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CN-121975392-A - Long-acting protective antibacterial paint with intelligent response and synergistic defense and preparation method thereof

CN121975392ACN 121975392 ACN121975392 ACN 121975392ACN-121975392-A

Abstract

The invention discloses a long-acting protective antibacterial coating for intelligent response and cooperative defense and a preparation method thereof, belonging to the technical field of special coating for ships and ocean engineering; the intelligent functional microsphere has a core-shell structure, the inner core of the intelligent functional microsphere is titanium aluminum lithium phosphate particles, the outer shell of the intelligent functional microsphere is an anchoring layer, an environment response gel layer and a self-repairing protective layer which are sequentially coated on the surface of the inner core, the environment response gel layer is loaded with a functional reagent and can release the functional reagent in response to the change of the pH value, the hydrogen peroxide concentration or the temperature of the environment, the intelligent protective coating design strategy with novel structure and integrated functions is provided, and the novel material solution is provided for the long-acting surface protection in the fields of high-end equipment, ocean engineering and the like by accurately regulating and controlling the multi-scale structure of materials.

Inventors

  • Chen Kengun
  • XIANG JUNMING
  • YOU CHUANQI
  • DU XIAOBO
  • LIU LI
  • YAO JINDI
  • FENG HAOCHEN
  • Peng Qiuwu
  • ZHANG BAOYUE
  • ZHANG MIAO
  • FENG TONGJUN
  • WANG QIANG
  • Gan Limei
  • Liu Xiaozimo
  • GAO MANKE

Assignees

  • 海南电网有限责任公司海口变电运检分公司

Dates

Publication Date
20260505
Application Date
20260205

Claims (10)

