High-hydrophobicity tensile fluorine-containing acrylic resin paper waterproofing agent and preparation method thereof

Abstract

The invention discloses a high-hydrophobicity stretch-resistant fluorine-containing acrylic resin paper waterproof agent and a preparation method, and belongs to the field of waterproof material preparation. N, N-methylene bisacrylamide, 2-ethylhexyl acrylate, styrene, hydroxyethyl methylacrylate, acrylic acid, glyceryl acrylate and hexafluorobutyl methacrylate are used as reaction monomers; the preparation method comprises the following steps: carrying out a free radical polymerization reaction under the alkaline condition of 80-90 DEG C under the action of an initiator and an emulsifier by taking deionized water as a medium, carrying out heat preservation, and adjusting the obtained emulsion to be neutral, thereby obtaining the emulsion-like high-hydrophobicity stretch-resistant fluorine-containing acrylic resin paper waterproof agent. The polymer emulsion can form extremely low surface energy on the surface of the paper, so that water molecules are effectively prevented from entering the paper, an excellent hydrophobic effect is achieved, the tensile strength of the paper is further improved due to the fact that the cross-linking functional monomer is added into the polymer emulsion, and the comprehensive practicability is high.

Description

Technical Field

[0001] The invention belongs to the field of waterproof material preparation, and specifically relates to a highly hydrophobic and tensile-resistant fluorine-containing acrylic resin paper waterproofing agent and a preparation method thereof. Background Art

[0002] Acrylic resin is a high molecular polymer made by copolymerization of acrylic acid esters, methacrylic acid esters and other olefin monomers. It has good heat resistance, corrosion resistance, light resistance, weather resistance and excellent coating performance, and is widely used in coatings, adhesives and leather finishing agents. Traditional single solvent acrylic resin has poor thermal stability, poor water resistance and chemical resistance, and high surface energy. There are certain limitations in application. With the enhancement of health and environmental protection concepts, traditional solvent acrylic resins have begun to be abandoned and replaced by safer, greener, and low-VOC water-based acrylic resins.

[0003] Fluorine-containing polymers have the characteristics of "three highs" and "two phobias", which are specifically reflected in high chemical inertness, high thermal stability, high surface activity, and hydrophobicity and oleophobicity. They can be used as textile fiber finishing agents, leather finishing agents, anti-corrosion coatings, etc. The film formed by the acrylic emulsion with fluorocarbon structure side chains has extremely low surface energy and high thermal stability, and the addition of fluorine-containing functional monomers can make the polymer have excellent anti-aging properties, thermal stability, low dielectric constant, friction and unique low surface free energy, so that the prepared resin exhibits outstanding hydrophobic and anti-fouling properties. Fluorine-containing acrylic resin not only maintains the original characteristics of ordinary polyacrylates, but also exhibits strong surface properties. Due to its unique and excellent properties, it is widely used in many high-tech fields.

[0004] There are many types of waterproofing agents for papermaking, which can be roughly divided into two categories. One is natural polymers, such as carboxymethyl cellulose, chitosan, starch, etc., and the other is synthetic polymers, such as alkyl ketene dimer, alkenyl succinic anhydride, styrene acrylate copolymers, etc. Since natural polymers have certain defects in the sizing and waterproofing effect, such as carboxymethyl cellulose has a weak waterproofing effect, it is usually used in combination with other waterproofing agents, while starch will affect other properties of paper, such as strength and air permeability. Synthetic polymers, such as alkyl ketene dimer, alkenyl succinic anhydride and other paper waterproofing agents, either have too high cost prices or have strict requirements on sizing conditions, which brings a relatively large burden to papermaking. By utilizing the low surface energy properties of fluorinated polymers, fluorinated monomers are used to modify styrene acrylate copolymers to synthesize fluorinated acrylic resin copolymers. Because of their high efficiency and unique waterproof properties, they have been 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, but its waterproof and mechanical properties can no longer meet current needs, which greatly limits its further application. Summary of the invention

[0005] In view of the problems existing in the prior art, the present invention provides a highly hydrophobic and tensile-resistant fluorinated acrylic resin paper waterproofing agent and a preparation method thereof, which solves the problem that the waterproofing performance and mechanical properties of the current fluorinated acrylic resin cannot meet the current needs when treating paper. The invention is safe, green and has a low production cost. The polymer emulsion can form an extremely low surface energy on the surface of the paper, thereby effectively preventing the entry of water molecules and achieving an excellent hydrophobic effect. Since a cross-linking functional monomer is added to the polymer emulsion, the tensile strength of the paper is further improved, and the comprehensive practicality is high.

