High-molecular polymer waterproof coating and preparation method thereof

Abstract

The invention discloses a high-molecular polymer waterproof coating and a preparation method thereof, and relates to the technical field of high-molecular materials. The invention discloses a high-molecular polymer waterproof coating. The coating is prepared from the following raw materials in parts by weight: 40 to 60 parts of modified acrylic emulsion, 1 to 5 parts of cerium oxide, 0.5 to 2 parts of silane coupling agent KH-550, 10 to 30 parts of modified epoxy resin, 5 to 15 parts of castor oil-based polyol, 0.1 to 0.5 part of dibutyltin dilaurate, 3 to 8 parts of nano montmorillonite, 0.5 to 2 parts of sodium polyacrylate, 0.5 to 2 parts of acrylate flatting agent, 3 to 10 parts of tributyl citrate and 1 to 3 parts of methylhexahydrophthalic anhydride. 0.1-1 part of triphenyl phosphite, 1-5 parts of urea-formaldehyde resin coated epoxy resin microcapsules, 0.5-1 part of polydimethylsiloxane, 1-3 parts of nano-zinc oxide, 5-10 parts of aluminum hydroxide and 1-2 parts of titanium dioxide. The coating is excellent in waterproof performance, capable of self-repairing damage and achieving antibacterial, fireproof and self-cleaning effects, the performance of modified substances is improved through complex reactions, and the coating is excellent in building waterproof performance, sanitary safety and the like and has wide application prospects.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and specifically to a polymer waterproof coating. Background Art

[0002] In many fields such as construction and industry, waterproof treatment has always been a key link to ensure the safety and long-term operation of facilities. At present, many defects have emerged in the practical application of traditional waterproof coatings. Taking asphalt-based waterproof coatings as an example, although they are low-cost and have a mature process, they are extremely easy to crack in low-temperature environments and flow easily at high temperatures, resulting in a significant reduction in the waterproof effect and being unable to meet the waterproof requirements under extreme climate conditions. Common polymer waterproof coatings, although improving performance to a certain extent, still have shortcomings in functional integration and long-term stability.

[0003] With the booming development of modern architecture, building structures are becoming more complex and functional requirements are increasingly diverse. For buildings such as high-rise office buildings and large commercial complexes, roof waterproofing needs to resist long-term ultraviolet radiation, rain erosion, and drastic temperature fluctuations; underground buildings such as subways and underground parking lots face the continuous threat of groundwater seepage, which poses strict requirements on the waterproof durability, weather resistance, and anti-seepage ability of waterproof coatings. In the industrial field, facilities such as chemical storage tanks and pipelines come into contact with various chemical media, and the chemical corrosion resistance of ordinary coatings is difficult to meet the requirements, and corrosion leakage is likely to occur, leading to potential safety hazards and economic losses.

[0004] At the same time, society's attention to the health, safety, and environmental protection performance of the building environment is increasing day by day. In places such as hospitals, schools, and food processing plants, waterproof coatings are required to have antibacterial functions to prevent the growth of microorganisms and ensure the health of personnel; public buildings with a large number of people attach great importance to fire safety and require coatings to have good flame retardant properties. In addition, environmental protection regulations are becoming increasingly strict, and the problem of high volatile organic compound emissions in the production and use of traditional waterproof coatings needs to be solved urgently. Developing green and environmentally friendly waterproof coatings has become a trend in the industry. Therefore, developing a polymer waterproof coating with excellent comprehensive performance, diverse functions, and environmental friendliness is the key to solving the current industry dilemma. Summary of the Invention

[0005] Aiming at the deficiencies of the prior art, the present invention provides a polymer waterproof coating, which solves the above problems.

[0006] To achieve the above objectives, the present invention is realized through the following technical solutions: A polymer waterproof coating contains the following raw materials in parts by weight: 40 - 60 parts of modified acrylic emulsion, 1 - 5 parts of cerium oxide, 0.5 - 2 parts of silane coupling agent KH - 550, 10 - 30 parts of modified epoxy resin, 5 - 15 parts of castor oil - based polyol, 0.1 - 0.5 parts of dibutyltin dilaurate, 3 - 8 parts of nano - montmorillonite, 0.5 - 2 parts of sodium polyacrylate, 0.5 - 2 parts of acrylate leveling agent, 3 - 10 parts of tributyl citrate, 1 - 3 parts of methylhexahydrophthalic anhydride, 0.1 - 1 parts of triphenyl phosphite, 1 - 5 parts of urea - formaldehyde resin - coated epoxy resin microcapsules, 0.5 - 1 parts of polydimethylsiloxane, 1 - 3 parts of nano - zinc oxide, 5 - 10 parts of aluminum hydroxide, and 1 - 2 parts of titanium dioxide.

