Flame-retardant anti-sticking waterproof board and preparation method thereof

Abstract

The invention discloses a flame-retardant anti-sticking waterproof board and a preparation method thereof in the field of anti-sticking waterproof boards, and the anti-sticking waterproof board comprises a base material layer, a self-adhesive glue layer and a flame-retardant film coating layer, the flame-retardant coating layer is prepared from the following components in parts by weight: acrylic emulsion, aluminum hydroxide, ammonium polyphosphate, lignosulfonate, a flame-retardant additive, a cross-linking agent, pigment filler and an auxiliary agent. The waterproof performance of the self-adhesive layer of the anti-adhesive waterproof board is improved, and the flame-retardant additive is added, so that the flame-retardant performance of the flame-retardant coating layer is improved. The high-strength material is selected as the base material layer, only the SBS modified asphalt is adopted as the main component of the self-adhesive layer, and the asphalt has natural waterproofness, is good in fluidity in a thermal state and easy to coat and construct, and in a flame-retardant coating film, the fireproof and heat-resistant dual effects are achieved through compounding of multiple inorganic and organic chemical substances.

Description

Technical Field

[0001] The present invention belongs to the technical field of anti-sticking waterproof sheets, and specifically relates to a flame-retardant anti-sticking waterproof sheet and a preparation method thereof. Background Art

[0002] With the rapid development of the construction industry and the increasing requirements for the waterproof performance of residential and public buildings, various waterproof materials have emerged continuously. Among them, waterproof sheets are widely used in fields such as roofs, underground structures, tunnels, and water tanks due to their advantages of convenient construction, strong integrity, and excellent impermeability. However, traditional waterproof sheets still have obvious deficiencies in terms of fire safety and the easy adhesion of contaminants on the surface after construction.

[0003] On the one hand, with the continuous increase in high-rise buildings and large public buildings, fire safety has become an important consideration in design and construction. Conventional waterproof sheets are mostly made of high molecular polymers (such as polyethylene, polypropylene, PVC, etc.), which have a relatively low pyrolysis temperature and are prone to generating a large amount of combustible volatiles when burning. This not only intensifies the fire in the initial stage of a fire but also releases toxic fumes, making it difficult to meet the dual requirements of the fire resistance limit and the control of smoke toxicity of waterproof materials in modern building fire codes. Therefore, it is imperative to develop waterproof sheet materials with excellent flame retardancy and waterproof functions.

[0004] On the other hand, after construction, the surface of the waterproof layer of roofs or underground structures often adheres to contaminants such as soil, dust, and residues of chemical building materials, which affects the adhesion effect of subsequent insulation layers, protective layers, or decorative layers, and even affects the service life of the waterproof layer. Currently, the common solution is to coat a release agent or a construction convenience film on the waterproof surface layer, but such methods have problems such as limited film layer life, susceptibility to physical or chemical damage, trouble in repeated construction, and increased costs.

[0005] In terms of the material system, the fire resistance limit of the sheet can be improved by introducing inorganic flame retardants (such as ammonium sesquiphosphate (APP), aluminum hydroxide (ATH), magnesium hydroxide (MDH), etc.) or organic flame retardant systems (such as phosphorus- and nitrogen-containing synergistic flame retardants) into the polymer matrix; at the same time, nano-fillers (such as nano-silicon, nano-perovskite) can be used in combination with polymers to synergistically toughen and improve the thermal stability. In addition, by using surface blending or co-extrusion technology, low surface energy materials (such as modified polytetrafluoroethylene, silicone-modified agents) are uniformly coated on the surface of the sheet, which can endow the waterproof sheet with persistent anti-sticking and anti-fouling properties. Summary of the Invention

[0006] In view of the above situation, to overcome the defects of the prior art, the present invention provides a flame-retardant self-adhesive waterproof board and its preparation method. By improving the waterproof performance of the self-adhesive layer of the self-adhesive waterproof board and adding flame-retardant additives, the flame-retardant performance of the flame-retardant coating layer is improved. The present invention selects high-strength materials as the base material layer, which not only provides good mechanical strength and tensile ability, ensures that the waterproof board will not be damaged due to external forces during actual use, but also effectively improves the durability of the waterproof board. SBS modified asphalt is used as the main component of the self-adhesive layer. Asphalt has natural waterproofness and good fluidity in the hot state, making it easy to coat and construct. In the flame-retardant coating film, through the compounding of various inorganic and organic chemical substances, the dual effects of fire prevention and heat resistance are achieved.

[0007] To achieve the above object, the technical solution adopted by the present invention is as follows: The present invention provides a flame-retardant self-adhesive waterproof board, which comprises a base material layer, a self-adhesive layer and a flame-retardant coating layer;

[0008] Preferably, the thickness of the self-adhesive layer is 1.5 - 2 mm;

[0009] Preferably, the thickness of the flame-retardant coating layer is 150 - 200 μm;

[0010] Preferably, the base material layer comprises at least one of high-density polyethylene non-woven fabric, glass fiber reinforced polypropylene composite board, and polyester fiber non-woven fabric;

[0011] Selecting high-strength base materials provides high-strength structural support, not only enhancing the physical strength of the waterproof board, but also effectively improving the waterproof ability;