[0006] The present invention is achieved through the following technical solutions: A method for preparing a highly hydrophobic and stretch-resistant fluorine-containing acrylic resin paper waterproofing agent comprises the following steps: using N,N-methylenebisacrylamide, isooctyl acrylate, styrene, hydroxyethyl methacrylate, acrylic acid, glyceryl acrylate and hexafluorobutyl methacrylate as reaction monomers, using deionized water as a medium, carrying out a free radical polymerization reaction under alkaline conditions of 80-90 DEG C under the action of an initiator and an emulsifier, and then keeping the temperature, and then adjusting the obtained emulsion to neutrality to obtain a highly hydrophobic and stretch-resistant fluorine-containing acrylic resin paper waterproofing agent.

[0007] A further improvement of the present invention is: Hexafluorobutyl methacrylate is component I, isooctyl acrylate and styrene are component II, hydroxyethyl methacrylate, acrylic acid, glyceryl acrylate and N,N-methylenebisacrylamide are component III, hexafluorobutyl methacrylate accounts for 28% of the total mass M of component I, component II, component III, initiator and emulsifier, component II accounts for 52% of M, the mass ratio of isooctyl acrylate and styrene is 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. The specific steps include: S1, isooctyl acrylate, styrene, hydroxyethyl methacrylate, acrylic acid, glyceryl acrylate and hexafluorobutyl methacrylate are uniformly mixed to obtain an oily system; dissolving an initiator and sodium bicarbonate in deionized water to obtain an initiation system; S2, at 80-90° C., dropwise adding the oily system, the initiating system and the N,N-methylenebisacrylamide aqueous solution into the aqueous solution of the emulsifier, and then keeping the temperature for 30-60 minutes to obtain an emulsion; S3, after the emulsion is cooled to room temperature, the pH of the cooled emulsion is adjusted to be neutral, the obtained emulsion is filtered and the filtrate is collected to obtain a highly hydrophobic and tensile resistant fluorine-containing acrylic resin paper waterproofing agent. The initiator in S1 is ammonium persulfate or potassium persulfate. The emulsifier described in S2 is nonionic octylphenol polyoxyethylene ether and anionic allyloxy nonylphenol propanol polyoxyethylene ether ammonium sulfate, and the mass ratio of nonionic octylphenol polyoxyethylene ether and anionic allyloxy nonylphenol propanol polyoxyethylene ether ammonium sulfate is 1:2. In S1, the mass ratio of initiator, sodium bicarbonate and deionized water is (1.2-2.4): (1.8-3.6):300; 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 aqueous solution of the emulsifier, the mass ratio of anionic allyloxy nonylphenol propanol polyoxyethylene ether ammonium sulfate to deionized water is (1-2.4): (40-70).

[0008] S2 adds the oily system, initiator system and N,N-methylenebisacrylamide aqueous solution to the aqueous solution of the emulsifier at a constant rate for 3-4 hours, and then keeps warm. S3 uses 28% by mass of ammonia water to adjust the pH of the cooled emulsion to neutral. S3 Filter the resulting emulsion through a 200 mesh filter. A highly hydrophobic and stretch-resistant fluorinated acrylic resin paper waterproofing agent obtained by the preparation method of any one of the above highly hydrophobic and stretch-resistant fluorinated acrylic resin paper waterproofing agents.

