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CN-122011750-A - Low-smoke halogen-free flame-retardant high-temperature nylon composite material and preparation method thereof

CN122011750ACN 122011750 ACN122011750 ACN 122011750ACN-122011750-A

Abstract

The invention discloses a low-smoke halogen-free flame-retardant high-temperature nylon composite material which comprises, by weight, 58.4-98.4 parts of high-temperature nylon, 20-30 parts of glass fibers, 13-15.5 parts of diethyl aluminum hypophosphite, 1-3 parts of Ti 3 C 2 T x (MXene) flame-retardant synergist, 0.5-1 part of silane coupling agent, 0.1-0.5 part of internal lubricating heat stabilizer, 0.2-0.5 part of compound antioxidant and 0.4-1.2 parts of lubricant. The invention prepares the low-smoke halogen-free flame-retardant high-temperature nylon composite material by modifying Ti 3 C 2 T x with a silane coupling agent and compounding with ADP, the ADP leads the flame retardant grade to be increased from UL 94V-2 to V1, the oxygen index is obviously improved, the total heat release amount is reduced, after adding modified Ti 3 C 2 T x , the flame retardant reaches V0 when adding 13 parts of ADP, the oxygen index is continuously improved, and the total smoke generation amount is obviously reduced. The two-dimensional lamellar carbon layer blocks oxygen, adsorbs volatile matters, is flame-retardant in cooperation with ADP, keeps heat resistance and mechanical properties, solves the problems of inflammability, dripping ignition and dense smoke, and meets the requirements of safety and environmental protection.

Inventors

  • RAO DESHENG
  • CHEN YUNFENG
  • Chen Ruoken
  • TANG NING

Assignees

  • 广东奇德新材料股份有限公司

Dates

Publication Date
20260512
Application Date
20260325

Claims (10)