[0012] Preferably, the preparation raw materials of the self-adhesive layer specifically include the following components in parts by weight: 60 - 65 parts of matrix asphalt, 5 - 8 parts of SBS copolymer (styrene-butadiene-styrene block copolymer), 5 - 10 parts of tackifier, 3 - 5 parts of plasticizer, 0.5 - 1.0 part of antioxidant, 0.2 - 0.5 part of anti-aging agent, 1 - 2 parts of filler, and 0.1 - 0.2 part of antiseptic and mildew-proof agent;

[0013] The high density of asphalt endows it with good water vapor barrier ability. The introduction of SBS copolymer enables the waterproof layer to maintain its stability in the environment of thermal expansion and contraction and effectively avoids the formation of cracks. The function of the tackifier is to improve the adhesion of the adhesive layer and ensure that the waterproof board can firmly adhere to various substrates;

[0014] Preferably, the tackifier comprises at least one of polyvinyl chloride tackifier, rosin, polyester resin, styrene-isoprene copolymer, and C5 petroleum resin;

[0015] Preferably, the plasticizer includes at least one of dioctyl phthalate, diisononyl phthalate, di-n-octyl phthalate, glyceryl trioctanoate, and epoxidized soybean oil;

[0016] Preferably, the antioxidant includes at least one of butyl hydroxybenzoic acid, 2,6-di-tert-butyl-p-cresol, and tris(2,4-di-tert-butylphenyl) phosphite;

[0017] Preferably, the anti-aging agent includes at least one of N-nitrosodicyclohexylamine and 2,6-di-tert-butyl-p-cresol;

[0018] Preferably, the filler includes at least one of silica, talc, calcium carbonate, carbon black, and chopped polyester fiber;

[0019] Preferably, the antiseptic and mildew-proof agent includes at least one of benzoic acid, chlorinated aniline, and biphenyl alcohol;

[0020] Preferably, the flame-retardant coating layer includes the following components in parts by weight: 25-35 parts of acrylic emulsion, 30-40 parts of aluminum hydroxide, 10-15 parts of ammonium polyphosphate, 1-5 parts of lignosulfonate, 3-7 parts of flame-retardant additive, 1-3 parts of cross-linking agent, 5-10 parts of pigment and filler, and 2-4 parts of auxiliary agent;

[0021] Preferably, the acrylic emulsion includes at least one of polymethyl acrylate emulsion, acrylate-methyl methacrylate copolymer emulsion, and acrylic / styrene copolymer emulsion;

[0022] Preferably, the cross-linking agent includes at least one of diisophorone peroxide, MDI, TDI, and methyltrichlorosilane;

[0023] Preferably, the pigment and filler includes at least one of titanium dioxide, carbon black, aluminum powder, barium titanate, and iron oxide red;

[0024] Preferably, the auxiliary agent includes at least one of rheology aid, dispersion aid, wetting agent, defoamer, and preservative;

[0025] Preferably, the auxiliary agent includes at least one of nitrified paraffin, carbomer, hydroxypropyl methylcellulose, polycarboxylic acid dispersant, sulfonate dispersant, sodium stearate, calcium stearate, polyether defoamer, silicone oil defoamer, sodium benzoate, and methylisothiazolinone;

[0026] As a common inorganic flame retardant, aluminum hydroxide releases water vapor when heated, thereby absorbing heat and reducing the temperature of fire spread. Ammonium polyphosphate is an effective phosphorus-based flame retardant that can form a stable carbonized layer to isolate oxygen and reduce flame spread. Lignosulfonate not only has good flame retardant effect but also helps to improve the adhesion and stability of the coating film;

[0027] Preferably, the preparation method of the flame retardant additive specifically includes the following steps:

[0028] S1. Dissolve melamine in 1,4-dioxane, add sodium methoxide, and after mixing evenly, introduce flowing nitrogen, then add phosphorus oxychloride. After stirring and reacting for 30 minutes, raise the reaction temperature to 80 - 90 °C and continue to react for 6 - 8 hours. After the reaction, cool, wash, filter, collect the filtrate, remove the solvent by reduced pressure concentration, purify and dry to obtain phosphorylated melamine;

[0029] S2. Take the phosphorylated melamine prepared in step S1 and dissolve it in tetrahydrofuran. Transfer it to an ice-water bath, introduce nitrogen, and slowly add cyanuric chloride. After stirring and mixing evenly, raise the reaction temperature to 30 - 40 °C and react for 1 - 2 hours. Then add borane dimethyl sulfide and continue to react for 8 - 12 hours. After cooling to room temperature, perform suction filtration, collect the solid, and dry to obtain the flame retardant additive;

[0030] Preferably, in step S1, the mass ratio between melamine and sodium methoxide is 1:0.35 - 0.5;

[0031] Preferably, in step S1, the mass ratio between melamine and phosphorus oxychloride is 1:0.35 - 0.5;

[0032] Preferably, in step S2, the mass concentration of the phosphorylated melamine in tetrahydrofuran is 0.05 - 0.1 g / mL;

[0033] Preferably, in step S2, the added mass of cyanuric chloride is 36% - 55% of the mass of the phosphorylated melamine;

[0034] Preferably, in step S2, the mass-volume ratio between the phosphorylated melamine and borane dimethyl sulfide is 3 - 4.5 g / mL.

