Search

CN-122011865-A - Invisible waterproof agent based on double-lock slow release microspheres and preparation method thereof

CN122011865ACN 122011865 ACN122011865 ACN 122011865ACN-122011865-A

Abstract

The invention discloses a invisible waterproof agent based on double-lock slow-release microspheres and a preparation method thereof. The invisible waterproof agent is composed of a super-crosslinked polymer composite system and a water-based main system, wherein the super-crosslinked polymer composite system is formed by in-situ polymerization of phenyl modified siloxane, a polymerization monomer, a catalyst, a silane coupling agent and graphene quantum dots. According to the invention, graphene quantum dots are introduced into an in-situ polymerization super-crosslinked polymer carrier, so that a double composite action mechanism of covalent anchoring-pi stacking is constructed, and the fine regulation and control of the release dynamics of the hydrophobing agent are realized. The double-lock cooperative intelligent release mechanism formed by the invention enables the release of the hydrophobing agent to be changed into stress triggering-grading response from the traditional pore canal diffusion, and the response to the coating damage is more direct, the repair is quicker and the service life is longer. The invention realizes high loading capacity and firm package of the hydrophobing agent and solves the problems of complex process, unstable load and easy leakage of the traditional two-step method.

Inventors

  • FANG LIANG
  • WU JIAHUA
  • LIU ZIQIANG
  • GAO FENG
  • JIANG YOU

Assignees

  • 黄山华康新材料科技股份有限公司

Dates

Publication Date
20260512
Application Date
20260210

Claims (10)

