio of 1:1, N,N-methylenebisacrylamide accounts for 1% of M, acrylic acid accounts for 5% of M, glyceryl acrylate accounts for 3.5% of M, hydroxyethyl methacrylate accounts for 4.5% of M, initiator accounts for 0.5% of M, and emulsifier accounts for 5.5% of M.

[0010] Specifically, the following steps are included:

[0011] S1, isooctyl acrylate, styrene, hydroxyethyl methacrylate, acrylic acid, glyceryl acrylate and hexafluorobutyl methacrylate are mixed evenly to obtain an oily system;

[0012] The initiator and sodium bicarbonate were dissolved in deionized water to obtain the initiation system;

[0013] S2, at 80-90℃, the oily system, the initiating system and the aqueous solution of N,N-methylenebisacrylamide are added dropwise to the aqueous solution of the emulsifier, and then kept at this temperature for 30-60 minutes to obtain the emulsion;

[0014] S3. After the emulsion cools to room temperature, adjust the pH of the cooled emulsion to neutral, then filter the obtained emulsion and collect the filtrate to obtain a highly hydrophobic, tensile-resistant fluorinated acrylic resin paper waterproofing agent.

[0015] The initiator in S1 is ammonium persulfate or potassium persulfate.

[0016] The emulsifier described in S2 is a nonionic octylphenol polyoxyethylene ether and anionic allyloxynonylphenol propanol polyoxyethylene ether ammonium sulfate, with a mass ratio of 1:2.

[0017] In S1, the mass ratio of initiator, sodium bicarbonate, and deionized water is (1.2-2.4): (1.8-3.6):300;

[0018] In the N,N-methylenebisacrylamide aqueous solution described in S2, the mass ratio of N,N-methylenebisacrylamide to deionized water is 1:40, and in the emulsifier aqueous solution, the mass ratio of anionic allyloxynonylphenol propanol polyoxyethylene ether ammonium sulfate to deionized water is (1-2.4):(40-70).

[0019] S2 adds the oily system, the initiating system, and the aqueous solution of N,N-methylenebisacrylamide dropwise to the aqueous solution of the emulsifier at a constant rate for 3-4 hours, and then keeps it at a constant temperature.

[0020] S3 uses 28% ammonia water by mass to adjust the pH of the cooled emulsion to neutral.

[0021] S3 is the emulsion obtained by filtering through a 200-mesh filter.

[0022] The highly hydrophobic, tensile-resistant fluorinated acrylic resin paper waterproofing agent obtained by any one of the above methods.

[0023] Compared with the prior art, the present invention has the following beneficial technical effects:

[0024] This invention discloses a method for preparing a highly hydrophobic, tensile-resistant fluorinated acrylic resin paper waterproofing agent, wherein hydroxyethyl methacrylate, acrylic acid, and glyceryl acrylate are acrylic functional monomers, and the acrylic functional monomers and N , N Methylenebisacrylamide is a crosslinking monomer that, through free radical polymerization with hexafluorobutyl methacrylate, isooctyl acrylate, and styrene under alkaline conditions (80-90°C) with an initiator and emulsifier, forms a fluorinated acrylic resin waterproofing agent. Due to the introduction of the fluorinated monomer hexafluorobutyl methacrylate into the polymerization process, it possesses a unique long-chain fluoroalkyl structure, resulting in extremely low surface free energy and imparting excellent hydrophobicity to paper; [The remaining text appears to be incomplete and requires further context.] N , N Methylenebisacrylamide is a hydrophilic functional monomer; its addition increases the hydrophilicity of the system and improves the crosslinking performance of the adhesive. The epoxy groups in glyceryl acrylate undergo ring-opening reactions under high temperature and alkaline conditions, producing self-crosslinking and forming a self-crosslinking network structure. This network structure can crosslink with the hydroxyl groups on natural fibers, forming an interpenetrating network structure and enhancing the adhesion between fibers, thus greatly improving the bonding strength of the paper. Styrene, as a hard monomer, has a high glass transition temperature, imparting cohesive strength to the polymer. This invention uses deionized water as a medium for the emulsion polymerization of fluorinated acrylates. The resulting emulsion-like fluorinated acrylic resin waterproofing agent can form extremely low surface energy on the paper surface, effectively preventing water molecules from entering and achieving excellent hydrophobic effects. Due to the addition of crosslinking functional monomers to the polymer emulsion, the tensile strength of the paper is further improved. It is environmentally friendly, stable, green, and safe, suitable for industrial production. When used in internal sizing of paper pulp, the baked paper can achieve a water contact angle of up to 135.6° and a Cobb value of only 15.6-25.9 g / m³. 2 It exhibits excellent waterproof and stain-removing properties, and has high overall practicality. Attached Figure Description

[0025] Figure 1a This is a schematic diagram of the reaction of the reagent portion of the waterproofing agent of the present invention.

