High-temperature-resistant long-carbon-chain bio-based nylon reinforced composite material and preparation method thereof

Abstract

The invention provides a high-temperature-resistant long-carbon-chain bio-based nylon reinforced composite material and a preparation method thereof, and belongs to the technical field of composite materials. Comprising the following steps: (1) adding long-chain diacid, aromatic diacid and diacid ionic liquid into water, raising the temperature, adding multi-branched amine, ammoniated nanoparticles and ammoniated graphene coated ceramic particles, controlling the temperature, and conveying pentamethylene diamine to obtain a reaction solution; and (2) replacing air in the reaction liquid with inert gas, raising the temperature to control the pressure, carrying out heat and pressure preservation reaction, reducing the pressure, continuing to raise the temperature, carrying out stirring reaction, vacuumizing, discharging, wiredrawing and pelletizing to prepare the high-temperature-resistant long-carbon-chain bio-based nylon reinforced composite material. The antistatic flame-retardant polypropylene composite material has the advantages of favorable mechanical properties, high temperature resistance, heat stability, flame retardancy, dyeing property, wear resistance, softness and the like, high heat conductivity, favorable antistatic property, obviously higher flame retardancy and wide application prospect.

Description

Technical Field

[0001] The present invention relates to the technical field of composite materials, and in particular to a high-temperature resistant long carbon chain bio-based nylon reinforced composite material and a preparation method thereof. Background Art

[0002] Nylon (polyamide) is the most widely used thermoplastic engineering plastic both domestically and internationally. It boasts excellent properties such as toughness, wear resistance, impact resistance, fatigue resistance, corrosion resistance, and oil resistance, making it widely used in automotive parts, electronics, and machinery. Flame-retardant nylon materials, particularly in automotive electronics and other fields, require flame retardancy, environmental protection, and health.

[0003] Among nylon chemical products, nylon 66 is a high-strength, heat-resistant and stable variety. It is a product made by the condensation of adipic acid and hexamethylenediamine, with a melting point of up to 260°C. However, there has been no breakthrough in the raw material hexamethylenediamine for the synthesis of PA66 in China, and most of the technologies are blocked by foreign patents and companies. At the same time, PA66 is a petroleum-based nylon product, and its synthesis requires a large amount of polymerization monomers from the petroleum industry. However, the consumption of petroleum resources and the increasingly serious environmental problems it brings are not in line with the concept of sustainable development and environmental protection. Therefore, the development of green and environmentally friendly nylon products is of great significance.

[0004] Bio-based long-chain nylon, typically made from bio-castor oil, boasts a short carbon footprint and environmental friendliness. It also features 10 or more methylene groups between adjacent amide groups, long methylene chains, and polar amide groups. However, nylon materials often suffer from poor heat resistance, thermal stability, and insufficient mechanical properties. Summary of the Invention

[0005] The purpose of the present invention is to provide a high-temperature resistant long-carbon-chain bio-based nylon reinforced composite material and a preparation method thereof, which has good mechanical properties, high-temperature resistance, thermal stability, flame retardancy, dyeing performance, wear resistance and softness, high thermal conductivity, good antistatic properties, significantly improved flame retardancy, and broad application prospects.

[0006] The technical solution of the present invention is achieved as follows: The present invention provides a method for preparing a high-temperature resistant long carbon chain bio-based nylon reinforced composite material, comprising the following steps: (1) adding a long-chain diacid, an aromatic diacid, and a diacid ionic liquid to water, raising the temperature, adding a multi-branched amine, aminated nanoparticles, and aminated graphene-coated ceramic particles, controlling the temperature, feeding pentamethylenediamine, detecting the pH value of the system, stopping feeding pentamethylenediamine, and obtaining a reaction solution; (2) The air in the reaction liquid is replaced with an inert gas, the temperature is increased, the pressure is controlled, the reaction is carried out under heat and pressure, the temperature is further increased under reduced pressure, the reaction is stirred, vacuumed, discharged, drawn, and pelletized to obtain a high-temperature resistant long-carbon-chain bio-based nylon reinforced composite material.

[0007] As a further improvement of the present invention, the mass ratio of the long-chain diacid, aromatic diacid, diacid ionic liquid, multi-branched amine, aminated nanoparticles, and aminated graphene-coated ceramic particles in step (1) is 10-15:2-4:1-3:3-5:2-3:1-3, the pH value of the system is 7.2-7.4, the temperature is increased to 60-65°C, and the controlled temperature is 60-70°C; the long-chain diacid is selected from at least one of 1,10-decanedioic acid, 1,11-undecanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, and 1,18-octadecanediol, and the aromatic diacid is selected from at least one of terephthalic acid, phthalic acid, isophthalic acid, and pyromellitic acid.