[0007] Further, the modified epoxy resin synthesizes a hyperbranched polymer by introducing trimethylolpropane and methyl acrylate to form a highly branched three - dimensional network structure, which has high toughness and strong adhesion.

[0008] Further, the modified acrylic emulsion forms an organic - inorganic hybrid network and multi - block copolymer structure by introducing nano - silver particles, polyurethane prepolymer, and epoxy resin, which can inhibit bacterial reproduction and has water resistance.

[0009] Further, the specific preparation steps of the modified epoxy resin are as follows: A1. Introduce high - purity nitrogen into the reaction kettle, then add epoxy resin and acid anhydride curing agent and stir evenly, and raise the temperature to 120 °C for reaction; A2. After the reaction is completed, transfer the substance to a high - speed stirrer, then slowly add nano - silica and stir evenly, and then perform ultrasonic dispersion. During the ultrasonic process, dropwise add titanate coupling agent; A3. First add trimethylolpropane to the three - necked flask, then dropwise add methyl acrylate, raise the temperature to 120 °C to synthesize the hyperbranched polymer, and then add the product obtained in A2 and the hyperbranched polymer to the reaction kettle together, set the temperature to 100 °C, and continuously stir and react to obtain the modified epoxy resin.

[0010] Further, the flow rate of nitrogen introduced in A1 is 30 L / h, and the introduction time is 15 minutes; during the curing reaction, stir at a speed of 200 r / min for 3 hours; the dosage ratio of epoxy resin to acid anhydride curing agent is 100 g:25 g.

[0011] Further, the rotation speed of the high - speed stirrer in A2 is 1500 r / min, stir for 1 hour, and then perform ultrasonic dispersion for 1 hour; during the ultrasonic process, use a constant - pressure dropping funnel to dropwise add titanate coupling agent at a rate of 0.5 mL / min; the dosage ratio of nano - silica to titanate coupling agent is 5 g:2 mL.

[0012] Further, the stirring speed of the hyperbranched polymerization reaction in A3 is 300 r / min, and the stirring time is 6 hours; the stirring speed in the reaction kettle is 150 r / min, and the reaction time is 3 hours; the dosage ratio of trimethylolpropane, methyl acrylate, and the product of A2 is 10 g: 40 mL: 100 g.

[0013] At 120 °C, the acid anhydride groups of the acid anhydride curing agent and the epoxy groups of the epoxy resin undergo a ring-opening addition reaction. One carbonyl group in the acid anhydride group first combines with the oxygen atom of the epoxy group to open the epoxy ring, and then the other carbonyl group undergoes an esterification reaction with the hydroxyl group generated after the epoxy ring opening, gradually forming a crosslinked structure, preliminarily curing the epoxy resin, and improving its hardness and heat resistance; the molecular structure of the titanate coupling agent contains an inorganic group and an organic group. The inorganic group can chemically react with the hydroxyl groups on the surface of nano-silica to form a chemical bond connection; the organic group can interact with the epoxy resin molecules and play a bridging role between nano-silica and epoxy resin through physical entanglement or chemical bonding, enhancing the compatibility and bonding force between the two, and significantly improving the strength, toughness, and wear resistance of the material.

[0014] Further, the preparation steps of the modified acrylic emulsion are as follows: B1. Turn on the nitrogen replacement device, introduce nitrogen, then add acrylic emulsion, heat up to 80 °C, add potassium persulfate, and at the same time turn on the stirring device. Under stirring, slowly dropwise add the quaternary ammonium salt monomer. After the reaction is completed, naturally cool to room temperature to obtain an acrylic emulsion grafted with the quaternary ammonium salt monomer. B2. Take the acrylic emulsion after the first modification, place it in an ultrasonic dispersion device, add nano-silver particles and sodium dodecylbenzenesulfonate, turn on the ultrasonic dispersion equipment, and add a silane coupling agent to the system during this period. B3. Place the three-necked flask containing diisocyanate and polyether polyol in an oil bath, heat up to 80 °C, stir and react to generate a polyurethane prepolymer; then add the product of A2 to the three-necked flask, add dibutyltin dilaurate catalyst, lower the temperature of the oil bath to 60 °C, and then add ethylenediamine chain extender, and react together to obtain the modified acrylic emulsion.

