Search

CN-121991501-A - High-wear-resistance halogen-free fireproof composite material and preparation method thereof

CN121991501ACN 121991501 ACN121991501 ACN 121991501ACN-121991501-A

Abstract

The invention relates to the technical field of high polymer materials, and discloses a high-wear-resistance halogen-free fireproof composite material and a preparation method thereof. The high wear-resistant halogen-free fireproof composite material comprises, by weight, 40-60 parts of PA9T, 6-10 parts of a modified flame retardant, 8-12 parts of carbon fibers, 0.5-1 part of an antioxidant, 1-3 parts of a wear-resistant powder, 1-2 parts of a compatilizer and 1-3 parts of modified lignin. The modified flame retardant provided by the invention endows the material with halogen-free environment-friendly and flame-retardant characteristics through the synergistic effect of phosphorus, nitrogen and boron elements, and the modified lignin improves the compatibility with nylon through hydrophobic modification, and meanwhile, the modified lignin has excellent wear resistance and mechanical properties, and the service life of the material is prolonged.

Inventors

  • CAO HONGXING

Assignees

  • 东莞拓步特高分子材料有限公司

Dates

Publication Date
20260508
Application Date
20260104

Claims (10)

  1. 1. The high wear-resistant halogen-free fireproof composite material is characterized by comprising, by weight, 40-60 parts of PA9T, 6-10 parts of modified flame retardant, 8-12 parts of carbon fiber, 0.5-1 part of antioxidant, 1-3 parts of wear-resistant powder, 1-2 parts of compatilizer and 1-3 parts of modified lignin; the modified flame retardant is prepared by the following steps: Step A1, mixing pentaerythritol and phosphorus oxychloride, stirring for 1.5 hours at 60 ℃ under the protection of nitrogen, heating to 105 ℃, carrying out reflux reaction for 10 hours, and carrying out reduced pressure distillation and vacuum drying after the reaction is finished to obtain an intermediate product 1; Step A2, mixing the intermediate product 1 and N, N-dimethylformamide, placing the mixture in an oil bath environment, heating to 80 ℃, stirring for 10min, adding 3, 5-diamino-1, 2, 4-triazole, reacting for 6h, and after the reaction is finished, carrying out vacuum filtration, washing and vacuum drying to obtain an intermediate product 2; And A3, mixing the 4-formylphenylboric acid, the intermediate product 2 and absolute ethyl alcohol, stirring, heating to 80 ℃ under the protection of nitrogen, carrying out reflux reaction for 2 hours, and filtering, washing and vacuum drying after the reaction is finished to obtain the modified flame retardant.
  2. 2. The high wear-resistant halogen-free fireproof composite material according to claim 1, wherein the dosage ratio of pentaerythritol to phosphorus oxychloride in the step A1 is 0.8-1mol:4-5mol.
  3. 3. The high wear-resistant halogen-free fireproof composite material according to claim 1, wherein the dosage ratio of the intermediate product 1, N-dimethylformamide and 3, 5-diamino-1, 2, 4-triazole in the step A2 is 0.5-0.7mol:150-200mL:0.95-1.35mol.
  4. 4. The high wear-resistant halogen-free fireproof composite material according to claim 1, wherein the dosage ratio of the 4-formylphenylboronic acid to the intermediate product 2 to the absolute ethanol in the step A3 is 0.2-0.4mol:0.1-0.2mol:150-200mL.
  5. 5. The high wear resistant halogen-free fire resistant composite of claim 1 wherein the modified lignin is prepared by the steps of: Step B1, adding 1-adamantanecarboxylic acid, 1, 2-epoxydodecane and tetrahydrofuran into a polymerization tube, sealing the polymerization tube after liquid nitrogen freezing-vacuumizing-nitrogen introducing-thawing three times, and reacting for 20 hours at 70 ℃ to obtain an adamantane derivative; Step B2, mixing the adamantane derivative and epoxy chloropropane, heating to 90 ℃, adding tetramethyl ammonium bromide, heating to 100 ℃ for reaction for 6 hours, then cooling to room temperature, adding 3wt% sodium hydroxide aqueous solution, stirring for 1 hour, washing with deionized water, separating, and distilling under reduced pressure to obtain the epoxyadamantane derivative; And B3, mixing the enzymatic hydrolysis lignin and N, N-dimethylformamide, heating to 100 ℃, then adding an epoxyadamantane derivative and 1, 8-diazabicyclo [5.4.0] undec-7-ene, stirring and reacting for 24 hours in a nitrogen atmosphere, cooling to room temperature, dropwise adding acetic acid and stirring for 5 minutes, dropwise adding the acetic acid into methanol and precipitating under stirring, washing with methanol for 2 times, washing with deionized water for 2 times, and freeze-drying to obtain the modified lignin.
  6. 6. The high wear-resistant halogen-free fireproof composite material according to claim 5, wherein the dosage ratio of 1-adamantanecarboxylic acid, 1, 2-epoxydodecane and tetrahydrofuran in the step B1 is 0.3-0.5mol:0.3-0.5mol:100-150mL.
  7. 7. The high wear-resistant halogen-free fireproof composite material according to claim 5, wherein the dosage ratio of adamantane derivative, epichlorohydrin, tetramethylammonium bromide, sodium hydroxide aqueous solution and deionized water in the step B2 is 0.1-0.3mol:0.5-1.5mol:2-6mmol:4.5-13.5 mL/100 mL.
  8. 8. The high wear-resistant halogen-free fireproof composite material according to claim 5, wherein the amount ratio of lignin, N-dimethylformamide, an epoxyadamantane derivative, 1, 8-diazabicyclo [5.4.0] undec-7-ene, acetic acid, methanol and deionized water used in the step B3 is 10g:50-60mL:0.03-0.04mol:0.003-0.004mol:12-14mL:400 mL.
  9. 9. The high wear-resistant halogen-free fireproof composite material according to claim 1, wherein the carbon fiber is chopped carbon fiber with the diameter of 0.4-0.9 microns, the antioxidant is one of antioxidant 1010, antioxidant 1076 and antioxidant 168, the wear-resistant powder is one of nano silicon dioxide, alumina and calcium carbonate, and the compatilizer is maleic anhydride grafted polyethylene.
  10. 10. A method of preparing the high wear resistant halogen-free fire resistant composite material of any one of claims 1-9, wherein the high wear resistant halogen-free fire resistant composite material is prepared by the steps of: s1, weighing raw materials in parts by weight, drying PA9T in a dehumidifying dryer at 100 ℃ for 7 hours, and controlling the moisture to be less than 0.03% for later use; And S2, adding the PA9T, the modified lignin, the compatilizer and the antioxidant into an extruder through a main feeding port, adding the carbon fiber into the extruder through a first side feeding port, adding the modified flame retardant and the wear-resistant powder into the extruder through a second side feeding port, and carrying out melt blending, cooling, air drying and granulating at 280-350 ℃ to obtain the high wear-resistant halogen-free fireproof composite material.