[0009] Compared with the prior art, the present invention has the following beneficial technical effects: The invention discloses a method for preparing a highly hydrophobic and 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 -Methylene bisacrylamide is a cross-linking monomer. It is polymerized with hexafluorobutyl methacrylate, isooctyl acrylate and styrene under the action of initiator and emulsifier, and forms fluorinated acrylic resin waterproofing agent by free radical polymerization under alkaline conditions of 80-90°C. Since hexafluorobutyl methacrylate, a fluorinated monomer, is introduced into the polymerization, it has a unique long-chain fluoroalkyl structure and thus has extremely low surface free energy, which can give the paper good hydrophobicity. N , N -Methylenebisacrylamide is a hydrophilic functional monomer. Its addition will increase the hydrophilicity of the system and improve the cross-linking performance of the adhesive. The epoxy group in glyceryl acrylate will undergo a ring-opening reaction under high temperature and alkaline conditions, produce self-crosslinking, and form a self-crosslinking network structure. It can undergo a cross-linking reaction with the hydroxyl group on the natural fiber to form an interpenetrating network structure and enhance the adhesion between the fibers, thereby greatly improving the bonding strength of the paper. Styrene is a hard monomer with a high glass transition temperature, which gives the polymer cohesion. The emulsion polymerization of the fluorinated acrylate of the present invention uses deionized water as a medium, and the obtained emulsion-like fluorinated acrylic resin waterproofing agent can form an extremely low surface energy on the surface of the paper, thereby effectively preventing the entry of water molecules and achieving an excellent hydrophobic effect. Since the cross-linking functional monomer is added to the polymer emulsion, the tensile strength of the paper is further improved, which is pollution-free to the environment, has stable performance, is green and safe, and is suitable for industrial production. It is used for sizing in paper pulp. The water contact angle of the baked and formed paper can reach up to 135.6°, and the cobb value is only 15.6-25.9g / m 2 , showing good waterproof and decontamination performance, and high comprehensive practicality. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] Figure 1a It is a reaction schematic diagram of the reaction reagent part of the waterproofing agent of the present invention.

[0011] Figure 1b It is a schematic structural diagram of the waterproofing agent of the present invention.

[0012] Figure 2 It is the FTIR spectrum of the waterproofing agent described in the present invention.

[0013] Figure 3 This is a test diagram of the mechanical properties of the sizing paper of the present invention.

[0014] Figure 4a Schematic diagram of the contact angle of the base paper of the present invention.

[0015] Figure 4b Schematic diagram of the contact angle of the sized paper of the present invention.

[0016] Figure 5 The cobb paper change diagram of the sized paper when different fluorine-containing monomer addition amounts are added in the present invention.

[0017] Figure 6 Schematic diagram of scanning electron microscope of base paper of the present invention.

[0018] Figure 7 Schematic diagram of scanning electron microscope of sized paper of the present invention. DETAILED DESCRIPTION

[0019] The present invention is further described in detail below in conjunction with specific embodiments, which are intended to explain the present invention rather than to limit it.

[0020] The invention discloses a highly hydrophobic and tensile resistant fluorine-containing acrylic resin paper waterproofing agent, the components of which include component I, component II, component III, an initiator and an emulsifier, wherein component I is hexafluorobutyl methacrylate (G02), component II is styrene (St) and isooctyl acrylate (EHA) in a mass ratio of 1:1, and component III is a mixture of acrylic functional monomers and N,N-methylenebisacrylamide (MBA); wherein component I accounts for 28% of the total mass of all components, component II accounts for 52% of the total mass of all components, component III accounts for 14% of the total mass of all components, the initiator accounts for 0.5% of the total mass of all components, and the emulsifier accounts for 5.5% of the total mass of all components.

[0021] 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.

[0022] The initiator is a persulfate, specifically one of ammonium persulfate or potassium persulfate.

[0023] The emulsifiers are non-ionic octylphenol polyoxyethylene ether (OP-10) and anionic allyloxy nonylphenol propanol polyoxyethylene ether ammonium sulfate (DNS-86), and the composite mass ratio of the two is 1:2.

[0024] The present invention discloses a method for preparing a highly hydrophobic and tensile-resistant fluorinated acrylic resin paper waterproofing agent, which specifically comprises the following steps: S1, weigh the emulsifier into a three-necked flask, add a certain amount of deionized water, the mass ratio of DNS-86 and deionized water is (1 -2.4): (40-70), and use it as the base material.

[0025] S2, dissolving N,N-methylenebisacrylamide in a certain amount of deionized water, wherein the mass ratio of N,N-methylenebisacrylamide to deionized water is 1:40, to prepare a water-soluble monomer A.

[0026] S3, stir isooctyl acrylate and styrene evenly, then add hydroxyethyl methacrylate, acrylic acid, glyceryl acrylate, and finally add hexafluorobutyl methacrylate, and mix evenly. This is used as the oily mixed monomer B for later use.

