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CN-120775459-B - Flame-retardant self-repairing wood epoxy coating and preparation method and application thereof

CN120775459BCN 120775459 BCN120775459 BCN 120775459BCN-120775459-B

Abstract

The invention discloses a flame-retardant and self-repairing wood epoxy coating and a preparation method and application thereof, and belongs to the technical field of epoxy resins. The preparation method comprises the steps of (1) uniformly mixing vanillin, epoxy chloropropane and tetrabutylammonium bromide, reacting, cooling, dropwise adding an aqueous solution of NaOH, continuing the reaction, washing, drying, precipitating, drying again to obtain the bio-based epoxy resin for standby, (2) uniformly mixing methanol and hydrochloric acid, heating, condensing and refluxing, adding gamma-aminopropyl triethoxysilane, reacting, cooling, adding tetrahydrofuran, washing, vacuum drying to obtain cage-type polysilsesquioxane, and (3) dissolving the cage-type polysilsesquioxane in an organic solvent, adding the bio-based epoxy resin, uniformly stirring, standing and solidifying to obtain the product. According to the invention, the vanillin is used for constructing the epoxy resin containing the imine bond, so that the self-repairing and excellent flame retardant performance of the epoxy resin are realized.

Inventors

  • SHI JUNYOU
  • WEN MINGYU
  • LIANG YUQING
  • XU WENBIAO
  • Lv Linxi
  • ZHAO XUEFENG
  • Yang Xujiao
  • JIANG TIANYAO

Assignees

  • 山东理工大学
  • 北华大学

Dates

Publication Date
20260508
Application Date
20250718

Claims (7)

  1. 1. The preparation method of the flame-retardant and self-repairing wood epoxy coating is characterized by comprising the following steps of: (1) Uniformly mixing vanillin, epichlorohydrin and tetrabutylammonium bromide, reacting, cooling, dropwise adding an aqueous solution of NaOH, continuing the reaction, washing, drying, precipitating, and drying again to obtain the bio-based epoxy resin for later use; The mass fraction of the NaOH aqueous solution is 50 percent, and the mass ratio of the vanillin to the epichlorohydrin to the tetrabutylammonium bromide to the NaOH aqueous solution is 20:48.8:1:26.4; (2) Mixing methanol and hydrochloric acid uniformly, heating, condensing and refluxing, adding gamma-aminopropyl triethoxysilane, reacting, cooling, adding tetrahydrofuran, washing, and vacuum drying to obtain cage polysilsesquioxane; the volume ratio of the methanol to the hydrochloric acid to the gamma-aminopropyl triethoxysilane to the tetrahydrofuran is 100:15:15.2:200; (3) Dissolving cage-type polysilsesquioxane in an organic solvent, adding bio-based epoxy resin, uniformly stirring, standing, and solidifying to obtain the flame-retardant and self-repairing wood epoxy coating; the organic solvent is methanol, and the mass ratio of the cage-type polysilsesquioxane to the organic solvent to the bio-based epoxy resin is 16 (80-160) to 100.
  2. 2. The method for preparing the flame-retardant and self-repairing wood epoxy coating according to claim 1, wherein in the step (1), the reaction temperature is 80 ℃, the time is 2 hours, the dropwise adding time is 15 minutes, and the continuous reaction temperature is 16 ℃ and the time is 3 hours.
  3. 3. The method for preparing the flame-retardant and self-repairing wood epoxy coating according to claim 1, wherein in the step (1), the washed reagent is deionized water, the dried reagent is anhydrous magnesium sulfate, the precipitated reagent is petroleum ether, and the re-drying temperature is 80 ℃ and the time is 2 hours.
  4. 4. The method for preparing the flame-retardant and self-repairing wood epoxy coating according to claim 1, wherein in the step (2), the temperature of the reaction is 90 ℃ and the time is 18 hours, the washing reagent is absolute ethyl alcohol, and the temperature of the vacuum drying is 40 ℃.
  5. 5. The method for preparing the flame-retardant and self-repairing wood epoxy coating according to claim 1, wherein in the step (3), the stirring time is 30min, and the curing procedure is that the curing is carried out at 80 ℃ for 2h and at 120 ℃ for 4h.
  6. 6. A flame retardant and self healing wood epoxy coating made by the method of any one of claims 1-5.
  7. 7. Use of the flame retardant and self healing wood epoxy coating prepared by the method of any one of claims 1-5 in the protection of wood materials.