Description

High-wear-resistance halogen-free fireproof composite material and preparation method thereof Technical Field The invention relates to the technical field of high polymer materials, in particular to a high-wear-resistance halogen-free fireproof composite material and a preparation method thereof. Background With the development of industrial automation and new energy equipment, the service environment of the material is strict, and wear resistance and fire resistance are required to be considered. The working condition of parts in the fields of mechanical transmission and the like is complex, the traditional rubber is short in wear resistance and poor in flame retardance, halogen flame retardant plastics are burnt to release toxicity, and the surface hardness and the wear resistance are difficult to meet the heavy-load friction requirement. Among many engineering nylon materials, PA9T (poly (nonylenediamine) is a typical representative of semi-aromatic nylon, and by virtue of its unique molecular structural design, it becomes a preferred material that combines severe working condition adaptability with processing convenience. Compared with the traditional general nylon and other aromatic nylon, the PA9T has the advantages of outstanding heat resistance, better processing compatibility and remarkable low water absorption, and the balance matching of the rigid benzene ring and the flexible methylene chain in the molecular chain ensures that the PA9T not only has high strength and high toughness, but also forms a wear-resistant microstructure due to good crystallization regularity. In the current research, how to realize the cooperative promotion of the flame retardant property and the wear resistance is still a core difficult problem, the addition of partial flame retardant can reduce the crystallinity and the interfacial binding force of the material, so that the wear resistance is reduced, and the wear-resistant filler with high filling quantity can interfere the dispersion of the flame retardant and the exertion of the flame retardant mechanism. Therefore, developing composite materials with excellent fireproof safety and long-acting wear resistance has become a key support for safety upgrading in the fields of high-end equipment manufacturing, rail transit and the like. The patent with application number CN201210128140.8 discloses an antibacterial flame-retardant nylon composite material, tetrabromobisphenol A is used as a flame retardant, so that the flame retardant property of the nylon composite material is improved, but the halogen-containing flame retardant has health hidden danger after long-term contact and can be decomposed in the environment to generate toxic derivatives, and the use of the nylon composite material is limited in many areas at present. The patent with the application number of CN201210411329.8 discloses a composite environment-friendly flame retardant for nylon 6 and nylon 6 flame retardant plastic, and the obtained composite environment-friendly flame retardant can improve the flame retardant property of nylon 6 by mixing the flame retardants such as dimethyl trimethylsilyl methylphosphonate, melamine cyanurate, antimony trioxide and the like, but the multi-component compound flame retardant not only improves the preparation cost, but also has higher addition amount and possibly reduces the mechanical property of nylon materials. Disclosure of Invention In order to solve the technical problems, the invention provides a high-wear-resistance halogen-free fireproof composite material and a preparation method thereof. The aim of the invention can be achieved by the following technical scheme: the high wear-resistant halogen-free fireproof composite material comprises, by weight, 40-60 parts of PA9T, 6-10 parts of a modified flame retardant, 8-12 parts of carbon fibers, 0.5-1 part of an antioxidant, 1-3 parts of a wear-resistant powder, 1-2 parts of a compatilizer and 1-3 parts of modified lignin; The carbon fiber is chopped carbon fiber with the diameter of 0.4-0.9 microns; The antioxidant is one of an antioxidant 1010, an antioxidant 1076 and an antioxidant 168; the wear-resistant powder is one of nano silicon dioxide, aluminum oxide and calcium carbonate; The compatilizer is maleic anhydride grafted polyethylene; the modified flame retardant is prepared by the following steps: Step A1, mixing pentaerythritol and phosphorus oxychloride, stirring for 1.5 hours at 60 ℃ under the protection of nitrogen, heating to 105 ℃, carrying out reflux reaction for 10 hours, and carrying out reduced pressure distillation and vacuum drying after the reaction is finished to obtain an intermediate product 1; further, the dosage ratio of pentaerythritol to phosphorus oxychloride is 0.8-1mol:4-5mol; In the step A1, the pentaerythritol and phosphorus oxychloride are subjected to phosphorylation reaction, the introduced phosphoryl provides reaction conditions for the subsequent phosphorylation reaction,