[0027] S4, dissolving the initiator and the pH moderator sodium bicarbonate in a certain amount of deionized water, wherein the mass ratio of the initiator, sodium bicarbonate and deionized water is (1.2-2.4): (1.8-3.6):300, to prepare an initiator aqueous solution C.

[0028] S5. At 80-90°C, slowly drop the solution prepared in steps S2, S3 and S4 into the dissolved base material in step S1. The dropping time is controlled at 3-4h. The dropping is performed through a constant pressure dropping funnel. After the dropping is completed, the emulsion is kept warm for 30-60min. After cooling to room temperature, 28% by mass ammonia water is used to adjust the pH of the emulsion to neutral. The filtrate is collected after filtering with a 200-mesh filter to obtain a fluorine-containing acrylic resin waterproofing agent.

[0029] Example 1 S1, at room temperature, take 1g OP-10 and 2g DNS-86 and add 60g deionized water to dissolve, and prepare as base material for later use; S2, 0.5 g of N , N -Methylenebisacrylamide was dissolved in 20 g of deionized water to prepare water-soluble monomer A; S3, weigh 15 g 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, stir thoroughly, and set aside as oily mixed monomer B.

[0030] S4, put 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 an initiator aqueous solution C.

[0031] Heat the water bath to 90°C, and begin to slowly add the solutions prepared in steps S2, S3, and S4 to the dissolved base material in step S1. Control the dropping time to 3 h, then keep warm for 1 h, and then cool to room temperature. Use 28% by mass ammonia water to adjust the pH to neutral, filter with a 200-mesh filter, and collect the filtrate to obtain a fluorine-containing acrylic resin waterproofing agent with a solid content of 28.6%.

[0032] Example 2 S1, at room temperature, take 0.8g OP-10 and 1.6g DNS-86 and add 50g deionized water to dissolve, and prepare as base material for later use; S2, 0.5 g of N , N -Methylenebisacrylamide was dissolved in 20 g of deionized water to prepare water-soluble monomer A; S3, weigh 15 g 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, finally add 10 g of hexafluorobutyl methacrylate, mix the above monomers evenly, stir thoroughly and set aside as oily mixed monomer B.

[0033] S4, put in a constant pressure dropping funnel, and then dissolve 0.18 g of ammonium persulfate and 0.27 g of sodium bicarbonate in 30 g of deionized water to prepare an initiator aqueous solution C.

[0034] Heat the water bath to 90°C, and begin to slowly add the solutions prepared in steps S2, S3, and S4 to the dissolved base material in step S1. Control the dropping time to 3 h, then keep warm for 1 h, and then cool to room temperature. Use 28% by mass ammonia water to adjust the pH to neutral, filter with a 200-mesh filter, and collect the filtrate to obtain a fluorine-containing acrylic resin waterproofing agent with a solid content of 28.8%.

[0035] Example 3 S1, at room temperature, take 1.2g OP-10 and 2.4g DNS-86 and add 70g deionized water to dissolve, and prepare as base material for later use; S2, 0.5 g of N , N -Methylenebisacrylamide was dissolved in 20 g of deionized water to prepare water-soluble monomer A; S3, weigh 15 g 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, finally add 25 g of hexafluorobutyl methacrylate, mix the above monomers evenly, stir thoroughly and set aside as oily mixed monomer B.

[0036] S4, put into a constant pressure dropping funnel, and then dissolve 0.24 g of ammonium persulfate and 0.36 g of sodium bicarbonate in 30 g of deionized water to prepare an initiator aqueous solution C.

[0037] Heat the water bath to 90°C, and begin to slowly add the solutions prepared in steps S2, S3, and S4 to the dissolved base material in step S1. Control the dropping time to 3 h, then keep warm for 1 h, and then cool to room temperature. Use 28% by mass ammonia water to adjust the pH to neutral, filter with a 200-mesh filter, and collect the filtrate to obtain a fluorine-containing acrylic resin waterproofing agent with a solid content of 29.2%.

[0038] Example 4 S1, at room temperature, take 0.5g OP-10 and 1g DNS-86 and add 40g deionized water to dissolve them and prepare them as base material for later use; S2, 0.5 g of N , N -Methylenebisacrylamide was dissolved in 20 g of deionized water to prepare water-soluble monomer A; S3, weigh 15 g 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, stir well, and set aside as oily mixed monomer B.