[0026] Figure 1b This is a schematic diagram of the structure of the waterproofing agent of the present invention.

[0027] Figure 2 This is the FTIR spectrum of the waterproofing agent described in this invention.

[0028] Figure 3 This is a test diagram of the mechanical properties of the sized paper according to the present invention.

[0029] Figure 4a This is a schematic diagram of the contact angle of the base paper of this invention.

[0030] Figure 4b This is a schematic diagram of the contact angle of the sizing paper of the present invention.

[0031] Figure 5 This is a graph showing the changes in Cobb paper produced by sizing paper with different amounts of fluorinated monomers added according to the present invention.

[0032] Figure 6 This is a scanning electron microscope (SEM) schematic diagram of the original paper of this invention.

[0033] Figure 7 This is a scanning electron microscope (SEM) schematic diagram of the sizing paper of the present invention. Detailed Implementation

[0034] The present invention will be further described in detail below with reference to specific embodiments. These descriptions are for explanation purposes only and are not intended to limit the scope of the invention.

[0035] This invention discloses a highly hydrophobic, tensile-resistant fluorinated acrylic resin paper waterproofing agent, comprising component I, component II, component III, an initiator, and an emulsifier. Component I is hexafluorobutyl methacrylate (GO2), component II is styrene (St) and isooctyl acrylate (EHA) in a 1:1 mass ratio, and component III is a mixture of acrylic functional monomers and N,N-methylenebisacrylamide (MBA). Component I accounts for 28% of the total mass of all components, component II accounts for 52%, component III accounts for 14%, the initiator accounts for 0.5%, and the emulsifier accounts for 5.5%.

[0036] The acrylic functional monomers include acrylic acid (AA), glyceryl acrylate (GMA), and hydroxyethyl methacrylate (HEMA). N,N-methylenebisacrylamide accounts for 1% of the total mass of all components, acrylic acid accounts for 5% of the total mass of all components, glyceryl acrylate accounts for 3.5% of the total mass of all components, and hydroxyethyl methacrylate accounts for 4.5% of the total mass of all components.

[0037] The initiator is a persulfate, specifically either ammonium persulfate or potassium persulfate.

[0038] The emulsifiers are nonionic octylphenol polyoxyethylene ether (OP-10) and anionic allyloxynonylphenol propanol polyoxyethylene ether ammonium sulfate (DNS-86), with a mass ratio of 1:2.

[0039] This invention discloses a method for preparing a highly hydrophobic, tensile-resistant fluorinated acrylic resin paper waterproofing agent, which specifically includes the following steps:

[0040] S1. Weigh the emulsifier into a three-necked flask, add a certain amount of deionized water, and the mass ratio of DNS-86 to deionized water is (1-2.4):(40-70), and use it as a base material for later use.

[0041] S2, N,N-methylenebisacrylamide is dissolved in a certain amount of deionized water, with the mass ratio of N,N-methylenebisacrylamide to deionized water being 1:40, to prepare water-soluble monomer A.

[0042] S3: Mix isooctyl acrylate and styrene evenly, then add hydroxyethyl methacrylate, acrylic acid, glyceryl acrylate, and finally hexafluorobutyl methacrylate, and mix evenly. This will be used as oily mixed monomer B for later use.

[0043] S4. Dissolve the initiator and pH modifier sodium bicarbonate in a certain amount of deionized water. The mass ratio of initiator, sodium bicarbonate and deionized water is (1.2-2.4): (1.8-3.6):300, which is used to prepare an initiator aqueous solution C.

[0044] S5. Under conditions of 80-90℃, slowly add the solutions prepared in steps S2, S3, and S4 to the base material dissolved in step S1. The addition time is controlled at 3-4 hours. The addition is carried out through a constant pressure dropping funnel. After the addition is completed, keep the emulsion warm for 30-60 minutes. After cooling to room temperature, adjust the pH of the emulsion to neutral using 28% ammonia water by mass. Filter the emulsion through a 200-mesh filter and collect the filtrate to obtain the fluorinated acrylic resin waterproofing agent.