  1. 1. The invisible waterproof agent based on the double-lock slow-release microspheres is characterized in that the invisible waterproof agent is formed by a super-crosslinked polymer composite system and a water-based main system by introducing graphene quantum dots into an in-situ polymerization super-crosslinked polymer carrier to construct a covalent anchoring-pi stacking double-composite action mechanism so as to realize fine regulation and control on the release dynamics of a hydrophobic agent; The super-crosslinked polymer composite system is formed by in-situ polymerization of the following raw materials, by mass, 2.0-4.0 parts of phenyl modified siloxane, 3.0-6.0 parts of a polymerization monomer, 0.1-0.4 parts of a catalyst, 1.0-2.0 parts of a silane coupling agent and 0.001-0.05 parts of graphene quantum dots.
  2. 2. The invisible waterproof agent based on the double-lock slow release microspheres according to claim 1, wherein, The water-based main system comprises, by mass, 75-82 parts of silicone-acrylate emulsion, 1.0-1.5 parts of polyurethane hardening agent, 2.0-3.0 parts of film forming auxiliary agent, 0.5-1.0 parts of wetting dispersant, 0.3-0.6 parts of defoamer, 0.2-0.5 parts of thickener and 8-12 parts of deionized water.
  3. 3. The invisible waterproof agent based on the double-lock slow release microsphere according to claim 1 is characterized in that the phenyl modified siloxane is at least one of phenyl hydrogen-containing silicone oil or hydroxyl end-capped phenyl silicone oil, the phenyl content of the phenyl modified siloxane is 20% -40%, the viscosity of the phenyl modified silicone oil is 300% -800 mPa.s, the phenyl modified siloxane is used as a coated hydrophobic repairing agent and also used as an organic phase medium for polymerization reaction in a system, and the phenyl modified siloxane can generate pi-pi stacking interaction with graphene quantum dots.
  4. 4. The invisible waterproof agent based on the double-lock slow release microsphere according to claim 1 is characterized in that the polymerized monomer comprises a crosslinking monomer and a comonomer, wherein the crosslinking monomer is divinylbenzene, the dosage of the divinylbenzene is 1.5-3.0 parts, and the dosage of the comonomer is benzene or toluene, and the dosage of the comonomer is 1.5-3.0 parts.
  5. 5. The invisible waterproof agent based on the double-lock slow release microspheres according to claim 4, wherein the dosage of the crosslinking monomer and the comonomer is 1:1, and the crosslinking monomer and the comonomer undergo Friedel-crafts alkylation under the action of a catalyst to form a three-dimensional super-crosslinked polymer network.
  6. 6. The invisible waterproof agent based on the double-lock slow release microsphere according to claim 5, wherein the graphene quantum dots are nanoparticles with the surface rich in carboxyl or hydroxyl and the size smaller than 10 nm, the addition amount of the nanoparticles is preferably 0.001% -0.05% of the total mass of the waterproof agent, and the graphene quantum dots can be combined with aromatic structures of phenyl modified siloxane and a super-crosslinked polymer network through pi-pi stacking effect in a system to form a reversible 'secondary dynamic lock', so that the release behavior of the hydrophobic agent is finely regulated.
  7. 7. The preparation method of the invisible waterproof agent based on the double-lock slow release microspheres is characterized by comprising the following specific steps of: Step 1, preparing hydrophobic slow-release microspheres by in-situ polymerization; Mixing phenyl modified siloxane, divinylbenzene and benzene in proportion in a drying reactor, stirring at normal temperature to form a uniform oil phase, cooling the system to 0-5 ℃, rapidly adding an anhydrous aluminum trichloride catalyst under stirring, keeping the low temperature for reaction for 1-2 hours, heating to 40-60 ℃ for continuous reaction for 6-12 hours, quenching the mixture after the reaction is finished, filtering, and washing to obtain a super-crosslinked polymer wet material loaded with a hydrophobic agent; Step 2, microsphere surface functionalization Dispersing the super-crosslinked polymer wet material in ethanol, adding a silane coupling agent KH792, and carrying out reflux reaction for 4-6 hours at 60-70 ℃, and separating, washing and drying after the reaction is finished to obtain the functional super-crosslinked polymer slow release microsphere with amino groups on the surface; Step 3, preparing a composite master batch; Mixing the functionalized super-crosslinked polymer slow release microspheres with a proper amount of deionized water, adding a formula amount of graphene quantum dots, and performing ultrasonic dispersion for 20-30 minutes under 300W power to enable the graphene quantum dots to be fully adsorbed and dispersed on the surfaces and gaps of the slow release microspheres to form uniform composite master batch dispersion; Step 4, compounding with an aqueous main system; placing the silicone-acrylate emulsion in a reaction kettle, stirring at a low speed, and slowly adding the composite master batch dispersion liquid into the emulsion; Step 5, adding and homogenizing an auxiliary agent; sequentially adding a film forming additive, a wetting dispersant and a defoaming agent under continuous stirring, and after the addition, raising the stirring rotation speed to 800-1000 rpm, and continuously stirring for 20-30 minutes; step 6, reinforcing and fixing the adhesion; The stirring speed is kept, a polyurethane hardening agent is added, stirring is continued to ensure uniform mixing, the rest deionized water is used for pre-dissolving the thickening agent and then is added into the system, the rotating speed is reduced to 200-300 rpm, and stirring is continued for 30-40 minutes; Step 7, curing and obtaining a finished product; And standing and curing the obtained product at normal temperature, and filtering the product by a precision filter to obtain an intelligent slow-release invisible waterproof agent finished product based on the in-situ polymerized super-crosslinked polymer.
  8. 8. The preparation method of the invisible waterproof agent based on the double-lock slow release microspheres according to claim 7 is characterized in that in the step 1, the in-situ polymerization reaction condition is that the reaction is carried out for 1-2 hours at the low temperature stage of 0-5 ℃, and the reaction is carried out for 6-12 hours at the temperature rising stage of 40-60 ℃.
  9. 9. The preparation method of the invisible waterproof agent based on the double-lock slow release microspheres according to claim 7 is characterized in that in the step 2, the surface functionalization condition is that reflux reaction is carried out for 4-6 hours at 60-70 ℃ in an ethanol solvent.
  10. 10. The method for preparing a invisible waterproof agent based on double-lock slow release microspheres according to claim 7, wherein in the step 7, the curing environment temperature is 20-30 ℃ and the relative humidity is 40-60%.