[0039] S4, put in a constant pressure dropping funnel, and then dissolve 0.12 g of ammonium persulfate and 0.18 g of sodium bicarbonate in 30 g of deionized water to prepare an initiator aqueous solution C.

[0040] Heat the water bath to 90°C, and begin to slowly drop the solutions prepared in steps S2, S3, and S4 into the dissolved base material in step S1. Control the dropping time to 4 h, then keep warm for 1 h, and then cool to room temperature. Use 28% by mass ammonia water to adjust the pH to neutral, filter with a 200-mesh filter, and collect the filtrate to obtain a fluorine-containing acrylic resin waterproofing agent with a solid content of 28.4%.

[0041] Figure 1aThe schematic diagram of the reaction of the synthetic reagent part of the waterproofing agent is shown in Figure 1. The initiator is ammonium persulfate. Figure 1b It can be seen that the monomers are successfully synthesized into linear polymer compounds through free radical polymerization.

[0042] Figure 2 This is the FTIR spectrum of the waterproofing agent. It can be seen from the figure that 2925 and 2860 cm -1 The peaks that appear belong to the stretching vibration peaks of CH in -CH3 and -CH2, 1727 cm -1 Carbonyl absorption peak appears, 1245-1020cm -1 The peak that appears belongs to -CF ２ and -CF ３ The stretching vibration peak of -COC- and the absorption peak of G02 at 1631 cm -1 The peak that appears belongs to the stretching vibration peak of the amide carbonyl group, 756cm -1 、702 cm -1 The two sharp absorption peaks at 1460 cm -1 The presence of an absorption peak at 1640 cm -1 There is no characteristic absorption peak of carbon-carbon double bond nearby, which shows that all monomers are completely polymerized through double bonds, and strong covalent bonds have been formed between monomers through emulsion polymerization.

[0043] Figure 3 This is a test chart of mechanical properties of sized paper. The bleached kraft pulp was beaten with a standard beater, with a beating degree of 25°SR. Then, the internal sizing method was used to copy the sized and unsized paper samples. The paper samples were hot pressed, dried and finally cut into dumbbell shapes. The tensile test was carried out using a servo material multifunctional high and low temperature control tensile machine. The total length of the sample was 75mm, the middle width was 4mm, and the TRD-500kgf sensor was used. The test speed was 10mm / min. From the figure, it can be seen that the tensile strength of the unsized paper is 8.2MPa, while the tensile strength of the paper after the waterproofing agent is sized can reach 18.9MPa. It can be seen that the waterproofing agent has further improved the mechanical properties of the paper.

[0044] Figure 4a Schematic diagram of the contact angle of the base paper of the present invention. From the figure, it can be seen that the contact angle of the base paper to water is 48.6°, which shows that the base paper does not have an obvious waterproof effect.

[0045] Figure 4bSchematic diagram of the contact angle of the sized paper of the present invention. From the figure, it can be seen that the contact angle of the paper to water after the waterproofing agent is applied can reach 135.6°. It can be seen that the waterproofing effect of the paper after the waterproofing agent is applied is greatly improved, indicating that the comprehensive practicality of the waterproofing agent is high.

[0046] Figure 5 This is the cobb value change diagram of sized paper when different fluorinated monomer addition amounts are added. From the figure, it can be seen that with the increase of hexafluorobutyl methacrylate (G02) content, the cobb value of sized paper gradually decreases. This is because as the hydrophobic components in the polymer increase, the hydrophobic fluorinated groups can inhibit water molecules from penetrating into the interior of the paper through the surface of the paper, so the cobb value of the paper continues to decrease. It can be seen that the waterproofing agent can significantly improve the waterproof performance of paper.

[0047] Figure 6 Schematic diagram of scanning electron microscope of the base paper of the present invention. From the figure, it can be seen that the surface of the paper without adding waterproofing agent is uneven, has many holes, is arranged in disorder, and the fibers are not woven very tightly.

[0048] Figure 7 The SEM diagram of the sized paper of the present invention shows that the paper with the waterproofing agent added has tighter fiber arrangement and weaving, smaller gaps between fibers, improved paper uniformity, and a smooth surface. It can be seen that the waterproofing agent is attached to the inside of the pulp fibers to form a firm mesh-like interwoven structure.