[0015] Further, the nitrogen flow rate in B1 is 20 L / h, the introduction time is 30 minutes, the stirring speed during the reaction process is 200 r / min, the stirring time is 15 minutes, and during this period, the quaternary ammonium salt monomer is slowly added dropwise at a rate of 0.5 g / min through a constant pressure dropping funnel. After the dropping is completed, continue to react for 3 hours. The dosage ratio of acrylic emulsion, potassium persulfate, and quaternary ammonium salt monomer is 100 g: 0.5 g: 10 g.

[0016] Further, the ultrasonic power in B2 is set to 300 W, the temperature is controlled at 30 °C, and ultrasonic treatment is carried out for 2 hours. During this period, 0.1 mL of silane coupling agent is added to the system every 30 minutes. The dosage ratio of the acrylic emulsion, silver nanoparticles, and sodium dodecylbenzenesulfonate after the first modification is 50 g: 0.2 g: 0.3 g.

[0017] Further, in B3, when the polyurethane prepolymer reacts, the stirring speed is 300 r / min and the stirring duration is 2 hours. After adding dibutyltin dilaurate, the stirring speed is adjusted to 250 r / min and stirring is carried out for 2 hours. After adding ethylenediamine chain extender, stirring is continued for 2 hours. The dosage ratio of diisocyanate, polyether polyol, A2 product, dibutyltin dilaurate, and ethylenediamine is 20 g: 30 g: 30 g: 0.1 g: 0.05 g.

[0018] Potassium persulfate decomposes under heating conditions to generate sulfate radicals, which initiate the free radical polymerization reaction of double bonds in the acrylic emulsion; the double bonds in the quaternary ammonium salt monomer undergo grafting reactions with the polymer chains of the acrylic emulsion under the action of free radicals, introducing quaternary ammonium salt groups into the molecular chains of the acrylic emulsion and endowing the emulsion with antibacterial properties because quaternary ammonium salts have the effect of destroying bacterial cell membranes, thereby inhibiting the growth of microorganisms.

[0019] One end of the silane coupling agent reacts with the hydroxyl groups or other active sites on the surface of silver nanoparticles, and the other end interacts with the acrylic emulsion molecules, enhancing the binding force between silver nanoparticles and the emulsion and improving the antibacterial properties of the emulsion. At the same time, silver nanoparticles can also improve the stability and weather resistance of the emulsion to a certain extent.

[0020] The isocyanate groups of diisocyanate undergo stepwise addition polymerization reactions with the hydroxyl groups of polyether polyol to form a polyurethane prepolymer containing a large number of free isocyanate groups; the isocyanate groups of the polyurethane prepolymer undergo chemical reactions with active groups such as hydroxyl groups and amino groups in the acrylic emulsion under the action of a catalyst. At the same time, the ethylenediamine chain extender further makes the molecular chain grow and crosslink, forming a polyurethane-acrylate interpenetrating network structure. This interpenetrating network structure combines the advantages of polyurethane and acrylate, significantly improving the water resistance, abrasion resistance, flexibility, and mechanical strength of the emulsion.

[0021] A preparation method of a polymer waterproof coating specifically includes the following steps: S1. Add the modified acrylic emulsion to a stirring kettle, start stirring, and sequentially add cerium oxide, nano-montmorillonite, sodium polyacrylate, and silane coupling agent KH-550, and stir evenly. S2. Control the temperature at 60 °C, and slowly add the modified epoxy resin, castor oil-based polyol, and dibutyltin dilaurate under stirring. S3, lower the temperature to 40°C, add acrylate leveling agent, tributyl citrate, methyl hexahydrophthalic anhydride, triphenyl phosphite, urea-formaldehyde resin-coated epoxy resin microcapsules in sequence under stirring, and stir evenly; S4, add polydimethylsiloxane, nano zinc oxide, aluminum hydroxide and titanium dioxide, and stir evenly; S5. Add the above substances into a sand mill, select zirconium oxide beads as the grinding medium, set the speed to 1500r / min, grind for 3 hours, and transfer the coating dispersed by mechanical grinding to a vacuum degassing device for treatment to obtain a waterproof coating; Furthermore, in S1, the stirring speed is 300 r / min, the modified acrylic emulsion is added and stirred for 30 minutes, and then cerium oxide, nano-montmorillonite, sodium polyacrylate and silane coupling agent KH-550 are added in sequence, and each substance is stirred for 15 minutes after addition; in S2, the stirring speed is 400 r / min, and stirring is carried out for 30 minutes; in S3, the stirring speed is 400 r / min, and stirring is carried out for 30 minutes; in S4, the stirring speed is 200 r / min, and stirring is carried out for 40 minutes; in S5, the speed is set to 1500 r / min, grinding is carried out for 3 hours, the vacuum degassing equipment is set to a vacuum degree of -0.08 MPa and a temperature of 30°C, and degassing is continued for 40 minutes.