Description

Flame-retardant self-repairing wood epoxy coating and preparation method and application thereof Technical Field The invention relates to the technical field of epoxy resin, in particular to a flame-retardant and self-repairing wood epoxy coating, and a preparation method and application thereof. Background Natural lumber has been used for construction materials, fuel and furniture because of its versatility, renewable and aesthetic appeal. However, wood is easily burned, constituting a risk to asset and human safety. The fireproof paint is coated on the surface of wooden material to raise fireproof performance. However, the traditional petroleum-based epoxy resin has the problems of non-reproducibility, environmental hazard and the like. Therefore, how to develop a novel wood epoxy coating is a problem that needs to be solved by those skilled in the art. Disclosure of Invention In view of the above, the invention aims to provide a flame-retardant and self-repairing wood epoxy coating, and a preparation method and application thereof, so as to solve the defects in the prior art. In order to achieve the above purpose, the present invention adopts the following technical scheme: The preparation method of the flame-retardant and self-repairing wood epoxy coating comprises the following steps: (1) Uniformly mixing vanillin, epichlorohydrin and tetrabutylammonium bromide, reacting, cooling, dropwise adding an aqueous solution of NaOH, continuing the reaction, washing, drying, precipitating, and drying again to obtain bio-based epoxy resin (VE) for later use; (2) Mixing methanol and hydrochloric acid uniformly, heating, condensing and refluxing, adding gamma-aminopropyl triethoxysilane (KH-550), reacting, cooling, adding tetrahydrofuran, washing, and vacuum drying to obtain cage-type polysilsesquioxane (OA-POSS); (3) Dissolving cage-type polysilsesquioxane in an organic solvent, adding bio-based epoxy resin, stirring uniformly, standing, and solidifying to obtain the flame-retardant and self-repairing wood epoxy coating (VE/OA-POSS). Further, in the step (1), the mass fraction of the NaOH aqueous solution is 50wt%, and the mass ratio of the vanillin, the epichlorohydrin, the tetrabutylammonium bromide and the NaOH aqueous solution is 20:48.8:1:26.4. The method has the further beneficial effects that the vanillin is derived from the derivative of the lignin of the wood, belongs to biomass raw materials, is taken from the wood, is used for the wood, and realizes recycling. Further, in the step (1), the reaction temperature was 80℃for 2 hours, the dropwise addition time was 15 minutes, and the reaction was continued at 16℃for 3 hours. Further, in the step (1), the washed reagent is deionized, the dried reagent is anhydrous magnesium sulfate, the precipitated reagent is petroleum ether, and the re-drying temperature is 80 ℃ and the time is 2 hours. Further, in the step (2), the volume ratio of the methanol, the hydrochloric acid, the gamma-aminopropyl triethoxysilane and the tetrahydrofuran is 100:15:15.2:200. Further, in the step (2), the reaction temperature is 90 ℃ and the reaction time is 18 hours, the washed reagent is absolute ethanol, and the vacuum drying temperature is 40 ℃. In the step (3), the organic solvent is methanol, and the mass ratio of the cage-type polysilsesquioxane to the organic solvent to the bio-based epoxy resin is 16 (80-160): 100. The preparation method has the further beneficial effects that the biological-based epoxy resin (VE) and the curing agent cage-type polysilsesquioxane (OA-POSS) are used for constructing a thermosetting biological-based flame-retardant epoxy resin crosslinking system, a small amount of methanol is taken as a solvent, and the mixture is uniformly mixed and then is left stand for standby, wherein each 100g of VE corresponds to 16g of OA-POSS (namely, each 1g of VE needs 0.16g of OA-POSS). Wherein the volume of methanol is 5-10 times of the mass of OA-POSS, such as 80-160mL of methanol is added into 16g of OA-POSS. Further, in the step (3), stirring time is 30min, and the curing procedure is that 80 ℃ is cured for 2h and 120 ℃ is cured for 4h. The invention also discloses the flame-retardant and self-repairing wood epoxy coating prepared by the preparation method. The invention also claims the application of the flame-retardant and self-repairing wood epoxy coating prepared by the preparation method in wood material protection. Compared with the prior art, the invention has the following beneficial effects: according to the invention, the vanillin is used for constructing the epoxy resin containing the imine bond, so that the self-repairing and excellent flame retardant performance of the epoxy resin are realized. Drawings FIG. 1 is a synthetic route diagram of VE/OA-POSS; FIG. 2 is a FTIR diagram of VE (a) and VE/OA-POSS (b); FIG. 3 is a 1 H NMR chart of VE; FIG. 4 is a DSC curve of E-51/DDM (a) and VE/OA-POSS (b) at a ramp rate of 5-25 ℃ per minute and fitted curv