[0035] The present invention provides a preparation method of a flame retardant anti-sticking waterproof board, which specifically includes the following steps:

[0036] ① Place aluminum hydroxide, ammonium polyphosphate, and pigment filler in water, and at room temperature, mix at a speed of 3000 - 5000 rpm until the fineness is uniform to obtain an inorganic filler slurry;

[0037] ② Add acrylic emulsion to a stirring tank, slowly add the inorganic filler slurry described in step ①, stir until uniform, and sequentially add lignosulfonate and the flame retardant additive to obtain a premix;

[0038] ③ Add a crosslinking agent and additives to the premix described in step ②, adjust the pH to 7.5 - 8.5, stir until the system is stable and free of bubbles, dilute with water to a solid content of 40% - 50%, let stand and degas under vacuum to obtain a flame-retardant coating layer material;

[0039] ④ Heat the matrix asphalt to 140 - 150 °C to keep it flowing, raise the temperature to 170 - 180 °C, slowly add the SBS copolymer, and stir at a shear rate of 3000 - 5000 rpm for 30 - 45 min until the SBS is completely fused with the asphalt and the particles disappear to obtain SBS-modified asphalt;

[0040] ⑤ Take the SBS-modified asphalt described in step ④ and continue to add a tackifier in portions and stir for 15 - 20 min at 170 - 180 °C. According to 2000 - 3000 rpm, add a plasticizer, an antioxidant, an anti-aging agent, a filler, and an anti-corrosion and anti-mildew agent successively, stir for 5 - 10 min until evenly dispersed, keep the material standing for 5 min to allow the large bubbles to escape naturally, and slowly cool to below 140 °C to obtain a self-adhesive layer material;

[0041] ⑥ Take a base material layer, coat the self-adhesive layer material on the surface of the base material, after cooling and shaping, scrape the flame-retardant coating layer material on the surface of the base material, dry at a low temperature of 60 - 80 °C, cut and shape to obtain a flame-retardant self-adhesive waterproof board.

[0042] The beneficial effects achieved by the present invention are as follows:

[0043] The present invention provides a flame-retardant anti-adhesive waterproof board and a preparation method thereof. The present invention improves the waterproof performance of the self-adhesive layer of the anti-adhesive waterproof board and enhances the flame-retardant performance of the flame-retardant coating layer by adding flame-retardant additives. The present invention selects high-strength materials as the base material layer, which not only provides good mechanical strength and tensile capacity, ensures that the waterproof board will not be damaged due to external forces during actual use, but also effectively improves the durability of the waterproof board. SBS modified asphalt is used as the main component of the self-adhesive layer. Asphalt has natural waterproofness and good fluidity in the hot state, making it easy to coat and construct. SBS (styrene-butadiene-styrene triblock copolymer) is an elastomer that can increase the elasticity and flexibility of asphalt. The introduction of the SBS copolymer enables the waterproof layer to maintain its stability in the environment of thermal expansion and contraction and effectively avoids the formation of cracks. In the flame-retardant coating film, through the compounding of various inorganic and organic chemical substances, the dual effects of fire prevention and heat resistance are achieved. Aluminum hydroxide releases water to absorb heat and lower the temperature, and ammonium polyphosphate and phosphorylated melamine form a carbonized protective layer to synergistically inhibit the spread of flames and the propagation of high temperature. In the production process of the coating layer, through multi-step mixing, low-temperature drying and defoaming treatment, a flame-retardant layer with a dense structure and no pores is obtained, which quickly exerts heat insulation and carbonization effects when encountering fire. The flame-retardant additive described in the present invention contains both phosphate (or phosphoramide) groups and melamine / triazine ring structures. When heated, the phosphorus component generates polyphosphoric acid to promote the formation of a high-density carbonized layer, and the nitrogen component decomposes to release inert gases (N2, NH3), diluting combustible gases and absorbing heat. The two work together to significantly improve the flame-retardant efficiency. The presence of crosslinked triazine rings and P-N bonds enables the material to form a dense and continuous carbonized protective film at high temperatures, blocking the further transmission of heat and oxygen and delaying the decomposition of the base material. The phosphorylated melamine structure retains polyhydroxy / amino functional groups, which can form intermolecular hydrogen bonds or couplings with the base material, improving the dispersibility and mechanical properties of the composite material. After boron elements are incorporated into the crosslinked network, the crosslinked structure is further stabilized through multiple chemical bonds such as B-N and N-C. This stability helps to improve the high-temperature resistance and anti-decomposition ability of the material. In particular, when burning at high temperatures, the presence of boron can promote the formation of a denser carbonized layer, inhibit the spread of flames, and reduce the release of harmful gases. The combination of the base material layer and the self-adhesive layer not only improves the waterproof performance but also enhances the tensile strength and impact resistance. This enables the waterproof board to withstand greater external force impacts, such as the mechanical stress that may occur during construction. The materials of the flame-retardant anti-adhesive waterproof board can maintain good adhesion at lower temperatures and are suitable for construction in cold climate conditions. The self-adhesive layer can still maintain strong adhesion in a low-temperature environment, ensuring the waterproof effect. The strict control of the temperature and stirring speed in each step of the production process enables each layer of material to be evenly and stably mixed, ensuring the overall performance of the finished product. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1Infrared spectrum image of the flame retardant additive prepared in Example 1;

[0045] Figure 2 Flame retardancy performance result chart of the anti-sticking waterproof board prepared in Examples 1-3 and Comparative Examples 1-3 of the present invention;

[0046] Figure 3 Mechanical properties of the anti-sticking waterproof board prepared in Examples 1-3 and Comparative Examples 1-3 of the present invention.