[0022] The present invention provides a high molecular polymer waterproof coating and a preparation method thereof, which has the following beneficial effects: 1. In this coating, modified acrylic emulsion and modified epoxy resin cooperate with each other to form a dense waterproof membrane structure. Modified acrylic emulsion has good film-forming properties and water resistance, and can effectively block water penetration; modified epoxy resin enhances the adhesion and hardness of the coating, making the waterproof membrane more durable. The sheet structure of nano-montmorillonite plays a barrier role in the coating, extending the water penetration path and further improving the waterproof effect. It can be widely used in waterproof projects such as building roofs and basements to resist rainwater and groundwater erosion for a long time.

[0023] 2. The addition of self-repairing microcapsules gives the coating unique self-repairing properties. When the coating film is slightly damaged, the stress at the crack will cause the self-repairing microcapsules to rupture and release the internal repair agent. Urea-formaldehyde resin encapsulates epoxy resin microcapsules. The released epoxy resin undergoes a cross-linking reaction with the surrounding active groups under the action of catalysts such as dibutyltin dilaurate, filling the cracks and restoring the integrity of the coating film, greatly extending the service life of the waterproof coating and reducing the subsequent maintenance costs.

[0024] 3. The addition of nano-zinc oxide inhibits the growth and reproduction of microorganisms, prevents mildew and bacterial growth on the coating surface, maintains the cleanliness and hygiene of the coating, and is especially suitable for places with high hygiene requirements, such as bathrooms, kitchens, etc. Aluminum hydroxide decomposes endothermically when exposed to fire, forming a heat-insulating layer that prevents the spread of flames, improves the fire safety of the coating, reduces the fire risk, and safeguards the safety of personnel and property. When there is dirt on the coating surface, titanium dioxide can degrade the dirt under sunlight, keeping the coating clean, reducing the manual cleaning cost, and at the same time enhancing the aesthetic appearance and durability of the building.

[0025] 4. This polymer waterproof coating performs excellently in terms of environmental protection performance. It uses castor oil-based polyols, and the raw materials are derived from renewable resources, reducing the dependence on non-renewable resources such as petroleum and reducing the environmental pressure caused by coating production from the source. At the same time, no heavy-metal-containing additives are used in the coating formulation, avoiding the pollution risk of heavy metals to the soil and water bodies during production, use, and after disposal. Moreover, during the preparation and use of the coating, the release amount of volatile organic compounds is low, reducing the pollution of the atmospheric environment, reducing the possibility of environmental problems such as photochemical smog, protecting the air quality indoors and outdoors, and creating a healthy and environmentally friendly living and working environment for users. Specific embodiments

[0026] The technical solutions in the embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0027] Example 1. Prepare a polymer waterproof coating, and the preparation method is as follows: S1. Add 40 parts of modified acrylic emulsion to a stirring kettle, start stirring, set the stirring speed to 300 r / min and stir for 15 minutes. Then add 1 part of cerium oxide, 3 parts of nano-montmorillonite, 0.5 part of sodium polyacrylate, and 0.5 part of silane coupling agent KH-550 in sequence. Stir for 15 minutes after adding each substance. S2. Control the temperature at 60 °C, and slowly add 10 parts of modified epoxy resin, 5 parts of castor oil-based polyol, and 0.1 part of dibutyltin dilaurate under stirring. At the same time, increase the stirring speed to 400 r / min and stir for 30 minutes. S3. Lower the temperature to 40 °C, and add 0.5 part of acrylate leveling agent, 3 parts of tributyl citrate, 1 part of methylhexahydrophthalic anhydride, 0.1 part of triphenyl phosphite, and 1 part of urea-formaldehyde-coated epoxy resin microcapsules in sequence under stirring. Stir at a speed of 400 r / min for 30 minutes. S4. Add 0.5 part of polydimethylsiloxane, 1 part of nano-zinc oxide, 5 parts of aluminum hydroxide, and 1 part of titanium dioxide. Reduce the stirring speed to 200 r / min and stir for 40 min. S5. Add the above substances into a sand mill, select zirconia beads as the grinding medium, set the rotation speed at 1500 r / min, and grind for 3 hours. Transfer the paint after mechanical grinding and dispersion to a vacuum degassing device, and continuously degas for 40 minutes under the conditions of a vacuum degree of -0.08 Mpa and a temperature of 30 °C to obtain a waterproof paint.

