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CN-122011361-A - Phosphorus-containing flame-retardant nano fluid and preparation method and application thereof

CN122011361ACN 122011361 ACN122011361 ACN 122011361ACN-122011361-A

Abstract

The invention belongs to the technical field of flame retardance of polymer composite materials, and particularly discloses a preparation method of a phosphorus-containing flame retardance nano fluid, which comprises the following steps of uniformly mixing a neck-shaped layer coupling agent and a crown-shaped layer flexible polymer chain according to a proportion, vacuumizing and introducing nitrogen for multiple times to remove water and oxygen, bonding an organic functional group of the coupling agent with a terminal functional group of the flexible polymer chain, and completing a preliminary grafting reaction to obtain a solvent-free grafted polymer intermediate; the preparation method comprises the steps of carrying out surface functionalization treatment on the flame-retardant nano-cores to obtain functionalized flame-retardant nano-cores, uniformly dispersing the functionalized flame-retardant nano-cores in hydrolysate prepared by alcohol and water according to a proportion, adding dilute acid to adjust pH to obtain dispersion, adding the dispersion into a solvent-free grafted polymer intermediate, reacting to obtain a crude product of the phosphorus-containing flame-retardant nano-fluid, carrying out dialysis purification on the obtained crude product of the phosphorus-containing flame-retardant nano-fluid, filtering, rotary evaporating, concentrating and drying the reaction liquid after dialysis purification to obtain the phosphorus-containing flame-retardant nano-fluid.

Inventors

  • ZHAO XIAOMIN
  • GUO XIANXIN
  • LI XIANG
  • LI ZIMENG
  • HE TING
  • He Luoqi
  • XU XIAODONG

Assignees

  • 华侨大学

Dates

Publication Date
20260512
Application Date
20260414

Claims (10)

  1. 1. The preparation method of the phosphorus-containing flame-retardant nano fluid is characterized by comprising the following steps of: (1) Uniformly mixing a neck-shaped layer coupling agent and a crown-shaped layer flexible polymer chain according to a proportion, vacuumizing, introducing nitrogen for multiple times to remove water and oxygen, and carrying out grafting reaction for 3-24 hours at 60-110 ℃ to bond an organic functional group of the coupling agent with a terminal functional group of the flexible polymer chain, so as to complete a preliminary grafting reaction and obtain a solvent-free grafted polymer intermediate; (2) Performing surface functionalization treatment on the phosphorus-containing flame-retardant nano-core to obtain a functionalized phosphorus-containing flame-retardant nano-core; (3) Uniformly dispersing the functionalized phosphorus-containing flame-retardant nano-cores obtained in the step (2) in a mixed solvent prepared by alcohol and water according to a proportion, adding dilute acid to adjust the pH to obtain a dispersion liquid, and then adding the dispersion liquid into the solvent-free grafted polymer intermediate obtained in the step (1) to react to obtain a crude product of the phosphorus-containing flame-retardant nano-fluid; (4) Dialyzing and purifying the crude product of the phosphorus-containing flame-retardant nano fluid obtained in the step (3) for 48-96 hours; (5) And (3) filtering, rotary evaporating, concentrating and drying the reaction liquid after dialysis and purification in the step (4) to obtain the phosphorus-containing flame-retardant nano fluid, wherein the rotary evaporating, concentrating and drying temperature is 40-70 ℃ and the time is 0.5-5 h.
  2. 2. The method for preparing the phosphorus-containing flame-retardant nano fluid according to claim 1, wherein the neck-shaped layer coupling agent in the step (1) is one of an epoxy group-containing silane coupling agent, an amino group-containing silane coupling agent, a quaternary ammonium salt type silane coupling agent and a sulfonic acid group silane coupling agent, and the crown-shaped layer flexible polymer chain is one of polyetheramine, dimethyl octadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride, sodium nonylphenol polyoxyethylene ether sulfate, polyphosphite, polyalkyl (C1-C6) phosphonate, polyarylphosphonate, poly (2-carboxyethyl phenyl phosphinate), polyalkyl (C1-C6) borate and polyarylborate.
  3. 3. The method for preparing a phosphorus-containing flame-retardant nano-fluid according to claim 1, wherein the molar ratio of the neck-shaped layer coupling agent to the crown-shaped layer flexible polymer chain in the step (1) is (0.2-1.5): 1.
  4. 4. The method for preparing a phosphorus-containing flame-retardant nano-fluid according to claim 1, wherein the phosphorus-containing flame-retardant nano-core in the step (2) is one of aluminum phosphinate, zinc phosphinate, calcium phosphinate, magnesium phosphinate, aluminum diethylphosphinate, calcium diethylphosphinate, magnesium diethylphosphinate, zinc diethylphosphinate, aluminum diethylphenylphosphinate, aluminum dipropylphosphinate, aluminum isobutylphosphinate, aluminum methylethylphosphinate, zinc methylbutylphosphinate, zinc methylphenyl phosphinate, iron methylphosphinate, aluminum phenylphosphinate, ammonium polyphosphate, aluminum phosphate, zinc phosphate, iron phosphate, copper phosphate and cobalt phosphate.
  5. 5. The method for preparing a phosphorus-containing flame-retardant nano-fluid according to claim 1, wherein the surface functionalization treatment mode in the step (2) is one of hydrogen peroxide oxidation, alkaline piranha solution oxidation, hydrogen peroxide reflux, ultraviolet excitation and plasma treatment.
  6. 6. The method for preparing the phosphorus-containing flame-retardant nano fluid according to claim 1, wherein the volume ratio of alcohol to water in the mixed solvent in the step (3) is (8-10): 1, and the alcohol is one of isopropanol, ethylene glycol, methanol and ethanol.
  7. 7. The method for preparing a phosphorus-containing flame-retardant nano fluid according to claim 1, wherein in the step (3), the pH is 3-6, and the pH is adjusted by one of acetic acid, dilute hydrochloric acid and dilute sulfuric acid.
  8. 8. The method for preparing a phosphorus-containing flame-retardant nano-fluid according to claim 1, wherein the mass ratio of the functionalized phosphorus-containing flame-retardant nano-core to the mixed solvent in the step (3) is 1 (50-150), and the mass ratio of the dispersion liquid to the solvent-free grafted polymer intermediate is 1-2.
  9. 9. A phosphorus-containing flame-retardant nano-fluid prepared by the method for preparing a phosphorus-containing flame-retardant nano-fluid according to any one of claims 1 to 8.
  10. 10. Use of the phosphorous-containing flame retardant nano-class fluid according to claim 9.