  1. 1. The intelligent response and synergistic defense long-acting protective antibacterial coating is characterized by comprising matrix resin and intelligent functional microspheres dispersed in the matrix resin, wherein the intelligent functional microspheres are of a core-shell structure, the inner core of the intelligent functional microspheres is titanium aluminum lithium phosphate particles, the outer shell of the intelligent functional microspheres is an anchoring layer, an environment response gel layer and a self-repairing protective layer which are sequentially coated on the surface of the inner core, the environment response gel layer is loaded with a functional reagent, and the functional reagent can be released in response to the change of the pH value, the hydrogen peroxide concentration or the temperature of the environment.
  2. 2. The coating of claim 1, wherein the anchoring layer comprises a polymer having catechol groups and reactive amine groups at the ends thereof bonded to the surface of the lithium aluminum titanium phosphate particles by covalent and coordination bonds, the environmentally responsive gel layer is a crosslinked copolymer network of monomers including N-isopropylacrylamide and 3-acrylamidophenylboronic acid, the self-healing protective layer is a polymer layer crosslinked by dynamic metal coordination bonds, and the functional agent includes an antimicrobial agent and an anti-uv agent.
  3. 3. The coating of claim 2, wherein the dynamic metal coordination bond is a coordination bond formed by a zinc ion and an imidazole group, the antimicrobial agent is iodopropynyl butyl carbamate, and the anti-ultraviolet agent is 2-amino-9, 10-diphenyl anthracene.
  4. 4. The coating according to claim 1, wherein the matrix resin is an aqueous epoxy resin and is matched with an aqueous amine curing agent matched with the matrix resin; The paint comprises, by mass, 20-30 parts of intelligent functional microspheres, 3-8 parts of scaly zinc powder, 70-80 parts of aqueous epoxy resin emulsion and paint auxiliary agents with the total amount of 3.9-4.5 parts, wherein the viscosity of the paint is adjusted to 80 KU-100 KU by using water.
  5. 5. The coating of claim 4, wherein the coating aid comprises a wetting dispersant, a film forming aid, a rheology aid, and a defoamer.
  6. 6. A method for preparing a coating according to any one of claims 1 to 5, wherein the method comprises the steps of preparing intelligent functional microspheres and preparing intelligent protective coating, wherein the preparation of the intelligent functional microspheres comprises the following steps: S1, constructing an inner anchoring layer, namely carrying out surface pretreatment on titanium aluminum lithium phosphate particles, then reacting the titanium aluminum lithium phosphate particles with an anchoring coupling agent containing catechol groups and active amine groups, and grafting the titanium aluminum lithium phosphate particles to form a molecular brush on the surfaces of the titanium aluminum lithium phosphate particles to obtain LATP-Anchor; S2, constructing an intermediate environment response Gel layer, namely coating a layer of polymer Gel layer capable of responding to pH value, hydrogen peroxide concentration or temperature change on the surface of the LATP-Anchor through polymerization and crosslinking reaction, and loading a functional reagent to obtain LATP-Anchor-Gel-F; s3, constructing an outer self-repairing protective layer, namely coating a polymer layer crosslinked through dynamic metal coordination bonds on the surface of the LATP-Anchor-Gel-F to obtain the intelligent functional microsphere.
  7. 7. The preparation method of the titanium aluminum phosphate particles according to claim 6, wherein in the step S1, the surface pretreatment is carried out by adopting a dilute hydrochloric acid solution with the concentration of 0.8 mol/L-1.2 mol/L, etching the titanium aluminum phosphate particles at the temperature of 55 ℃ to 65 ℃, and the anchoring coupling agent is a product generated by amidation reaction of 3, 4-dihydroxybenzene propionic acid and polyetheramine.
  8. 8. The method of manufacturing according to claim 6, wherein step S2 comprises the sub-steps of: S21, synthesizing a double-response copolymer, namely copolymerizing N-isopropyl acrylamide, 3-acrylamidophenylboronic acid and glycidyl methacrylate under the action of ammonium persulfate to obtain the double-response copolymer; s22, in-situ crosslinking to construct a Gel layer, namely dispersing the LATP-Anchor in the dual-response copolymer system, adding a crosslinking agent glutaraldehyde, and reacting under the condition that the pH value is 9.0-10.0 to form a hydrogel coating layer to obtain LATP-Anchor-Gel; S23, post-functionalization of the hydrogel layer, namely bonding an antibacterial agent and an anti-ultraviolet agent, namely 2-amino-9, 10-diphenyl anthracene, into a network structure after the LATP-Anchor-Gel is redispersed through a chemical reaction, wherein the antibacterial agent is iodopropynyl butyl carbamate, and the anti-ultraviolet agent is 2-amino-9, 10-diphenyl anthracene.
  9. 9. The method of manufacturing according to claim 6, wherein step S3 comprises the sub-steps of: S31, constructing an interface transition layer, namely grafting gamma-aminopropyl triethoxysilane on the surface of the LATP-Anchor-Gel-F to form an amino transition layer; S32, coordination encapsulation, namely dispersing the particles subjected to interface treatment into polyurethane solution with imidazole groups on side chains, adding ethanol solution of zinc acetate, and performing crosslinking encapsulation through dynamic coordination bonds between zinc ions and the imidazole groups.
  10. 10. The method of claim 6, wherein the intelligent protective coating formulation comprises the steps of: S41, pre-dispersing, namely mixing intelligent functional microspheres, scaly zinc powder, a wetting dispersant, a defoaming agent and water, and dispersing at a high speed for 20-30 min at a rotating speed of 1200-1500 r/min to obtain pre-dispersed slurry; S42, paint mixing, namely mixing the pre-dispersed slurry with the aqueous epoxy resin emulsion, the film forming auxiliary agent, the rheological auxiliary agent and the defoamer for 15-20 min at 400-500 r/min; S43, adjusting the viscosity, namely adding water, adjusting the viscosity of the mixture to 80 KU-100 KU, standing and curing for 20-30 min after the viscosity reaches the standard; S44, curing, namely adding a matched aqueous amine curing agent, and stirring for 3-5 min at 300-400 r/min to obtain the coating.