[0028] Example 2. Prepare a polymer waterproof paint. The preparation method is as follows: S1. Add 60 parts of modified acrylic emulsion into a stirring kettle, start stirring, set the stirring speed at 300 r / min and stir for 15 minutes. Then add 5 parts of cerium oxide, 8 parts of nano-montmorillonite, 2 parts of sodium polyacrylate, and 2 parts of silane coupling agent KH-550 in sequence. Stir for 15 minutes after adding each substance. S2. Control the temperature at 60 °C, and slowly add 30 parts of modified epoxy resin, 15 parts of castor oil-based polyol, and 0.5 part of dibutyltin dilaurate under stirring. At the same time, increase the stirring speed to 400 r / min and stir for 30 minutes. S3. Lower the temperature to 40 °C, and add 2 parts of acrylate leveling agent, 10 parts of tributyl citrate, 3 parts of methylhexahydrophthalic anhydride, 1 part of triphenyl phosphite, and 5 parts of urea-formaldehyde coated epoxy resin microcapsules in sequence under stirring. Stir at a speed of 400 r / min for 30 minutes. S4. Add 1 part of polydimethylsiloxane, 3 parts of nano-zinc oxide, 10 parts of aluminum hydroxide, and 2 parts of titanium dioxide. Reduce the stirring speed to 200 r / min and stir for 40 min. S5. Add the above substances into a sand mill, select zirconia beads as the grinding medium, set the rotation speed at 1500 r / min, and grind for 3 hours. Transfer the paint after mechanical grinding and dispersion to a vacuum degassing device, and continuously degas for 40 minutes under the conditions of a vacuum degree of -0.08 Mpa and a temperature of 30 °C to obtain a waterproof paint.

[0029] Example 3. Prepare a polymer waterproof paint. The preparation method is as follows: S1. Add 50 parts of modified acrylic emulsion into a stirring kettle, start stirring, set the stirring speed at 300 r / min and stir for 15 minutes. Then add 3 parts of cerium oxide, 5 parts of nano-montmorillonite, 1 part of sodium polyacrylate, and 1 part of silane coupling agent KH-550 in sequence. Stir for 15 minutes after adding each raw material. S2. Control the temperature at 60 °C, and slowly add 20 parts of modified epoxy resin, 10 parts of castor oil-based polyol and 0.3 part of dibutyltin dilaurate under stirring, and at the same time increase the stirring speed to 400 r / min and stir for 30 min; S3. Lower the temperature to 40 °C, and successively add 1 part of acrylate leveling agent, 6 parts of tributyl citrate, 2 parts of methylhexahydrophthalic anhydride, 0.5 part of triphenyl phosphite, and 3 parts of urea-formaldehyde resin-coated epoxy resin microcapsules under stirring, and stir at a rotation speed of 400 r / min for 30 minutes; S4. Add 0.7 part of polydimethylsiloxane, 2 parts of nano-zinc oxide, 7 parts of aluminum hydroxide, and 1 part of titanium dioxide, lower the stirring speed to 200 r / min, and stir for 40 min; S5. Add the above substances into a sand mill, select zirconia beads as the grinding medium, set the rotation speed at 1500 r / min, grind for 3 hours, transfer the paint after mechanical grinding and dispersion to a vacuum degassing device, and under the conditions of a vacuum degree of -0.08 Mpa and a temperature of 30 °C, continuously degas for 40 minutes to obtain a waterproof paint.

[0030] Example 4. Prepare modified epoxy resin, and the preparation method is as follows: A1. Introduce high-purity nitrogen into the reaction kettle at a stable flow rate of 30 L / h for 15 min, then add 100 g of epoxy resin and 25 g of acid anhydride curing agent, stir at a speed of 200 r / min, and slowly raise the temperature of the reaction kettle to 120 °C and continuously stir for 3 hours; A2. After the reaction is completed, transfer the substance to a high-speed stirrer, slowly add 5 g of nano-silica, set the stirring speed at 1500 r / min, stir for 1 hour, and then ultrasonically disperse for 1 hour. During the process, use a constant pressure dropping funnel to drop 2 mL of titanate coupling agent at a rate of 0.5 mL / min; A3. First add 10 g of trimethylolpropane to a three-necked flask, then slowly drop 40 mL of methyl acrylate, raise the temperature to 120 °C, stir at a stirring speed of 300 r / min, and stir and react for 6 hours to synthesize a hyperbranched polymer. Then add the product obtained in 100 g A2 and the hyperbranched polymer into the reaction kettle together, set the temperature at 100 °C, and the stirring speed at 150 r / min, and react for 3 hours to obtain modified epoxy resin.