Description

Phosphorus-containing flame-retardant nano fluid and preparation method and application thereof Technical Field The invention belongs to the technical field of flame retardance of polymer composite materials, and particularly relates to a phosphorus-containing flame retardance nano fluid, a preparation method and application thereof. Background Epoxy resin (EP) is used as an important thermosetting polymer material, and has been widely applied to the key fields of aerospace, automobile manufacturing, electronic appliances, constructional engineering and the like by virtue of excellent mechanical strength, chemical corrosion resistance and electrical insulation property. However, the epoxy resin has the defect of low inherent thermal decomposition temperature, so that the epoxy resin is easy to burn in a high-temperature environment, and a large amount of smoke is released in the burning process, and the problem severely restricts the application expansion of the epoxy resin in a high-end flame-retardant requirement scene. Therefore, development of efficient and environment-friendly flame-retardant modification technology has become one of the core directions in the research field of epoxy resin functionalization modification. The nanoparticle has unique surface effect, volume effect, quantum size effect and macroscopic quantum tunneling effect, and can regulate and control the matrix performance through physical or chemical interaction with the polymer matrix, so that the nanoparticle/polymer composite material has excellent mechanical performance, photoelectric performance, thermal stability and flame retardance, and lays a solid foundation for the application of the nanoparticle/polymer composite material in the high-end field. In the practical application process, however, the inorganic nano particles have two main core application bottlenecks, namely firstly, the inorganic nano particles are difficult to realize uniform dispersion in a polymer matrix and are easy to agglomerate to form micron-sized agglomerates so as to lose the special nano effect, and secondly, the interface binding force between the nano particles and the polymer matrix is weak, and the problem of obvious interface incompatibility exists, so that the toughness of the composite material is obviously reduced. The above drawbacks greatly limit the application potential of nanoparticle/polymer composites, and therefore there is a need to develop new modification techniques to break through this application dilemma. The nanometer fluid is used as a novel organic-inorganic hybrid material and has a typical core-shell binary structure, inorganic nano particles are usually used as cores, silane coupling agents and the like are used as core-shell interface connecting media, and the crown layer is formed by organic flexible long chains. The unique core-shell structure enables the inorganic nano core to be uniformly coated by the organic shell, so that van der Waals acting force among nano particles can be effectively weakened, the agglomeration phenomenon of the nano particles can be remarkably relieved, meanwhile, the inherent physicochemical properties of the nano particles can be completely reserved, high-quality raw materials are provided for preparing the functional composite material, and the nano-core composite material has important academic research value and wide industrial application prospect. At present, related exploration of phosphorus-containing flame-retardant nano fluid and a preparation method thereof exists, but the existing preparation process has the defects of poor dispersibility and coating effect, easy agglomeration of nano particles and loss of nano effect, harsh preparation conditions, unfriendly environment, difficult realization of industrialized mass production, difficult compromise of flame retardance and mechanical property cooperativity, complex process, higher cost and incapability of meeting high-end application requirements. Therefore, it is very necessary to develop a new preparation method of the phosphorus-containing flame-retardant nano fluid. Disclosure of Invention The invention aims to overcome the defects of the prior art, and provides a phosphorus-containing flame-retardant nano fluid, a preparation method and application thereof, wherein an organic molecular chain is utilized to carry out surface modification on a nano flame-retardant material, a core-shell structure phosphorus-containing flame-retardant nano fluid is constructed, the dispersion uniformity of the nano flame-retardant material in an epoxy resin matrix is improved, the problem of interfacial compatibility of a composite material is solved, and the controllable preparation of a multifunctional epoxy resin composite material with high flame retardant efficiency, excellent mechanical strength and high transparency is realized. In order to achieve the purpose, one of the technical schemes of the invention is that a preparation method of