  1. 1. The low-smoke halogen-free flame-retardant high-temperature nylon composite material is characterized by comprising, by weight, 58.4 parts to 98.4 parts of high-temperature nylon, 20 parts to 30 parts of glass fibers, 13 parts to 15.5 parts of diethyl aluminum hypophosphite, 1 part to 3 parts of Ti 3 C 2 T x (MXene) flame-retardant synergist, 0.5 part to 1 part of silane coupling agent, 0.1 part to 0.5 part of internal lubricating heat stabilizer, 0.2 part to 0.5 part of compound antioxidant and 0.4 part to 1.2 parts of lubricant; The Ti 3 C 2 T x (MXene) flame retardant synergist is prepared through an etching reaction step and a product treatment and dispersion liquid preparation step.
  2. 2. The low smoke zero halogen flame retardant high temperature nylon composite material according to claim 1, wherein, Dissolving 16 g lithium fluoride (LiF) in 320 mL 9M hydrochloric acid (HCl), stirring for 30: 30 min until the solution is completely dissolved, slowly adding 50: 50 g Ti 3 AlC 2 into the mixed solution in 10: 10 min, stirring for 20: 20 min at room temperature, transferring to a 40 ℃ oil bath, continuously stirring for reaction for 24: 24h, enabling LiF and HCl to react to generate HF, selectively etching to remove an Al layer, obtaining a multilayer Ti 3 C 2 T x containing a surface functional group-T x , adding a large amount of deionized water/ethanol mixed solution after the reaction is finished, standing for 12: 12 h, removing supernatant after the product is settled, neutralizing the supernatant with an excessive Ca (OH) 2 solution, and repeating the process of adding water/ethanol, standing for 3 times for removing soluble impurities to finally obtain a multilayer Ti 3 C 2 T x (MXene) agglomerated precipitate product; The preparation method comprises the steps of carrying out centrifugal washing on the collected Ti 3 C 2 T x (MXene) agglomerated precipitate product for a plurality of times by using a large amount of deionized water until the pH value of upper liquid after centrifugation is close to 6, adding ethanol with the mass 4 times that of the product into the product, carrying out pulse ultrasonic treatment for 1 hour by using an ultrasonic cell disruption instrument, wherein the ultrasonic frequency is 20 kHz and the power is 320W, stripping, then centrifuging (1500 rpm and 5 min) to collect the upper liquid, obtaining Ti 3 C 2 T x (MXene) flame retardant synergist, and finally preparing the Ti 3 C 2 T x (MXene) flame retardant synergist solution with the mass 15 mg/ml and refrigerating for standby.
  3. 3. The low smoke zero halogen flame retardant high temperature nylon composite of claim 1, wherein the high temperature nylon is PA6T-66 or PA10T.
  4. 4. The low smoke zero halogen flame retardant high temperature nylon composite of claim 1 wherein the lubricant is one of polyethylene wax, montan wax, ester wax, silicone.
  5. 5. The low smoke zero halogen flame retardant high temperature nylon composite of claim 1, wherein the silane coupling agent is one of KH-550, KH-560, KH-570.
  6. 6. The low smoke zero halogen flame retardant high temperature nylon composite material according to claim 1, wherein the compound antioxidant is two or more of 626, 9228, GA-80, 1098, 1010, 1790.
  7. 7. The low-smoke halogen-free flame-retardant high-temperature nylon composite material of claim 6, wherein the compound antioxidant is prepared by compounding 9228 and 1098 according to a mass ratio of 1:1.
  8. 8. The low smoke zero halogen flame retardant high temperature nylon composite of claim 1 wherein the glass fiber is 10 micron thai mountain chopped glass fiber 301-HP.
  9. 9. A method of preparing a low smoke, halogen-free, flame retardant, high temperature nylon composite according to any one of claims 1-8, comprising the steps of: 1) Adding diethyl aluminum hypophosphite (ADP) into a Ti 3 C 2 T x (MXene) flame retardant synergist solution, adding the Ti 3 C 2 T x (MXene) flame retardant synergist solution and a silane coupling agent KH-560 accounting for 1-wt% of the total mass of the diethyl aluminum hypophosphite, performing ultrasonic dispersion (power 320W, 30 min), removing ethanol solvent in the Ti 3 C 2 T x (MXene) flame retardant synergist solution by rotary evaporation, and drying in a vacuum oven at 60 ℃ for 24 h to obtain a silane modified ADP/Ti 3 C 2 T x mixture; 2) Mixing materials, namely drying high-temperature nylon resin at 130 ℃ for 4 h, mixing the high-temperature nylon resin with the silane modified ADP/Ti 3 C 2 T x mixture, an internal lubricating heat stabilizer, a compound antioxidant and a lubricant in a high-speed mixer at room temperature, stirring for 5-10 min to be uniformly dispersed at the rotating speed of 600-800 rpm; 3) And (3) melt extrusion molding, namely adding the mixed materials into a double-screw extruder with the length-diameter ratio of 48:1, melt extruding, adding glass fibers from a side feeding port, controlling the melting temperature to be 290-320 ℃ and the screw rotating speed to be 200-500 rpm, and cooling, air-drying, granulating and sieving the extrudate to obtain the halogen-free flame-retardant high-temperature nylon composite material.
  10. 10. The low-smoke halogen-free flame-retardant high-temperature nylon composite material according to claim 9, wherein water cooling is adopted for cooling, the cooling water temperature is 20-30 ℃, the cooling time is 1-3 minutes, the surface moisture is removed by air drying through air flow blowing, the air speed is 2-5m/s, the granulating is adopted for rotary granulating cutters, the granulating length is 2-4mm, and a 20-40 mesh screen is adopted for sieving to remove overlong or overlong particles.