[0031] Example 5. Prepare modified acrylic emulsion, and the preparation method is as follows: B1. Turn on the nitrogen replacement device, introduce nitrogen into the four-necked flask at a flow rate of 20 L / h for 30 minutes, then add 100 g of acrylic emulsion, slowly raise the temperature to 80 °C, add 0.5 g of potassium persulfate, and at the same time turn on the stirring device and continuously stir at 200 r / min for 15 minutes. During the process, slowly drip 10 g of quaternary ammonium salt monomer into the system through a constant pressure dropping funnel at a rate of 0.5 g / min. After the dropping is completed, continue the reaction for 3 hours. After the reaction is completed, the system is naturally cooled to room temperature to obtain acrylic emulsion grafted with quaternary ammonium salt monomer; B2. Take 50 g of the acrylic emulsion after the first modification, place it in an ultrasonic dispersion device, add 0.2 g of silver nanoparticles and 0.3 g of sodium dodecylbenzenesulfonate, turn on the ultrasonic dispersion equipment, set the power to 300 W, control the temperature at 30 °C, and ultrasonicate for 2 hours. During this period, add 0.1 mL of silane coupling agent to the system every 30 minutes; B3. Place a three-necked flask containing 20 g of diisocyanate and 30 g of polyether polyol in an oil bath, heat up to 80 °C, and during the reaction, continuously stir at a speed of 300 r / min for 2 hours to generate a polyurethane prepolymer; then add 30 g of Product A2 to the three-necked flask, add 0.1 g of dibutyltin dilaurate catalyst, lower the oil bath to 60 °C, adjust the stirring speed to 250 r / min, continue stirring for 2 hours, then add 0.05 g of ethylenediamine chain extender, and continue to react at 60 °C for 2 hours to obtain a modified acrylic emulsion.

[0032] Comparative Example 1. Prepare a high molecular polymer waterproof coating, and the preparation method is as follows: Keep the other steps unchanged, and only replace the modified epoxy resin in Example 2 with epoxy resin without any treatment to prepare a high molecular polymer waterproof coating.

[0033] Comparative Example 2. Prepare a high molecular polymer waterproof coating, and the preparation method is as follows: Keep the other steps unchanged, and only replace the modified acrylic emulsion in Example 2 with acrylic emulsion without any treatment to prepare a high molecular polymer waterproof coating.

[0034] Performance test Test Items Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Tensile Strength (MPa) 3.5 4.0 3.8 2.0 1.5 Elongation at Break (%) 450 500 480 300 250 Adhesion (Cross-Cut Method, Grade) 1 1 1 2 3 Water Resistance (After Immersion for 7 Days, Coating Film Appearance) No Obvious Change No Obvious Change No Obvious Change Slight Whitening and Wrinkling Severe Blistering and Peeling Weather Resistance (After Artificial Accelerated Aging for 500h, Coating Film Appearance) Slight Color Fading, No Cracking or Peeling Slight Color Fading, No Cracking or Peeling Slight Color Fading, No Cracking or Peeling Obvious Color Darkening, A Few Cracks and Peeling Severe Color Darkening, A Large Number of Cracks and Peeling Waterproof Performance (Waterproof Time, h) ≥72 ≥96 ≥84 ≥48 ≥36 Self-Healing Performance (Crack Repair Rate, %) ≥80 ≥85 ≥82 ≥30 ≥20 Antibacterial Performance (Inhibitory Rate against Escherichia coli, %) ≥95 ≥98 ≥96 ≥70 ≥50 Flame Retardant Performance (Flame Retardant Grade) B1 Grade B1 Grade B1 Grade B2 Grade C Grade Hardness (Pencil Hardness) H H H HB 2B Chemical Resistance (After Immersion in 5% Hydrochloric Acid for 48h, Coating Film Appearance) No Obvious Change No Obvious Change No Obvious Change Slight Corrosion Marks Obvious Corrosion and Color Change Wear Resistance (Taber Abrasion Test, Abrasion Loss g) 0.05 0.04 0.045 0.12 0.18 Generally speaking, Examples 1, 2, and 3 using modified epoxy resin and modified acrylic emulsion are significantly superior to Comparative Example 1 and Comparative Example 2 in terms of various properties. The specific performance is as follows: Higher tensile strength and elongation at break, showing better strength and flexibility. It combines more firmly with the substrate, and the adhesion reaches the best level. It performs excellently in the water resistance and weather resistance tests, with no obvious change in the appearance of the coating film, while the comparative examples show problems such as varying degrees of whitening, wrinkling, peeling, etc. The water impermeable time is longer and the waterproof ability is stronger. The crack repair rate is greatly improved and the self-repair ability is significantly enhanced. The antibacterial rate against Escherichia coli is higher and the antibacterial effect is better. The flame retardant grade reaches B1 level, which is better than the B2 level and C level of the comparative examples. In the chemical corrosion resistance and abrasion resistance tests, there is no obvious change in the appearance of the coating film of the examples, and the abrasion resistance is better, while the comparative examples show corrosion marks and a higher wear amount.

