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CN-122011507-A - Bio-based flame retardant toughening agent and preparation method and application thereof

CN122011507ACN 122011507 ACN122011507 ACN 122011507ACN-122011507-A

Abstract

The invention provides a bio-based flame retardant toughening agent, and a preparation method and application thereof. The preparation method comprises the steps of firstly preparing a bio-based intermediate AA by utilizing arginine and amino trimethylene phosphonic acid through ionic reaction, then reacting the AA and tannic acid in a water phase, controlling the hydroxyl content and the P/N ratio of a product through adjusting the mass ratio of the AA to the TA, preparing a flame retardant AT, and finally preparing the bio-based flame retardant toughening agent through solvent blending of the AT and an epoxy modifier. The bio-based flame retardant toughening agent prepared by the invention integrates flame retardant, toughening and reactive compatibilization functions, is introduced into a polylactic acid (PLA) matrix, realizes dynamic vulcanization through molecular-level synergistic integration of phenolic structures, realizes reactive compatibilization by using epoxy groups, and plays a role of P/N synergistic flame retardance. In conclusion, the defects of flammability and intrinsic brittleness of the polylactic acid composite material are effectively overcome, and the polylactic acid composite material has the advantages of green and renewable raw materials and good application prospect.

Inventors

  • SU JUANJUAN
  • LU JUN

Assignees

  • 浙江理工大学

Dates

Publication Date
20260512
Application Date
20260204

Claims (10)

  1. 1. The preparation method of the bio-based flame retardant toughening agent is characterized by comprising the following steps of: (1) Adding amino trimethylene phosphonic acid into the arginine water solution, uniformly stirring for reaction, and performing post-treatment to obtain a bio-based flame retardant AA; (2) Under the stirring condition, the bio-based flame retardant AA reacts with tannic acid in water, and after the reaction is finished, the flame retardant AT is obtained through post-treatment; (3) Under the stirring condition, the flame retardant AT and the epoxy modifier are subjected to solution blending in a solvent, and then are dried in vacuum, so that the bio-based flame retardant toughening agent is obtained.
  2. 2. The method for preparing the bio-based flame retardant toughening agent according to claim 1, wherein in the step (1), the molar ratio of arginine to aminotrimethylene phosphonic acid is controlled to be (1-6): 1-3; the reaction temperature is 20-80 ℃ and the reaction time is 2-6 h.
  3. 3. The preparation method of the bio-based flame retardant toughening agent according to claim 1, wherein in the step (2), the mass ratio of the bio-based flame retardant AA to tannic acid is (0.5-6): 1-2; the reaction temperature is 20-60 ℃ and the reaction time is 1-5 h.
  4. 4. The method of preparing a bio-based flame retardant toughening agent according to claim 1, wherein in the step (3), the solvent used for the solution blending is selected from one or more of acetone, chloroform, methylene chloride and toluene; The epoxy modifier is one or more selected from epoxidized soybean oil, triglycidyl isocyanurate, styrene-glycidyl methacrylate, glycidyl methacrylate and ethylene-methyl methacrylate-glycidyl methacrylate.
  5. 5. The preparation method of the bio-based flame retardant toughening agent according to claim 1, wherein in the step (3), the mass ratio of the flame retardant AT to the epoxy modifier is (1-4): 1-8; the reaction temperature is 20-40 ℃ and the reaction time is 5-30 min.
  6. 6. The method of preparing a bio-based flame retardant toughening agent according to claim 1, wherein in the steps (1) and (2), the post-treatment process is the same, specifically as follows: and (3) sequentially performing liquid nitrogen prefreezing and freeze drying on the reaction liquid to obtain the corresponding flame retardant.
  7. 7. A bio-based flame retardant toughening agent, characterized in that it is prepared by the preparation method of any one of claims 1to 6.
  8. 8. The high-strength flame-retardant toughened polylactic acid composite material is characterized by being prepared by melt blending polylactic acid and the bio-based flame-retardant toughening agent in claim 7.
  9. 9. The high-strength, flame-retardant and toughened polylactic acid composite material according to claim 8, which is characterized by being prepared from the following components in percentage by mass: The addition amount of the polylactic acid is 85-99%; The addition amount of the bio-based flame retardant toughening agent is 1-15%; and the sum of the mass percentages of the polylactic acid and the bio-based flame retardant toughening agent is 100 percent.
  10. 10. The high-strength flame-retardant toughened polylactic acid composite material according to claim 8, wherein the time of melt blending is 6-12 min, the temperature of melt blending is 160-200 ℃, and the rotational speed of melt blending is 50-80 rpm.