[0047] The accompanying drawings are used to provide a further understanding of the present invention, and constitute a part of the specification. Together with the embodiments of the present invention, they are used to explain the present invention, and do not constitute a limitation to the present invention. Detailed implementation manners

[0048] The following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments; based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0049] Unless otherwise defined, all professional and scientific terms used herein have the same meaning as those familiar to those skilled in the art. In addition, any methods and materials similar or equivalent to the described content can be applied to the present invention. The preferred implementation methods and materials described herein are only for illustration purposes and do not limit the content of this application.

[0050] The experimental methods in the following embodiments are all conventional methods unless otherwise specified; the test materials and test strains used in the following embodiments are all obtained from commercial channels unless otherwise specified.

[0051] Example 1

[0052] This example provides a flame retardant anti-sticking waterproof board, and the anti-sticking waterproof board includes a base material layer, a self-adhesive layer and a flame retardant coating layer:

[0053] The thickness of the self-adhesive layer is 1.5 mm; the thickness of the flame retardant coating layer is 200 μm;

[0054] The preparation raw materials of the self-adhesive layer specifically include the following components in parts by weight: 60 parts of No. 70 petroleum asphalt, 5 parts of Li Changrong 3536 SBS copolymer, 5 parts of styrene-isoprene copolymer, 3 parts of dioctyl phthalate, 0.5 part of 2,6-di-tert-butyl-p-cresol, 0.2 part of anti-aging agent, 1 part of calcium carbonate, 0.1 part of chlorinated aniline;

[0055] The flame-retardant coating film layer comprises the following components in parts by weight: 30 parts of polymethyl acrylate emulsion, 35 parts of aluminum hydroxide, 12 parts of ammonium polyphosphate, 3 parts of lignosulfonate, 5 parts of flame-retardant additive, 2 parts of diisopropyl peroxydicarbonate, 8 parts of titanium dioxide, and 3 parts of polycarboxylic acid dispersant;

[0056] The preparation method of the flame-retardant additive specifically comprises the following steps:

[0057] S1. Accurately weigh 6.3 g of melamine and place it in a beaker. Add 25 mL of 1,4-dioxane to fully dissolve the melamine. Add 2.7 g of sodium methoxide. After mixing evenly at a speed of 120 rpm, introduce flowing nitrogen for 30 min. Then accurately weigh 2.45 g of phosphorus oxychloride and add it to the reaction system. Continue stirring for 30 min, then raise the reaction temperature to 85 °C. Keep the reaction temperature for 6 h. After the reaction cools to room temperature, wash the reaction system with deionized water and 0.1 M dilute hydrochloric acid, filter, collect the filtrate, concentrate under reduced pressure to remove the reaction solvent, and after purification, vacuum dry at 40 °C for 6 h to obtain phosphorylated melamine;

[0058] S2. Accurately weigh 5.0 g of the phosphorylated melamine prepared in step S1 and place it in a flask. Add 50 mL of dried tetrahydrofuran. After fully dissolving the phosphorylated melamine, transfer it to an ice-water bath. Control the temperature of the reaction system at 0 °C. Introduce flowing nitrogen for 30 min to displace the oxygen in the reaction system. Add 2.2 g of cyanuric chloride in three portions. Mix cyanuric chloride in the reaction system at a speed of 150 rpm for 30 min, then raise the reaction temperature to 40 °C. After reacting for 1 h, add 1.15 mL of borane dimethyl sulfide at a speed of 0.5 mL / min. Keep the reaction temperature for 8 h. After the temperature of the reaction system cools to room temperature, filter with suction, collect the solid, and vacuum dry at 60 °C for 12 h to obtain the flame-retardant additive;

[0059] The structure is analyzed by a Bruker Vertex 70 Fourier transform infrared spectrometer (FT-IR). Figure 1 For the infrared spectrum image of the flame-retardant additive prepared in Example 1, the absorption peak at ~3000 cm -1 belongs to the C-H stretching vibration. This peak reflects the residual aliphatic hydrocarbon structure in the sample, usually caused by organic solvents or aliphatic groups. The absorption peak in the range of 1650 - 1550 cm -1 is the C=N or C=C stretching vibration. This absorption peak usually corresponds to the conjugated heterocyclic or benzotriazine structure present in the sample, showing the conjugated characteristics of the amino and carbonyl groups in the melamine skeleton. The absorption peak in the range of 1250 - 1020 cm -1The absorption peaks in the range are related to the vibrations of P=O and P–N, indicating the characteristic peaks of the phosphate ester or phosphoramide structure. These peaks suggest the presence of phosphorylated melamine or similar functional groups in the sample. ~1150 cm -1 The absorption peak at ~800 cm corresponds to the B-N stretching vibration, which is the vibration mode of the B-N bond formed after the incorporation of boron into the melamine skeleton. -1 The absorption peak at ~800 cm is the breathing vibration of the triazine ring, which is a typical absorption peak in melamine compounds and reflects the structural characteristics of the melamine ring.

[0060] This embodiment also provides a preparation method of a flame-retardant anti-sticking waterproof board, which specifically includes the following steps:

[0061] ① Put aluminum hydroxide, ammonium polyphosphate, and pigments and fillers into water, and mix them at a speed of 5000 rpm at room temperature until the fineness is uniform to obtain an inorganic filler slurry.

[0062] ② Add acrylic emulsion to the stirring tank, add the inorganic filler slurry described in step ①, stir until uniform, and then add lignosulfonate and flame retardant additives in sequence to obtain a premix.

[0063] ③ Add a crosslinking agent and an auxiliary agent to the premix described in step ②, adjust the pH to 8.0, stir until the system is stable and there are no bubbles, dilute with water to a solid content of 41.2%, stand still and vacuum degas to obtain a flame-retardant coating layer material.