[0045] Example 1

[0046] S1, at room temperature, take 1g of OP-10 and 2g of DNS-86 and dissolve them in 60g of deionized water to prepare the base material for later use;

[0047] S2, 0.5 g of N , N -Methylenebisacrylamide was dissolved in 20 g of deionized water to prepare water-soluble monomer A;

[0048] S3, weigh 15 g each of styrene and isooctyl acrylate, stir evenly, then add 3 g of acrylic acid, 2 g of glyceryl acrylate and 2.5 g of hydroxyethyl methacrylate, mix evenly, and finally add 16 g of hexafluorobutyl methacrylate. Mix the above monomers evenly and stir thoroughly. This is prepared as oily mixed monomer B for later use.

[0049] S4, place it in a constant pressure dropping funnel, and then dissolve 0.20 g of ammonium persulfate and 0.30 g of sodium bicarbonate in 30 g of deionized water to prepare initiator aqueous solution C.

[0050] Heat the water bath to 90℃, and slowly add the solutions prepared in steps S2, S3, and S4 to the substrate dissolved in step S1. Control the adding time to 3 hours, then keep it at the temperature for 1 hour, and then cool it to room temperature. Adjust the pH to neutral using ammonia water with a mass percentage of 28%. Filter the solution through a 200-mesh filter and collect the filtrate to obtain a fluorinated acrylic resin waterproofing agent with a solid content of 28.6%.

[0051] Example 2

[0052] S1, at room temperature, dissolve 0.8g of OP-10 and 1.6g of DNS-86 in 50g of deionized water to prepare the base material for later use;

[0053] S2, 0.5 g of N , N -Methylenebisacrylamide was dissolved in 20 g of deionized water to prepare water-soluble monomer A;

[0054] S3, weigh 15 g each of styrene and isooctyl acrylate, stir evenly, then add 3 g of acrylic acid, 2 g of glyceryl acrylate and 2.5 g of hydroxyethyl methacrylate, mix evenly, and finally add 10 g of hexafluorobutyl methacrylate. Mix the above monomers evenly and stir thoroughly. This is used as oily mixed monomer B for later use.

[0055] S4 is placed in a constant pressure dropping funnel, and then 0.18 g of ammonium persulfate and 0.27 g of sodium bicarbonate are dissolved in 30 g of deionized water to prepare initiator aqueous solution C.

[0056] Heat the water bath to 90℃, and slowly add the solutions prepared in steps S2, S3, and S4 to the substrate dissolved in step S1. Control the adding time to 3 hours, then keep it at the temperature for 1 hour, and then cool it to room temperature. Adjust the pH to neutral using ammonia water with a mass percentage of 28%, filter it through a 200-mesh filter, and collect the filtrate to obtain a fluorinated acrylic resin waterproofing agent with a solid content of 28.8%.

[0057] Example 3

[0058] S1, at room temperature, dissolve 1.2g of OP-10 and 2.4g of DNS-86 in 70g of deionized water to prepare the base material for later use;

[0059] S2, 0.5 g of N , N -Methylenebisacrylamide was dissolved in 20 g of deionized water to prepare water-soluble monomer A;

[0060] S3, weigh 15 g each of styrene and isooctyl acrylate, stir evenly, then add 3 g of acrylic acid, 2 g of glyceryl acrylate and 2.5 g of hydroxyethyl methacrylate, mix evenly, and finally add 25 g of hexafluorobutyl methacrylate. Mix the above monomers evenly and stir thoroughly. This is used as oily mixed monomer B for later use.

[0061] S4 is placed in a constant pressure dropping funnel, and then 0.24 g of ammonium persulfate and 0.36 g of sodium bicarbonate are dissolved in 30 g of deionized water to prepare an initiator aqueous solution C.

[0062] Heat the water bath to 90℃, and slowly add the solutions prepared in steps S2, S3, and S4 to the substrate dissolved in step S1. Control the adding time to 3 hours, then keep it at the temperature for 1 hour, and then cool it to room temperature. Adjust the pH to neutral using ammonia water with a mass percentage of 28%. Filter the solution through a 200-mesh filter and collect the filtrate to obtain a fluorinated acrylic resin waterproofing agent with a solid content of 29.2%.