Description

Long-acting protective antibacterial paint with intelligent response and synergistic defense and preparation method thereof Technical Field The invention belongs to the technical field of special paint for ships and ocean engineering, and particularly relates to a long-acting protective antibacterial paint with intelligent response and synergistic defense and a preparation method thereof. Background The protective coating plays a vital role in the fields of ocean engineering, ship manufacturing, coastal infrastructure, chemical equipment and the like, and has the core functions of preventing corrosive media from corroding a substrate and prolonging the service life of a structure. Traditional epoxy and zinc-rich coatings rely mainly on passive protection mechanisms of physical shielding or sacrificial anodes, are difficult to provide continuous and active protection after the coatings are damaged or local corrosion is started, and generally lack response capability to specific environmental threats such as microbial corrosion. In recent years, researchers have tried to impart intelligent properties to coatings by adding corrosion inhibitors, antibacterial agents or self-repairing microcapsules, etc. to improve their protective efficacy and durability. However, the prior art often suffers from problems of single function, slow response or insufficient long-acting performance, such as that the physically doped active substances are easy to release or lose too early to realize on-demand supply, a single stimulus response system is difficult to adapt to complex corrosion scenes of multifactor coupling in marine environment, and the static crosslinked coating in the prior art lacks self-repairing capability after being damaged, so that the protective performance is irreversibly reduced. In addition, how to achieve stable loading, synergy and long-lasting maintenance of various functional components in the coating remains a technical difficulty in the art. Therefore, the intelligent protective coating which can integrate multiple functions of environment sensing, triggering release, cooperative corrosion inhibition and autonomous repair is developed, so that the intelligent protective coating can realize long-acting, self-adaptive and multi-level comprehensive defense in a practical severe environment, and has important significance for improving the reliability and full life cycle economy of important engineering equipment and facilities. Disclosure of Invention The invention aims to overcome the technical limitations of single function, slow response, poor long-acting performance, insufficient self-repairing capability and the like of the existing protective coating in coping with complex corrosion environments, and provides the long-acting protective antibacterial coating with intelligent response and cooperative defense and the preparation method. The technical scheme adopted by the invention is as follows: The intelligent response and synergistic defense long-acting protective antibacterial coating is characterized by comprising matrix resin and intelligent functional microspheres dispersed in the matrix resin, wherein the intelligent functional microspheres are of a core-shell structure, the inner core of the intelligent functional microspheres is titanium aluminum lithium phosphate particles, the outer shell of the intelligent functional microspheres is an anchoring layer, an environment response gel layer and a self-repairing protective layer which are sequentially coated on the surface of the inner core, the environment response gel layer is loaded with a functional reagent, and the functional reagent can be released in response to the change of the pH value, the hydrogen peroxide concentration or the temperature of the environment. Further, the anchoring layer comprises a polymer which is combined with the surface of the titanium aluminum lithium phosphate particles through covalent bonds and coordination bonds and contains catechol groups and active amine groups at the tail end, the environment response gel layer is a cross-linked copolymer network, monomers of the environment response gel layer comprise N-isopropyl acrylamide and 3-acrylamide phenylboric acid, the self-repairing protective layer is a polymer layer which is cross-linked through dynamic metal coordination bonds, and the functional agent comprises an antibacterial agent and an anti-ultraviolet agent. Further, the dynamic metal coordination bond is a coordination bond formed by zinc ions and imidazole groups, the antibacterial agent is iodopropynyl butyl carbamate, and the anti-ultraviolet agent is 2-amino-9, 10-diphenyl anthracene. Specifically, the matrix resin is aqueous epoxy resin and is matched with an aqueous amine curing agent matched with the matrix resin; The paint comprises, by mass, 20-30 parts of intelligent functional microspheres, 3-8 parts of scaly zinc powder, 70-80 parts of aqueous epoxy resin emulsion and paint auxiliar