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CN-122011689-A - Flame-retardant epoxy resin composite material based on reactive dye interface modification and preparation method thereof

CN122011689ACN 122011689 ACN122011689 ACN 122011689ACN-122011689-A

Abstract

The application discloses a flame-retardant epoxy resin composite material based on reactive dye interface modification and a preparation method thereof, wherein 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is filled in mesoporous silica pore channels through the design thought of pore channel limiting load-surface reactivity blocking, and multi-reactive group reactive dye is utilized for surface functionalization modification, so that integrated flame-retardant pigment particles with flame retardance, coloring and reactivity functions are constructed, and the synergistic improvement of flame retardance, coloring stability and dispersion performance is realized.

Inventors

  • QU JIANGANG
  • JIANG CANYU
  • Shao Haonan

Assignees

  • 南通大学

Dates

Publication Date
20260512
Application Date
20260330

Claims (9)

  1. 1. The preparation method of the flame-retardant epoxy resin composite material based on reactive dye interface modification is characterized by comprising the following steps of: S1, dispersing hexadecyl trimethyl ammonium bromide in deionized water, adding a sodium hydroxide solution to adjust the pH value, stirring for 30min at 60-90 ℃, dropwise adding tetraethyl orthosilicate, reacting for 1-6 h, and centrifuging, washing and freeze-drying to obtain hexadecyl trimethyl ammonium bromide@mesoporous silica; s2, dispersing the hexadecyl trimethyl ammonium bromide@mesoporous silica in a mixed solution of ethanol and hydrochloric acid, removing hexadecyl trimethyl ammonium bromide through 2-3 times of solvent extraction at 60-80 ℃, and centrifuging, washing and freeze-drying to obtain mesoporous silica; S3, mixing the mesoporous silica with 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, stirring for 1-3 hours at 60-90 ℃ and 60-100 kPa, heating to 120-150 ℃ for reacting for 1-3 hours, washing with ethanol and water, centrifuging, and freeze-drying to obtain flame-retardant mesoporous silica; S4, dispersing the flame-retardant mesoporous silica in a mixed solution of ethanol and water, adding a silane coupling agent at the temperature of 30-70 ℃, reacting for 1-3 hours, and centrifuging, washing and freeze-drying to obtain modified flame-retardant mesoporous silica; S5, dispersing the modified flame-retardant mesoporous silica in ethanol, adding an aqueous solution of reactive dye at the temperature of 30-90 ℃, reacting for 1-3 hours, and centrifuging, washing and freeze-drying to obtain flame-retardant colored mesoporous silica; S6, taking a mixture of epoxy resin and a curing agent, pre-polymerizing for 10-30 min at 60-90 ℃, adding the flame-retardant color mesoporous silica, and continuously reacting for 10-30 min at 60-90 ℃ to obtain a flame-retardant color mesoporous silica@epoxy resin prepolymer; S7, pouring the flame-retardant colored mesoporous silica@epoxy resin prepolymer into a mold, and curing the prepolymer in an oven to obtain the flame-retardant epoxy resin composite material.
  2. 2. The method according to claim 1, wherein in the step S1, the dosage ratio of the hexadecyl trimethyl ammonium bromide to the sodium hydroxide to the tetraethyl orthosilicate to the deionized water is (0.3-0.6) g (0.1-0.3) g (3-6) mL and 480mL.
  3. 3. The method according to claim 1, wherein in the step S2, the dosage ratio of the hexadecyl trimethyl ammonium bromide and the mesoporous silica to the ethanol to the hydrochloric acid is (0.5-1) g to 48mL (1-3) mL, and the solvent extraction time is 8-16 h.
  4. 4. The method according to claim 1, wherein in the step S3, the mass ratio of the mesoporous silica to the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1:1-3.
  5. 5. The method of claim 1, wherein in the step S4, the silane coupling agent is KH560 or KH550, the usage ratio of the mixed solution of the flame-retardant mesoporous silica and the silane coupling agent is (1-5) g (0.5-1) mL:50mL, and the volume ratio of the ethanol to the water in the mixed solution of the ethanol and the water is (1-30): 1.
  6. 6. The method according to claim 1, wherein in the step S5, the reactive dye is a double-reactive group reactive dye comprising reactive yellow 145, reactive red 195 or reactive blue 194, the concentration of the reactive dye aqueous solution is 150g/L, and the dosage ratio of the modified flame-retardant mesoporous silica to the ethanol to the reactive dye aqueous solution is (1-5) g to 50mL (1-5) mL.
  7. 7. The method according to claim 1, wherein in the step S6, the epoxy resin is e44 or e51 epoxy resin, the curing agent is amine curing agent, and the usage ratio of the flame-retardant color mesoporous silica to the epoxy resin to the curing agent is (0.5-5) g to 85g (5-15) g.
  8. 8. The method according to claim 1, wherein in step S7, the curing condition is 80 to 140 ℃ for 1 to 4 hours.
  9. 9. The composite material prepared and obtained by the preparation method of any one of claims 1-8 is characterized by comprising an epoxy resin matrix, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, a silane coupling agent, a reactive dye, a curing agent and flame-retardant colored mesoporous silica, wherein the epoxy resin accounts for 81.0% -93.9%, the curing agent accounts for 5.3% -14.9%, the mesoporous silica accounts for 0.1% -1.2%, the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide accounts for 0.2% -2.5%, the silane coupling agent accounts for 0.1% -1.05%, and the reactive dye accounts for 0.05% -0.7% by weight.