[0064] ④ Heat the matrix asphalt to 150 °C to keep it flowing, raise the temperature to 180 °C, slowly add the SBS copolymer, and stir at 5000 rpm for 5 min until the SBS is completely fused with the asphalt and the particles disappear to obtain SBS-modified asphalt.

[0065] ⑤ Take the SBS-modified asphalt described in step ④ and continue to add a tackifier in portions and stir for 20 min at 180 °C. Add a plasticizer, an antioxidant, an anti-aging agent, a filler, and an anti-corrosion and anti-mildew agent in sequence at 2000 rpm, stir for 5 min, stir until evenly dispersed, keep the material standing for 5 min to allow the large bubbles to escape naturally, and slowly cool down to below 140 °C to obtain a self-adhesive layer material.

[0066] ⑥ Take a base material layer, coat the self-adhesive layer material on the surface of the base material, after cooling and shaping, scrape the flame-retardant coating layer material on the surface of the base material, dry at a low temperature of 80 °C, and cut into shape to obtain a flame-retardant anti-sticking waterproof board.

[0067] Example 2

[0068] This embodiment provides a flame-retardant anti-sticking waterproof board, which consists of a base material layer, a self-adhesive layer, and a flame-retardant coating layer:

[0069] The thickness of the self - adhesive layer is 1.8 mm; the thickness of the flame - retardant coating layer is 150 μm;

[0070] The preparation raw materials of the self - adhesive layer specifically include the following components in parts by weight: 62 parts of No. 70 petroleum asphalt, 6 parts of Lee Chang Yung 3536 SBS copolymer, 6 parts of styrene - isoprene copolymer, 4 parts of dioctyl phthalate, 0.7 part of tris(2,4 - di - tert - butylphenyl) phosphite, 0.3 part of 2,6 - di - tert - butyl - p - cresol, 1.5 parts of silica, 0.15 part of chlorinated aniline;

[0071] The flame - retardant coating layer includes the following components in parts by weight: 28 parts of polymethyl acrylate emulsion, 38 parts of aluminum hydroxide, 13 parts of ammonium polyphosphate, 4 parts of lignosulfonate, 6 parts of flame - retardant additive, 2 parts of di - isophorone peroxide, 7 parts of titanium dioxide, 3 parts of methylisothiazolinone;

[0072] The preparation method of the flame - retardant additive specifically includes the following steps:

[0073] S1. Accurately weigh 6.3 g of melamine and place it in a beaker, add 25 mL of 1,4 - dioxane to fully dissolve melamine, add 2.15 g of sodium methoxide, mix evenly at a speed of 120 rpm, then pass in flowing nitrogen for 30 min. After that, accurately weigh 2.2 g of phosphorus oxychloride and add it to the reaction system. Continue to stir for 30 min, then raise the reaction temperature to 90 °C, keep the reaction temperature for 12 h. After the reaction cools to room temperature, wash the reaction system with deionized water and 0.1 M dilute hydrochloric acid, filter, collect the filtrate, concentrate under reduced pressure to remove the reaction solvent, purify, and then vacuum - dry at 40 °C for 6 h to obtain phosphorylated melamine;

[0074] S2. Accurately weigh 5.0 g of the phosphorylated melamine prepared in step S1 and place it in a flask, add 100 mL of dried tetrahydrofuran to fully dissolve the phosphorylated melamine, then transfer it to an ice - water bath, control the temperature of the reaction system at 0 °C, pass in flowing nitrogen for 30 min to displace the oxygen in the reaction system. Add 1.80 g of cyanuric chloride in three portions, mix cyanuric chloride in the reaction system at a speed of 150 rpm for 30 min, then raise the reaction temperature to 30 °C, react for 2 h. Then add 1.4 mL of borane dimethyl sulfide at a speed of 0.5 mL / min, keep the reaction temperature for 8 h. After the temperature of the reaction system cools to room temperature, filter, collect the solid, and vacuum - dry at 60 °C for 12 h to obtain the flame - retardant additive.

[0075] This embodiment also provides a preparation method of a flame - retardant anti - sticking waterproof board, which specifically includes the following steps:

[0076] ① Put aluminum hydroxide, ammonium polyphosphate, pigments and fillers, and a dispersant into water, and mix them at a speed of 3000 rpm at room temperature until the fineness is uniform to obtain an inorganic filler slurry;

[0077] ② Add acrylic emulsion to a stirring tank, slowly add the inorganic filler slurry described in step ①, stir until uniform, and sequentially add lignosulfonate and a flame retardant additive to obtain a premix;

[0078] ③ Add a crosslinking agent and an auxiliary agent to the premix described in step ②, adjust the pH to 8.5, stir until the system is stable and there are no bubbles, dilute with water to a solid content of 48.2%, let it stand for vacuum defoaming to obtain a flame retardant coating layer material;

[0079] ④ Heat the matrix asphalt to 140 °C, keep it flowing, raise the temperature to 170 °C, slowly add the SBS copolymer, and stir at 4000 rpm for 3 min until the SBS is completely fused with the asphalt and the particles disappear to obtain SBS modified asphalt;

[0080] ⑤ Take the SBS modified asphalt described in step ④ and continue to add a tackifier in portions and stir for 15 min at 170 °C. According to 3000 rpm, successively add a plasticizer, an antioxidant, an anti-aging agent, a filler, and an anti-corrosion and anti-mildew agent, stir for 10 min, stir until evenly dispersed, keep the material standing for 5 min to allow large bubbles to escape naturally, and slowly cool to below 140 °C to obtain a self-adhesive layer material;

[0081] ⑥ Take a base material layer, coat the self-adhesive layer material on the surface of the base material, after cooling and shaping, scrape the flame retardant coating layer material on the surface of the base material, dry it at a low temperature of 60 °C, and cut it into shape to obtain a flame retardant self-adhesive waterproof board.