Description

Low-smoke halogen-free flame-retardant high-temperature nylon composite material and preparation method thereof Technical Field The invention relates to the technical field of nylon composite materials, in particular to a low-smoke halogen-free flame-retardant high-temperature nylon composite material and a preparation method thereof. Background The current electronic and electric appliance and automobile industry continuously promote the requirements of high performance and light weight of products, and the plastic substitution process of metal parts is being accelerated. Under the background, the heat-resistant polyamide material has excellent heat resistance, hydrolysis resistance, chemical corrosion resistance, good fluidity and molding stability by virtue of the unique molecular structure advantage of the heat-resistant polyamide material, namely, by introducing aromatic groups to form varieties such as PA6T copolymer and PA9T, PA T, not only meets the severe requirements of SMT connectors, engine peripheral parts and the like on high-temperature environments, but also continuously expands the application field, and the market scale is rapidly expanded accordingly, so that the heat-resistant polyamide material becomes one of key engineering plastics for replacing metals. However, the molecular chain of the high-temperature resistant nylon is mainly based on the structural characteristic of a carbon chain, so that the intrinsic flame retardant performance of the nylon is insufficient, the Limiting Oxygen Index (LOI) is low, the vertical combustion grade can only reach UL 94V 2, obvious potential safety hazards exist in practical application (secondary fire disaster is caused by easy melting and dripping after ignition), and a large amount of dense smoke is released in the combustion process. Although the traditional halogen flame retardant can realize high-efficiency flame retardance and has small damage to the mechanical properties of materials, a large amount of dense smoke is still generated during combustion, and the traditional halogen flame retardant is subjected to increasingly strict regulation and elimination of market demands. Therefore, the technical bottlenecks of halogen-free flame retardance and smoke suppression modification of high-temperature-resistant nylon are broken through, and the problems of flammability, dripping ignition and dense smoke release are synchronously solved on the basis of maintaining the original heat resistance, mechanical property and other core properties of the material, so that the dual requirements of the high-end manufacturing field on safety and environmental friendliness are met. Disclosure of Invention The invention aims to provide a low-smoke halogen-free flame-retardant high-temperature nylon composite material and a preparation method thereof, and aims to solve the problems in the background technology. In order to achieve the above purpose, the present invention provides the following technical solutions: The low-smoke halogen-free flame-retardant high-temperature nylon composite material consists of, by weight, 58.4 parts to 98.4 parts of high-temperature nylon, 20 parts to 30 parts of glass fibers, 13 parts to 15.5 parts of diethyl aluminum hypophosphite, 1 part to 3 parts of Ti 3C2Tx (MXene) flame-retardant synergist, 0.5 part to 1 part of silane coupling agent, 0.1 part to 0.5 part of internal lubricating heat stabilizer, 0.2 part to 0.5 part of compound antioxidant and 0.4 part to 1.2 part of lubricant; The Ti 3C2Tx (MXene) flame retardant synergist is prepared through an etching reaction step and a product treatment and dispersion liquid preparation step. Further, the etching reaction step comprises the steps of dissolving 16 g lithium fluoride (LiF) in 320 mL 9M hydrochloric acid (HCl), stirring for 30: 30min until the solution is completely dissolved, then slowly adding 50: 50 g Ti 3AlC2 into the mixed solution in 10: 10min, stirring for 20: 20min at room temperature, transferring to a 40 ℃ oil bath, continuously stirring for reaction for 24: 24 h, enabling LiF and HCl to react to generate HF, selectively etching to remove an Al layer, obtaining a multilayer Ti 3C2Tx containing a surface functional group-T x, adding a large amount of deionized water/ethanol mixed solution after the reaction is finished, standing for 12: 12h, removing supernatant after the product is settled, neutralizing the supernatant with excessive Ca (OH) 2 solution, and repeating the process of adding water/ethanol-standing-settling-removing supernatant for 3 times to finally obtain a multilayer Ti 3C2Tx (MXene) agglomerate precipitate product; The preparation method comprises the steps of carrying out centrifugal washing on the collected Ti 3C2Tx (MXene) agglomerated precipitate product for a plurality of times by using a large amount of deionized water until the pH value of upper liquid after centrifugation is close to 6, adding ethanol with the mass 4 times that of the