Claims

1. A method for preparing a highly hydrophobic and tensile fluorinated acrylic resin paper waterproofing agent, characterized in that: With N,N-methylenebisacrylamide, isooctyl acrylate, styrene, hydroxyethyl methacrylate, acrylic acid, glyceryl acrylate and hexafluorobutyl methacrylate as reaction monomers and deionized water as medium, free radical polymerization reaction is carried out under alkaline conditions of 80-90°C under the action of an initiator and an emulsifier, and then the reaction mixture is kept warm, and the obtained emulsion is adjusted to neutrality to obtain a highly hydrophobic and tensile resistant fluorinated acrylic resin paper waterproofing agent.

2. The method for preparing the highly hydrophobic tensile resistant fluorinated acrylic resin paper waterproofing agent according to claim 1, characterized in that: Hexafluorobutyl methacrylate is component I, isooctyl acrylate and styrene are component II, hydroxyethyl methacrylate, acrylic acid, glyceryl acrylate and N,N-methylenebisacrylamide are component III, hexafluorobutyl methacrylate accounts for 28% of the total mass M of component I, component II, component III, initiator and emulsifier, component II accounts for 52% of M, the mass ratio of isooctyl acrylate and styrene is 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.

3. The method for preparing the highly hydrophobic tensile resistant fluorinated acrylic resin paper waterproofing agent according to claim 2, characterized in that: The specific steps include: S1, isooctyl acrylate, styrene, hydroxyethyl methacrylate, acrylic acid, glyceryl acrylate and hexafluorobutyl methacrylate are uniformly mixed to obtain an oily system; dissolving an initiator and sodium bicarbonate in deionized water to obtain an initiation system; S2, at 80-90° C., dropwise adding the oily system, the initiating system and the N,N-methylenebisacrylamide aqueous solution into the aqueous solution of the emulsifier, and then keeping the temperature for 30-60 minutes to obtain an emulsion; S3, after the emulsion is cooled to room temperature, the pH of the cooled emulsion is adjusted to be neutral, the obtained emulsion is filtered and the filtrate is collected to obtain a highly hydrophobic and tensile resistant fluorine-containing acrylic resin paper waterproofing agent.

4. The method for preparing the highly hydrophobic tensile resistant fluorinated acrylic resin paper waterproofing agent according to claim 3, characterized in that: The initiator in S1 is ammonium persulfate or potassium persulfate.

5. The method for preparing the highly hydrophobic tensile-resistant fluorinated acrylic resin paper waterproofing agent according to claim 3, characterized in that: The emulsifier described in S2 is nonionic octylphenol polyoxyethylene ether and anionic allyloxy nonylphenol propanol polyoxyethylene ether ammonium sulfate, and the mass ratio of nonionic octylphenol polyoxyethylene ether and anionic allyloxy nonylphenol propanol polyoxyethylene ether ammonium sulfate is 1:

2.

6. The method for preparing the highly hydrophobic tensile-resistant fluorinated acrylic resin paper waterproofing agent according to claim 5, characterized in that: In S1, the mass ratio of initiator, sodium bicarbonate and deionized water is (1.2-2.4): (1.8-3.6):300; 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 aqueous solution of the emulsifier, the mass ratio of anionic allyloxy nonylphenol propanol polyoxyethylene ether ammonium sulfate to deionized water is (1-2.4): (40-70).

7. The method for preparing the highly hydrophobic and tensile resistant fluorinated acrylic resin paper waterproofing agent according to claim 6, characterized in that: S2 adds the oily system, initiator system and N,N-methylenebisacrylamide aqueous solution to the aqueous solution of the emulsifier at a constant rate for 3-4 hours, and then keeps warm.

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

9. The method for preparing the highly hydrophobic and tensile resistant fluorinated acrylic resin paper waterproofing agent according to claim 3, characterized in that: S3 Filter the resulting emulsion through a 200 mesh filter.

10. A highly hydrophobic and stretch-resistant fluorinated acrylic resin paper waterproofing agent obtained by the preparation method of the highly hydrophobic and stretch-resistant fluorinated acrylic resin paper waterproofing agent according to any one of claims 1 to 9.

Images