[0082] Example 3

[0083] This example provides a flame retardant self-adhesive waterproof board, and the self-adhesive waterproof board comprises a base material layer, a self-adhesive layer and a flame retardant coating layer:

[0084] The thickness of the self-adhesive layer is 2.0 mm; the thickness of the flame retardant coating layer is 175 μm;

[0085] The preparation raw materials of the self-adhesive layer specifically include the following components in parts by weight: 63 parts of 70# petroleum asphalt, 7 parts of Lee Chang Yung 3536 SBS copolymer, 7 parts of C5 petroleum resin, 4.5 parts of diisononyl phthalate, 0.8 part of 2,6-di-tert-butyl-p-cresol, 0.4 part of 2,6-di-tert-butyl-p-cresol, 1.2 parts of talcum powder, 0.18 part of chloraniline;

[0086] The flame-retardant coating layer comprises the following components in parts by weight: 28 parts of polymethyl acrylate emulsion, 38 parts of aluminum hydroxide, 13 parts of ammonium polyphosphate, 4 parts of lignosulfonate, 6 parts of flame-retardant additive, 2 parts of diisopropyl peroxydicarbonate, 7 parts of titanium dioxide, and 3 parts of methylisothiazolinone;

[0087] The preparation method of the flame-retardant additive specifically comprises the following steps:

[0088] S1. Accurately weigh 3.25 g of melamine and place it in a beaker. Add 25 mL of 1,4-dioxane to fully dissolve the melamine. Add 2.7 g of sodium methoxide, mix evenly at a speed of 120 rpm, then introduce flowing nitrogen for 30 min. Accurately weigh 3.0 g of phosphorus oxychloride and add it to the reaction system. Continue stirring for 30 min, then raise the reaction temperature to 80 °C, maintain the reaction temperature for 9 h. After the reaction cools to room temperature, wash the reaction system with deionized water and 0.1 M dilute hydrochloric acid, filter, collect the filtrate, concentrate under reduced pressure to remove the reaction solvent, purify, and then vacuum dry at 40 °C for 6 h to obtain phosphorylated melamine;

[0089] S2. Accurately weigh 5.0 g of the phosphorylated melamine prepared in step S1 and place it in a flask. Add 75 mL of dried tetrahydrofuran, fully dissolve the phosphorylated melamine, then transfer it to an ice-water bath, control the temperature of the reaction system at 0 °C, introduce flowing nitrogen for 30 min to displace the oxygen in the reaction system. Add 2.76 g of cyanuric chloride in three portions, mix cyanuric chloride in the reaction system at a speed of 150 rpm for 30 min, then raise the reaction temperature to 35 °C, react for 2 h, then add 1.7 mL of borane dimethyl sulfide at a speed of 0.5 mL / min, maintain the reaction temperature for 8 h. After the temperature of the reaction system cools to room temperature, filter with suction, collect the solid, and vacuum dry at 60 °C for 12 h to obtain the flame-retardant additive;

[0090] This embodiment also provides a preparation method of a flame-retardant anti-sticking waterproof board, which specifically comprises the following steps:

[0091] ① Place aluminum hydroxide, ammonium polyphosphate, and pigment filler in water, and mix at a speed of 5000 rpm at room temperature until the fineness is uniform to obtain an inorganic filler slurry;

[0092] ② Add acrylic emulsion to a stirring tank, slowly add the inorganic filler slurry described in step ①, stir until uniform, and sequentially add lignosulfonate and flame-retardant additive to obtain a premix;

[0093] ③ Add a crosslinking agent and an auxiliary agent to the premix described in step ②, adjust the pH to 7.5, stir until the system is stable and there are no bubbles, dilute with water to a solid content of 45.8%, stand and vacuum defoam to obtain the flame-retardant coating layer material;

[0094] ④ Heat the base asphalt to 150 °C, keep it flowing, raise the temperature to 180 °C, slowly add the SBS copolymer, and stir for 5 min under shear at 5000 rpm until the SBS is completely fused with the asphalt and the particles disappear, obtaining SBS modified asphalt;

[0095] ⑤ Take the SBS modified asphalt described in step ④ and continue to add the tackifier in portions and stir for 20 min at 180 °C. Then, add the plasticizer, antioxidant, anti-aging agent, filler, and anti-corrosion and mildew-proof agent successively at 2000 rpm and stir for 5 min until evenly dispersed. Keep the material standing for 5 min to allow the large air bubbles to escape naturally, and slowly cool down to below 140 °C to obtain the self-adhesive layer material;

[0096] ⑥ Take the base material layer, coat the self-adhesive layer material on the surface of the base material. After cooling and shaping, scrape the flame-retardant coating film layer material on the surface of the base material, dry it at a low temperature of 80 °C, and cut it into shape to obtain the flame-retardant self-adhesive waterproof board.

[0097] Comparative Example 1

[0098] This comparative example provides a self-adhesive waterproof board and its preparation method. The difference from Example 1 is only that the flame-retardant coating film layer component does not include a flame-retardant additive, and the other components and component contents are the same as those in Example 1.