[0035] In summary, the modified polymer waterproof coating exhibits excellent properties in terms of mechanical properties, durability, waterproofness, self-repair ability, antibacterial property, flame retardancy, chemical corrosion resistance and abrasion resistance, and has high application value.

[0036] The above content is only an example and illustration of the present invention. Those skilled in the art of this technology can make various modifications or supplements to the described specific embodiments or use similar ways to replace them. As long as they do not deviate from the invention or exceed the scope defined by this claims, they should fall within the protection scope of the present invention.

Claims

1. A polymer waterproof coating, characterized in that: It contains the following raw materials in parts by weight: 40-60 parts of modified acrylic emulsion, 1-5 parts of cerium oxide, 0.5-2 parts of silane coupling agent KH-550, 10-30 parts of modified epoxy resin, 5-15 parts of castor oil-based polyol, 0.1-0.5 parts of dibutyltin dilaurate, 3-8 parts of nano-montmorillonite, 0.5-2 parts of sodium polyacrylate, 0.5-2 parts of acrylate leveling agent, 3-10 parts of tributyl citrate, 1-3 parts of methylhexahydrophthalic anhydride, 0.1-1 part of triphenyl phosphite, 1-5 parts of urea-formaldehyde resin-coated epoxy resin microcapsules, 0.5-1 part of polydimethylsiloxane, 1-3 parts of nano-zinc oxide, 5-10 parts of aluminum hydroxide, and 1-2 parts of titanium dioxide; The modified epoxy resin synthesizes a hyperbranched polymer by introducing trimethylolpropane and methyl acrylate to form a highly branched three-dimensional network structure, which has high toughness and strong adhesion; The modified acrylic emulsion forms an organic-inorganic hybrid network and multi-block copolymer structure by introducing nano-silver particles, polyurethane prepolymer and epoxy resin, inhibits bacterial reproduction and has water resistance.

2. The polymer waterproof coating according to claim 1, wherein: The specific preparation steps of the modified epoxy resin are as follows: A1. Introduce high-purity nitrogen into the reaction kettle, then add epoxy resin and acid anhydride curing agent and stir evenly, and raise the temperature to 120 °C for reaction; A2. After the reaction is completed, transfer the substance to a high-speed stirrer, then slowly add nano-silica and stir evenly, and then perform ultrasonic dispersion. During the ultrasonic process, titanate coupling agent is added dropwise; A3. First add trimethylolpropane to the three-necked flask, then dropwise add methyl acrylate, raise the temperature to 120 °C to synthesize the hyperbranched polymer, and then add the product obtained in A2 and the hyperbranched polymer to the reaction kettle together, set the temperature to 100 °C, and continuously stir and react to obtain the modified epoxy resin.

3. The high molecular polymer waterproof coating according to claim 2, characterized in that: In A1, the flow rate of nitrogen introduced is 30 L / h, and the introduction time is 15 minutes; during the curing reaction, it is stirred at a speed of 200 r / min for 3 hours; the dosage ratio of epoxy resin to acid anhydride curing agent is 100 g:25 g.

4. A polymer waterproof coating according to claim 2, characterized in that: In A2, the rotation speed of the high-speed stirrer is 1500 r / min, and it is stirred for 1 hour, and then ultrasonically dispersed for 1 hour; during the ultrasonic process, a constant-pressure dropping funnel is used to dropwise add the titanate coupling agent at a rate of 0.5 mL / min; the dosage ratio of nano-silica to titanate coupling agent is 5 g:2 mL.

5. The polymer waterproof coating according to claim 2, characterized in that: In A3, the stirring speed of the hyperbranched polymerization reaction is 300 r / min, and the stirring time is 6 hours; the stirring speed in the reaction kettle is 150 r / min, and the reaction time is 3 hours; the dosage ratio of trimethylolpropane, methyl acrylate and the product of A2 is 10 g:40 mL:100 g.