Description

Bio-based flame retardant toughening agent and preparation method and application thereof Technical Field The invention belongs to the technical field of flame retardance of high polymer materials, and particularly relates to a bio-based flame retardant toughening agent, a preparation method and application thereof. Background With the increasing importance of global environmental protection and sustainable development, the impact of plastic pollution on the ecological environment has attracted a great deal of attention. The development of biobased and biodegradable polymers is an effective approach to solve this problem. Polylactic acid (PLA) has been widely used in the fields of drug delivery, food packaging, textile industry, etc., as a typical bio-based degradable aliphatic polyester, by virtue of its good biocompatibility. However, the further application of polylactic acid in the engineering field is severely limited by the performance defect of the polylactic acid, namely, on one hand, the polylactic acid is extremely easy to burn and has a large fire safety hazard, and on the other hand, the polylactic acid shows extremely high intrinsic brittleness, the elongation at break is usually lower than 10 percent, and the notch impact strength is only about 3 kJ/m < 2 >. Therefore, the method overcomes the inflammability and brittleness defect of the polylactic acid while keeping the green and environment-friendly characteristics of the polylactic acid, and has important technical value for expanding the application range of the polylactic acid composite material. The existing polylactic acid (PLA) flame-retardant and toughening modification technology generally depends on a single traditional flame retardant (such as ammonium polyphosphate and APP), and lacks deep exploration of a multifunctional efficient synergistic system. However, the prior art has significant limitations in practical applications in that attempts to improve PLA flame retardancy and toughness are often accompanied by significant decreases in the tensile strength of the material. The reason for this is mainly that the interface compatibility between the flame retardant, the toughening phase and the PLA matrix is poor, so that stable interface bonding is difficult to form, and the mechanical property of the composite material is unbalanced. Therefore, how to integrate the flame retardant function and the toughening function into a synergistic system and realize the improvement of the comprehensive performance of the material on the premise of ensuring good compatibility with the PLA matrix is a technical problem to be solved in the field at present. Disclosure of Invention In order to solve the problems in the prior art, the invention provides a bio-based flame retardant toughening agent, a preparation method and application thereof, and the preparation method is environment-friendly, and a multifunctional additive integrating flame retardant, toughening and reactive compatibility functions is constructed by using bio-based raw materials. The invention provides a high-strength flame-retardant toughened polylactic acid composite material. By introducing the bio-based flame retardant toughening agent, the material effectively solves the defects of flammability and brittleness of polylactic acid, simultaneously remarkably improves the interface compatibility between the flame retardant toughening agent and a matrix, and overcomes the defect that the toughness and the flame retardant property are difficult to be compatible in the traditional modification. The preparation method disclosed by the invention is simple in procedure, mild in reaction condition and suitable for industrial production. A preparation method of a bio-based flame retardant toughening agent comprises the following steps: (1) Adding amino trimethylene phosphonic acid into the arginine water solution, uniformly stirring for reaction, and performing post-treatment to obtain a bio-based flame retardant AA; (2) Under the stirring condition, the bio-based flame retardant AA reacts with tannic acid in water, and after the reaction is finished, the flame retardant AT is obtained through post-treatment; (3) Under the stirring condition, the flame retardant AT and the epoxy modifier are subjected to solution blending in a solvent, and then are dried in vacuum, so that the bio-based flame retardant toughening agent is obtained. In the step (1): in the step, arginine (Ar) and amino trimethylene phosphonic Acid (ATMP) are subjected to ion exchange reaction in a water phase to prepare the phosphorus-nitrogen type flame retardant. Wherein, the arginine water solution is prepared by dissolving arginine in deionized water. Preferably, the molar ratio of arginine to amino trimethylene phosphonic acid is controlled to (1-6): 1-3. Further preferably 1 (0.5-3). Still more preferably 1:1. Preferably, the reaction temperature is 20 to 80 ℃. More preferably 30 to 60 ℃. Still more preferably 30