Description

Invisible waterproof agent based on double-lock slow release microspheres and preparation method thereof Technical Field The invention belongs to the technical field of building chemical protective materials, relates to an invisible waterproof agent based on double-lock slow-release microspheres and a preparation method thereof, and in particular relates to an intelligent slow-release invisible waterproof agent for building outer walls and a preparation method thereof. The waterproof agent directly encapsulates the hydrophobic functional component in the super-crosslinked polymer network through an innovative in-situ polymerization nano-composite process, and introduces graphene quantum dots as a regulating unit, so that the waterproof agent has the characteristics of long-acting self-repairing, high transparency, super-hydrophobicity, high durability and the like. Background The building outer wall is exposed to the complex natural environments such as rainwater, ultraviolet rays, pollutants, freeze thawing cycle and the like for a long time, and the problems of water seepage, microcrack, weathering, dirt adhesion, performance attenuation and the like are easy to occur. Although the traditional waterproof materials such as organic silicon, acrylic resin and the like have certain protection effect, the traditional waterproof materials have the defects of single function and insufficient durability, and particularly have limited protection life due to the lack of the capability of active repair after damage. In order to improve durability, the prior art introduces an intelligent slow release concept, namely, a hydrophobic agent is loaded in a porous carrier in advance and then is doped with a coating, so that self-repairing after damage is realized. Among them, inorganic mesoporous materials (such as silica) are the main technological path. However, such inorganic carrier-based schemes have several inherent drawbacks, firstly, the surface of the inorganic carrier is generally hydrophilic, the hydrophobic agent is effectively adsorbed only through complicated chemical modification (such as amination), the process is complicated and the cost is increased, secondly, the compatibility of the inorganic nano particles and the organic resin matrix is poor, the transparency and the stability of the coating are easily affected, and finally, the release mechanism is mainly simple diffusion after physical adsorption, the release behavior is not intelligent enough, and the precise response to external damage or environmental change is difficult to realize. In addition, the process of the two-step method (firstly synthesizing the carrier and then impregnating and loading) has the essential limitation that the loading process depends on the inherent pore diameter and surface chemistry of the carrier, the loading rate of the hydrophobe is limited, the binding force is weak, leakage easily occurs in the initial stage of storage or use, and the long-acting repairing capability is reduced. Therefore, development of a novel carrier capable of realizing efficient loading, firm combination and intelligent response and a simplified process matched with the novel carrier are very important for promoting practical application of the intelligent self-repairing waterproof coating. The super cross-linked polymer is a kind of organic porous material with high specific surface area formed by aromatic monomer through Friedel-crafts reaction, etc., and has intrinsically hydrophobic skeleton and excellent compatibility with organic hydrophobic agent. If the loading of the hydrophobizing agent and the generation of the polymer network can be completed in one step, the technical bottleneck is hopeful to be overcome fundamentally. However, how to combine the material characteristics with the preparation process innovation of the waterproof agent, and how to further finely regulate the release kinetics (such as release rate, response sensitivity and repair durability) of the hydrophobic agent on the premise of ensuring the high transparency of the coating, so that the release kinetics are more matched with the complex damage mode of the coating in actual use, is still a technical difficulty to be broken through in the field. The prior art lacks an effective means for performing fine tuning control on the release interface on the nano scale, which limits further improvement and practical application of the performance of the intelligent self-repairing coating. Disclosure of Invention The invention aims at providing an invisible waterproof agent based on double-lock slow-release microspheres and a preparation method thereof, in particular to an intelligent slow-release invisible waterproof agent based on in-situ polymerized super-crosslinked polymer, which has high transparency, excellent waterproof property, excellent wear resistance and long-acting self-repairing function. According to the invention, graphene quantum dots are introduced into a