Description

Flame-retardant epoxy resin composite material based on reactive dye interface modification and preparation method thereof Technical Field The application belongs to the technical field of polymer composite materials, and particularly relates to a flame-retardant epoxy resin composite material based on reactive dye interface modification and a preparation method thereof. Background Epoxy resins occupy a central role in the fields of coating, electronic packaging, aerospace composite materials and the like due to their excellent mechanical properties, strong adhesion, chemical corrosion resistance and electrical insulation. However, its inherent flammability, as well as the problem of easily releasing a large amount of smoke and producing droplets during combustion, severely limits its application in high-end fields where flame retardance is a requirement. To overcome this disadvantage, the prior art has often employed the modification of epoxy resins by the addition of flame retardants. Among them, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and its derivatives are considered as efficient flame retardant modifiers for epoxy resins because they can exert dual flame retarding mechanisms of gas phase and condensed phase simultaneously by virtue of high phosphorus content, excellent thermal stability and the like. However, DOPO, as a small molecule flame retardant, is susceptible to migration and volatilization when directly added to an epoxy resin matrix, and has limited compatibility with the matrix, resulting in difficulty in ensuring long-term flame retardant effect and stability of the material. Aiming at the problem that the small molecular flame retardant is easy to migrate, researchers introduce a porous material for loading. Mesoporous silica is an ideal carrier because of its high specific surface area, good thermal stability and regular pore structure. The liquid flame retardant or the phase-change flame retardant can be effectively loaded by a vacuum auxiliary dipping method. At present, although research is attempted to introduce mesoporous silica loaded with flame retardant into epoxy resin, the method often leads to agglomeration of nano particles, uneven dispersion in a matrix, and further stress concentration is caused, so that the mechanical property of the composite material is obviously reduced. Meanwhile, with the improvement of the requirements of the market on the color diversity of the coating, the defect of single color of the epoxy resin coating is increasingly highlighted. Reactive dyes, while bright in color, often suffer from the problems of stability affected by interaction of the dye with the flame retardant, formulation complexity and cost rise caused by multi-component systems when compounded with flame retardant systems. The reactive dye with multiple reactive groups can be combined with mesoporous silica through a silane coupling agent, and simultaneously the reactive dye is added into a prepolymer of epoxy resin for simultaneous curing, and residual reactive groups after the reaction can be subjected to a crosslinking reaction with the curing agent or the epoxy resin, so that the dispersion uniformity of particles in the epoxy resin can be greatly improved by virtue of formed covalent bonds. However, the current research focuses on the single synthesis of flame-retardant particles, the multifunctional integration and the simplification of the synthesis process are not fully considered, meanwhile, the synthesized particles do not have reactive groups and cannot be combined with epoxy resin, the particles are easily agglomerated due to Van der Waals force, the mechanical properties of the epoxy resin are further damaged, and part of the research adopts liquid flame retardant to stir and load at normal temperature, so that the efficiency is low, and meanwhile, the liquid phase is easier to leak compared with the phase-change flame retardant. Taking the prior patent as an example, CN103788408A discloses a DOPO modified inorganic flame retardant and a preparation method thereof, the invention combines DOPO and silicon dioxide by taking a silica coupling agent as a bridge, and the prepared flame retardant material has better flame retardant property and mechanical property when being applied to glass fiber, but the synthesis process is complicated, the heat treatment time is too long, so that the flame retardant material does not have color flame retardant integration and economic benefit. Meanwhile, the particles do not have groups which react with epoxy resin, the particles are easy to agglomerate in the curing process of the epoxy resin, and further the dispersion performance is influenced, CN120441988A discloses a flame-retardant modified ABS plastic and a preparation method thereof, a synthesized metal organic framework ZIF-67 of the flame-retardant modified ABS plastic has a complete pore structure, and a flame-retardant material is synthesized by continuously