[0099] Comparative Example 2

[0100] This comparative example provides a self-adhesive waterproof board and its preparation method. The difference from Example 1 is only that the preparation method of the flame-retardant additive does not include step S2, and the other components and component contents are the same as those in Example 1.

[0101] Comparative Example 3

[0102] This comparative example provides a self-adhesive waterproof board and its preparation method. The difference from Example 1 is only that the raw materials for preparing the self-adhesive layer do not include the SBS copolymer, and the other components and component contents are the same as those in Example 1.

[0103] Experimental Example 1

[0104] This experimental example conducts a flame retardancy test on the self-adhesive waterproof boards prepared in Examples 1 - 3 and Comparative Examples 1 - 3. According to GB / T8626-2017 "Determination of the Chemical Smoke Generation of Building Materials and Products under Thermal Radiation Conditions", the flame retardant performance of the self-adhesive waterproof boards prepared in Examples 1 - 3 and Comparative Examples 1 - 3 is tested. The sample quality is clean on the surface, and it is equilibrated at 23 ± 2 °C and 50 ± 5% RH for at least 24 h. The sample is fixed under the radiation heating plate at the top of the smoke density chamber, and the common heat flux = 50 kW / m 2, the atmosphere inside the box is usually inert or air, maintaining a weak convection (wind speed ≤ 0.5 m / s) to exclude locally high-concentration smoke, and recording the smoke generation rate index and the total smoke generation amount in 600 s.

[0105] Figure 2 This is the flame retardancy performance result diagram of the anti-sticking waterproof boards prepared in Examples 1-3 and Comparative Examples 1-3 of the present invention. As shown in the figure, as shown in the figure, the flame retardant effect of the flame retardant anti-sticking waterproof board prepared by the present invention is prominent, and the smoke generation rate index is between 12-15 m 2 / s 2 and the total smoke generation amount in 600 s is controlled below 100 m 2 . The lower the smoke generation rate index, the slower the material generates thick smoke in the early stage of a fire. The lower the total smoke generation amount in 600 s, it indicates that the growth of the smoke released during the combustion of the material is more gentle, indicating that the flame retardant anti-sticking waterproof board prepared by the present invention has good flame retardant performance.

[0106] Experimental Example 2

[0107] This experimental example conducts peel strength tests on the anti-sticking waterproof boards prepared in Examples 1-3 and Comparative Examples 1-3. According to GB / T23457-2009, the peel strength of the waterproof board with post-cast concrete under two working conditions of thermal aging (80 °C, 168 h) and peel strength after immersion in water for 90 d after bonding with post-cast concrete is mainly tested.

[0108] Figure 3 This is the mechanical properties of the anti-sticking waterproof boards prepared in Examples 1-3 and Comparative Examples 1-3 of the present invention. After thermal aging and immersion treatment, the anti-sticking waterproof boards prepared in Examples 1-3 of the present invention have obvious mechanical advantages. The peel strength of the anti-sticking waterproof board after thermal aging treatment is significantly higher than that after immersion treatment, and after the anti-sticking waterproof boards prepared in Examples 1-3 of the present invention are treated by immersion in water, their peel strength can still remain above 5 N / mm. Compared with Comparative Example 3, it can show that SBS modified asphalt has an outstanding contribution to the waterproofness of the waterproof board.

[0109] Although the embodiments of the present invention have been shown and described, for those of ordinary skill in the art, it can be understood that various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention.

[0110] The above describes the present invention and its implementation manners. Such description is not restrictive. What is shown in the drawings is only one of the implementation manners of the present invention, and the actual application is not limited thereto. Generally speaking, if those of ordinary skill in the art are inspired by it and, without departing from the gist of the present invention, design in a non-creative way similar ways and embodiments to the technical solution, they shall fall within the protection scope of the present invention.

Claims

1. A flame-retardant anti-adhesive waterproof board, characterized in that: The anti-sticking waterproof board comprises a base material layer, a self-adhesive layer and a flame-retardant coating layer; The flame-retardant coating layer comprises the following components in parts by weight: 25-35 parts of acrylic emulsion, 30-40 parts of aluminum hydroxide, 10-15 parts of ammonium polyphosphate, 1-5 parts of lignosulfonate, 3-7 parts of flame-retardant additive, 1-3 parts of cross-linking agent, 5-10 parts of pigment filler, and 2-4 parts of auxiliary agent; The preparation method of the flame-retardant additive specifically comprises the following steps: S1. Dissolve melamine in 1,4-dioxane, add sodium methoxide, mix evenly, then introduce flowing nitrogen, add phosphorus oxychloride, stir and react for 30 min, then raise the reaction temperature to 80-90 °C, and continue to react for 6-8 h. After the reaction, cool, wash and filter, collect the filtrate, concentrate under reduced pressure to remove the solvent, purify and dry to obtain phosphorylated melamine; S2. Take the phosphorylated melamine prepared in step S1, dissolve it in tetrahydrofuran, transfer it to an ice-water bath, introduce nitrogen, slowly add cyanuric chloride, stir and mix evenly, then raise the reaction temperature to 30-40 °C, react for 1-2 h, add borane dimethyl sulfide and continue to react for 8-12 h, then cool to room temperature, filter by suction, collect the solid, dry to obtain the flame-retardant additive.