[0063] Example 4

[0064] S1, at room temperature, dissolve 0.5g of OP-10 and 1g of DNS-86 in 40g of deionized water to prepare the base material for later use;

[0065] S2, 0.5 g of N , N -Methylenebisacrylamide was dissolved in 20 g of deionized water to prepare water-soluble monomer A;

[0066] S3, weigh 15 g each of styrene and isooctyl acrylate, stir evenly, then add 3 g of acrylic acid, 2 g of glyceryl acrylate and 2.5 g of hydroxyethyl methacrylate, mix evenly, and finally add 4.5 g of hexafluorobutyl methacrylate. Mix the above monomers evenly and stir thoroughly. This is used as oily mixed monomer B for later use.

[0067] S4 is placed in a constant pressure dropping funnel, and then 0.12 g of ammonium persulfate and 0.18 g of sodium bicarbonate are dissolved in 30 g of deionized water to prepare an initiator aqueous solution C.

[0068] Heat the water bath to 90℃, and slowly add the solutions prepared in steps S2, S3, and S4 to the substrate dissolved in step S1. Control the adding time to 4 hours, then keep it at the temperature for 1 hour, and then cool it to room temperature. Adjust the pH to neutral using ammonia water with a mass percentage of 28%, filter it through a 200-mesh filter, and collect the filtrate to obtain a fluorinated acrylic resin waterproofing agent with a solid content of 28.4%.

[0069] Figure 1a This is a schematic diagram of the reaction in the reagent part of the waterproofing agent synthesis, using ammonium persulfate as an initiator. From Figure 1b It can be seen that the monomers were successfully synthesized into a linear polymer compound through free radical polymerization.

[0070] Figure 2 This is the FTIR spectrum of the waterproofing agent. From the graph, we can see that 2925 and 2860 cm⁻¹... -1 The peak that appears belongs to the stretching vibration peak of CH in -CH3 and -CH2, 1727 cm⁻¹. -1 A carbonyl absorption peak appears, 1245–1020 cm⁻¹ -1 The peak that appears belongs to -CF ２ and -CF ３ The stretching vibration peak and the absorption peak of -COC- indicate that G02 participated in the copolymerization reaction, as shown at 1631 cm⁻¹. -1 The peak that appears is the stretching vibration peak of the amide carbonyl group, at 756 cm⁻¹. -1 702 cm -1 The two sharp absorption peaks at 1460 cm⁻¹ are due to the -CH stretching vibration on the aromatic ring. -1 The presence of an absorption peak at 1640 cm⁻¹ confirms the presence of a benzene ring. -1 The absence of characteristic absorption peaks for carbon-carbon double bonds in the vicinity indicates that all monomers have fully polymerized through double bonds, and strong covalent bonds have been formed between the monomers through emulsion polymerization.

[0071] Figure 3To test the mechanical properties of sized paper, bleached sulfate wood pulp was beaten using a standard beater at a freeness of 25°SR. Then, using an in-pulp sizing method, sized and unsized paper samples were taken. The samples were hot-pressed, dried, and finally cut into dumbbell shapes. Tensile strength tests were conducted using a servo-controlled multi-functional high and low temperature tensile testing machine. The total sample length was 75 mm, and the center width was 4 mm. A TRD-500 kgf sensor was used, and the testing speed was 10 mm / min. The graph shows that the tensile strength of the unsized paper is 8.2 MPa, while the tensile strength of the paper sized with the waterproofing agent reaches 18.9 MPa. This indicates that the waterproofing agent further improves the mechanical properties of the paper.

[0072] Figure 4a This is a schematic diagram of the contact angle of the base paper of the present invention. As can be seen from the figure, the contact angle of the base paper with water is 48.6°, which indicates that the base paper does not have a significant waterproof effect.

[0073] Figure 4b This is a schematic diagram of the contact angle of the sized paper of the present invention. As can be seen from the figure, the contact angle of the paper with water after being sized with the waterproofing agent can reach 135.6°. This shows that the waterproofing effect of the paper after being sized with the waterproofing agent is greatly improved, indicating that the waterproofing agent has high overall practicality.

[0074] Figure 5 The graph shows the changes in the Cobb value of sized paper with different amounts of fluorinated monomers. As can be seen from the graph, the Cobb value of the sized paper gradually decreases with the increase of hexafluorobutyl methacrylate (GO2) content. This is because as the hydrophobic components in the polymer increase, the hydrophobic fluorinated groups can inhibit water molecules from penetrating through the paper surface into the paper interior. Therefore, the Cobb value of the paper continuously decreases. It can be seen that this waterproofing agent can significantly improve the waterproof performance of the paper.