6. A high molecular polymer waterproof coating according to claim 1, characterized in that: The specific preparation steps of the modified acrylic emulsion are as follows: B1. Turn on the nitrogen replacement device, introduce nitrogen, then add acrylic emulsion, raise the temperature to 80 °C, add potassium persulfate, and at the same time turn on the stirring device. Under the stirring state, slowly dropwise add the quaternary ammonium salt monomer. After the reaction is completed, naturally cool to room temperature to obtain the acrylic emulsion grafted with the quaternary ammonium salt monomer; B2. Take the acrylic emulsion after the first modification, place it in an ultrasonic dispersion device, add silver nanoparticles and sodium dodecylbenzenesulfonate, turn on the ultrasonic dispersion equipment, and add a silane coupling agent to the system during this period; B3. Place a three-necked flask containing diisocyanate and polyether polyol in an oil bath, heat up to 80 °C, and stir to react to form a polyurethane prepolymer; then add the product of A2 to the three-necked flask, and add dibutyltin dilaurate catalyst. The temperature of the oil bath is lowered to 60 °C, and then an ethylenediamine chain extender is added, and they react together to obtain a modified acrylic emulsion.

7. A polymer waterproof coating according to claim 6, wherein: In B1, the nitrogen flow rate is 20 L / h, the flow-through time is 30 minutes, the stirring speed during the reaction process is 200 r / min, the stirring time is 15 minutes. During this period, the quaternary ammonium salt monomer is slowly added dropwise at a rate of 0.5 g / min through a constant pressure dropping funnel. After the dropping is completed, the reaction continues for 3 hours. The dosage ratio of the acrylic emulsion, potassium persulfate, and quaternary ammonium salt monomer is 100 g: 0.5 g: 10 g.

8. The waterborne polymer waterproof coating according to claim 6, characterized in that: In B2, the ultrasonic power is set to 300 W, the temperature is controlled at 30 °C, and ultrasonic treatment is carried out for 2 hours. During this period, 0.1 mL of silane coupling agent is added to the system every 30 minutes. The dosage ratio of the acrylic emulsion after the first modification, silver nanoparticles, and sodium dodecylbenzenesulfonate is 50 g: 0.2 g: 0.3 g.

9. The polymer waterproof coating according to claim 6, characterized in that: In B3, when the polyurethane prepolymer reacts, the stirring speed is 300 r / min, the stirring time is 2 hours. After adding dibutyltin dilaurate, the stirring speed is adjusted to 250 r / min and stirred for 2 hours. After adding the ethylenediamine chain extender, stirring continues for 2 hours. The dosage ratio of diisocyanate, polyether polyol, product of A2, dibutyltin dilaurate, and ethylenediamine is 20 g: 30 g: 30 g: 0.1 g: 0.05 g.

10. A preparation method of a polymer waterproof coating, characterized in that: Specifically, it includes the following steps: S1. Add the modified acrylic emulsion to a stirring kettle, start stirring, and sequentially add cerium oxide, nano-montmorillonite, sodium polyacrylate, and silane coupling agent KH-550, and stir evenly; S2. Control the temperature at 60 °C, and slowly add the modified epoxy resin, castor oil-based polyol, and dibutyltin dilaurate under stirring and continue stirring; S3. Lower the temperature to 40 °C, and sequentially add acrylate leveling agent, tributyl citrate, methylhexahydrophthalic anhydride, triphenyl phosphite, and urea-formaldehyde resin-coated epoxy resin microcapsules under stirring, and stir evenly; S4. Add polydimethylsiloxane, nano-zinc oxide, aluminum hydroxide, and titanium dioxide, and stir evenly; S5. Add the above substances to a sand mill, select zirconia beads as the grinding medium, set the rotation speed to 1500 r / min, and grind for 3 hours. The paint after mechanical grinding and dispersion is transferred to a vacuum degassing device for treatment to obtain a waterproof paint. The stirring speed in S1 is 300 r / min. After adding the modified acrylic emulsion, stir for 30 minutes, and then successively add cerium oxide, nano-montmorillonite, sodium polyacrylate, and silane coupling agent KH-550. Stir for 15 minutes after adding each substance; the stirring speed in S2 is 400 r / min, and stir for 30 minutes; the stirring speed in S3 is 400 r / min, and stir for 30 minutes; the stirring speed in S4 is 200 r / min, and stir for 40 minutes; in S5, the rotation speed is set at 1500 r / min, grind for 3 hours, the vacuum degassing equipment is set with a vacuum degree of -0.08 Mpa and a temperature of 30 °C, and continuously degas for 40 minutes.