2. A flame-retardant anti-sticking waterproof board according to claim 1, characterized in that: The base material layer comprises at least one of high-density polyethylene non-woven fabric, glass fiber reinforced polypropylene composite board, and polyester fiber non-woven fabric; The preparation raw materials of the self-adhesive layer specifically comprise the following components in parts by weight: 60-65 parts of matrix asphalt, 5-8 parts of SBS copolymer, 5-10 parts of tackifier, 3-5 parts of plasticizer, 0.5-1.0 part of antioxidant, 0.2-0.5 part of anti-aging agent, 1-2 parts of filler, and 0.1-0.2 part of antiseptic and mildew-proof agent.

3. The flame-retardant anti-sticking waterproof board according to claim 2, wherein: The thickness of the self-adhesive layer is 1.5-2 mm; the thickness of the flame-retardant coating layer is 150-200 μm.

4. A flame-retardant anti-sticking waterproof board according to claim 3, characterized in that: The tackifier comprises at least one of polyvinyl chloride tackifier, rosin, polyester resin, styrene-isoprene copolymer, and C5 petroleum resin; The plasticizer comprises at least one of dioctyl phthalate, diisononyl phthalate, di-n-octyl phthalate, glyceryl trioctanoate, and epoxidized soybean oil; The antioxidant comprises at least one of butyl hydroxybenzoic acid, 2,6-di-tert-butyl-p-cresol, and tris(2,4-di-tert-butylphenyl) phosphite; The anti-aging agent comprises at least one of N-nitrosodicyclohexylamine and 2,6-di-tert-butyl-p-cresol; The filler comprises at least one of silica, talcum powder, calcium carbonate, carbon black, and short-cut polyester fiber; The antiseptic and mildew-proof agent comprises at least one of benzoic acid, chlorinated aniline, and biphenyl alcohol; 5. A flame-retardant anti-sticking waterproof board according to claim 4, characterized in that: The acrylic emulsion comprises at least one of poly(methyl acrylate) emulsion, acrylate-methyl methacrylate copolymer emulsion, and acrylic / styrene copolymer emulsion; The cross-linking agent comprises at least one of diisophorone peroxide, MDI, TDI, and methyltrichlorosilane; The pigment filler comprises at least one of titanium dioxide, carbon black, aluminum powder, barium titanate, and iron oxide red; The auxiliary agent comprises at least one of rheology auxiliary agent, dispersion auxiliary agent, wetting agent, defoaming agent, and preservative.

6. A flame-retardant anti-sticking waterproof board according to claim 5, characterized in that: The auxiliary agent includes at least one of nitrified paraffin, carbomer, hydroxypropyl methylcellulose, polycarboxylate dispersant, sulfonate dispersant, sodium stearate, calcium stearate, polyether defoamer, silicone oil defoamer, sodium benzoate, and methylisothiazolinone.

7. A flame-retardant anti-sticking waterproof board according to claim 6, characterized in that: In step S1, the mass ratio between the melamine and sodium methoxide is 1:0.35 - 0.5; the mass ratio between the melamine and phosphorus oxychloride is 1:0.35 - 0.

5.

8. A flame-retardant anti-sticking waterproof board according to claim 7, characterized in that: In step S2, the mass concentration of the phosphorylated melamine in tetrahydrofuran is 0.05 - 0.1 g / mL; in step S2, the added mass of cyanuric chloride is 36% - 55% of the mass of the phosphorylated melamine.

9. A flame-retardant anti-sticking waterproof board according to claim 8, characterized in that: In step S2, the mass-volume ratio between the phosphorylated melamine and borane dimethyl sulfide is 3 - 4.5 g / mL.

10. The preparation method of a flame-retardant anti-sticking waterproof board according to any one of claims 1-9, characterized in that: Specifically, it includes the following steps: ① Place aluminum hydroxide, ammonium polyphosphate, pigments and fillers, and a dispersant in water, and mix them at a speed of 3000 - 5000 rpm at room temperature until the fineness is uniform to obtain an inorganic filler slurry. ② Add acrylic emulsion to a stirring tank, slowly add the inorganic filler slurry described in step ①, stir until uniform, and sequentially add lignosulfonate and a flame retardant additive to obtain a premix. ③ To the premix described in step ②, add a crosslinking agent and an auxiliary agent, adjust the pH to 7.5 - 8.5, stir until the system is stable and free of bubbles, dilute with water to a solid content of 40% - 50%, stand still and vacuum defoam to obtain a flame retardant coating layer material. ④ Heat the matrix asphalt to 140 - 150 °C to keep it flowing, raise the temperature to 170 - 180 °C, slowly add the SBS copolymer, and stir at a shear of 3000 - 5000 rpm for 30 - 45 min until the SBS is completely fused with the asphalt and the particles disappear to obtain SBS modified asphalt. ⑤ Take the SBS modified asphalt described in step ④ and continue to add a tackifier in portions and stir for 15 - 20 min at 170 - 180 °C. According to 2000 - 3000 rpm, successively add a plasticizer, an antioxidant, an anti-aging agent, a filler, and an anti-corrosion and anti-mildew agent, stir for 5 - 10 min until evenly dispersed, keep the material standing for 5 min to allow large bubbles to escape naturally, and slowly cool down to below 140 °C to obtain a self-adhesive layer material. ⑥ Take a base material layer, coat the self-adhesive layer material on the surface of the base material, after cooling and shaping, scrape the flame retardant coating layer material on the surface of the base material, dry it at a low temperature of 60 - 80 °C, cut it into shape to obtain a flame retardant self-adhesive waterproof board.

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