[0075] Figure 6 This is a scanning electron microscope (SEM) schematic diagram of the paper used in this invention. As can be seen from the diagram, the surface of the paper without added waterproofing agent is uneven and has many pores arranged in a disordered manner, and the fibers are not tightly woven.

[0076] Figure 7 This is a scanning electron microscope (SEM) schematic diagram of the sized paper of the present invention. The diagram shows that the paper with added waterproofing agent exhibits a tighter fiber arrangement and weave, smaller gaps between fibers, improved paper uniformity, and a smooth, flat surface. This indicates that the waterproofing agent adheres to the interior of the pulp fibers, forming a robust, interwoven network structure.

Claims

1. A method for preparing a highly hydrophobic, stretch-resistant, fluorine-containing acrylic resin paper waterproofing agent, characterized by, Using N,N-methylenebisacrylamide, isooctyl acrylate, styrene, hydroxyethyl methacrylate, acrylic acid, glyceryl acrylate, and hexafluorobutyl methacrylate as monomers, and deionized water as the medium, a free radical polymerization reaction was carried out under alkaline conditions at 80-90℃ with the aid of an initiator and emulsifier, followed by heat preservation. Hexafluorobutyl methacrylate was component I, isooctyl acrylate and styrene were component II, and hydroxyethyl methacrylate, acrylic acid, glyceryl acrylate, and N,N-methylenebisacrylamide were component III. Hexafluorobutyl methacrylate accounted for 28% of the total mass M of components I, II, III, initiator, and emulsifier; component II accounted for 52% of M; the mass ratio of isooctyl acrylate to styrene was 1:1; N,N-methylenebisacrylamide accounted for 1% of M; acrylic acid accounted for 5% of M; glyceryl acrylate accounted for 3.5% of M; and hydroxyethyl methacrylate accounted for 4.5% of M. The initiator accounts for 0.5% of M, and the emulsifier accounts for 5.5% of M. The initiator is ammonium persulfate or potassium persulfate, and the emulsifier is nonionic octylphenol polyoxyethylene ether and anionic allyloxynonylphenol propanol polyoxyethylene ether ammonium sulfate. The mass ratio of nonionic octylphenol polyoxyethylene ether and anionic allyloxynonylphenol propanol polyoxyethylene ether ammonium sulfate is 1:

2. The resulting emulsion is then adjusted to neutral to obtain a highly hydrophobic, tensile-resistant fluorinated acrylic resin paper waterproofing agent, which specifically includes the following steps: S1, isooctyl acrylate, styrene, hydroxyethyl methacrylate, acrylic acid, glyceryl acrylate and hexafluorobutyl methacrylate are mixed evenly to obtain an oily system; The initiator and sodium bicarbonate were dissolved in deionized water in a mass ratio of (1.2-2.4): (1.8-3.6):300 to obtain the initiation system. S2, at 80-90℃, the oily system, the initiating system and the aqueous solution of N,N-methylenebisacrylamide are added dropwise to the aqueous solution of the emulsifier at a constant rate for 3-4 hours, and then kept at the temperature for 30-60 minutes to obtain the emulsion; S3. After the emulsion cools to room temperature, adjust the pH of the cooled emulsion to neutral, then filter the obtained emulsion and collect the filtrate to obtain a highly hydrophobic, tensile-resistant fluorinated acrylic resin paper waterproofing agent.

2. The preparation method of the highly hydrophobic, tensile-resistant fluorinated acrylic resin paper waterproofing agent according to claim 1, characterized in that, In the N,N-methylenebisacrylamide aqueous solution described in S2, the mass ratio of N,N-methylenebisacrylamide to deionized water is 1:40, and in the emulsifier aqueous solution, the mass ratio of anionic allyloxynonylphenol propanol polyoxyethylene ether ammonium sulfate to deionized water is (1-2.4):(40-70).

3. The preparation method of the highly hydrophobic, tensile-resistant fluorinated acrylic resin paper waterproofing agent according to claim 1, characterized in that, S3 uses 28% ammonia water by mass to adjust the pH of the cooled emulsion to neutral.

4. The method of claim 1, wherein the highly hydrophobic, tensile-stretching, fluorinated acrylic resin paper waterproofing agent is characterized by, S3 is the emulsion obtained by filtering through a 200-mesh filter.

5. A highly hydrophobic, tensile-resistant fluorinated acrylic resin paper waterproofing agent obtained by the preparation method of the highly hydrophobic, tensile-resistant fluorinated acrylic resin paper waterproofing agent according to any one of claims 1 to 4.

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