[0008] As a further improvement of the present invention, the preparation method of the polybranched amine is as follows: S1. Pentaerythritol was added to dichloromethane, followed by thionyl chloride. The reaction was stirred and the solvent and excess thionyl chloride were removed under reduced pressure to produce pentaerythritol tetrachloride, which has the following structure: ; S2. Pentaerythritol and ethylenediamine were added to acetonitrile, heated to reflux with stirring, and the solvent was removed under reduced pressure. The product was recrystallized from methanol, filtered, washed, and dried to obtain a polybranched amine having the following structure: .

[0009] As a further improvement of the present invention, the molar ratio of pentaerythritol to thionyl chloride in step S1 is 1:4-4.2, and the stirring reaction time is 1-2 hours; the molar ratio of pentaerythritol to ethylenediamine in step S2 is 1:4-4.1, and the heating reflux stirring reaction time is 4-8 hours.

[0010] As a further improvement of the present invention, the preparation method of the ammoniated nanoparticles is as follows: 8-12 parts by weight of aminosilane are dissolved in 120-150 parts by weight of ethanol, 3-7 parts by weight of concentrated hydrochloric acid and 5-8 parts by weight of water are added, the mixture is stirred for reaction for 8-12 hours, centrifuged, washed, and dried to obtain the ammoniated nanoparticles; The aminosilane is selected from at least one of γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane, N-β (aminoethyl)-γ-aminopropyltriethoxysilane, N-β (aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl)-γ-aminopropylmethyldiethoxysilane, and diethylenetriaminopropyltrimethoxysilane.

[0011] As a further improvement of the present invention, the structural formula of the diacid ionic liquid is shown in Formula I:

[0012] Formula I; Wherein, X = H2SO4, CH3SO3H, p-TsOH, CF3SO3H, CF3COOH.

[0013] As a further improvement of the present invention, the preparation method of the ammoniated graphene-coated ceramic particles is as follows: T1. Ball-mill the ceramic particles and sieve them to obtain ceramic powder; T2 graphene oxide was added to water, ceramic powder was added, stirred and mixed, and spray dried to obtain pleated graphene oxide-coated ceramic powder; T3. Add the pleated graphene oxide-coated ceramic powder to a Tris-HCl solution, add dopamine hydrochloride, heat and stir to react, filter, wash, and dry to obtain ammoniated graphene-coated ceramic particles.

[0014] As a further improvement of the present invention, the mesh size of the sieve sieved in step T1 is 100-200 mesh; the mass ratio of graphene oxide to ceramic powder in step T2 is 3-5:8-10; the pH value of the Tris-HCl solution in step T3 is 8.5-9.5, the mass ratio of the pleated graphene oxide-coated ceramic powder to dopamine hydrochloride is 10:3-4, and the temperature of the heating and stirring reaction is 45-55°C, and the time is 3-5h.

[0015] As a further improvement of the present invention, the temperature of the heating in step (2) is 210-230°C, the controlled pressure is 2-3 MPa, the heat and pressure maintaining reaction time is 2-4 hours, the temperature of the continued temperature increase is 240-260°C, and the stirring reaction time is 2-4 hours.

[0016] The present invention further protects a high-temperature resistant long-carbon-chain bio-based nylon reinforced composite material prepared by the above-mentioned preparation method.

[0017] The present invention has the following beneficial effects: In the preparation of bio-based nylon, this invention uses long-chain diacids, aromatic diacids, and diacid ionic liquids as diacids. Long-chain diacids can be obtained through biofermentation, replacing petrochemical monomers, reducing carbon emissions and addressing import dependence. Copolymerization of the aromatic diacids with diamines creates a structure of alternating rigid benzene rings and flexible chains, raising the glass transition temperature (Tg) and meeting long-term thermal aging requirements.

[0018] A special diacid ionic liquid is also added to the diacid of the present invention, which has a higher thermal decomposition temperature. Its introduction can keep the polymer stable in a wider temperature range and is not prone to thermal degradation, thereby improving the high temperature resistance of the polymer. At the same time, the ionic liquid monomer has a stable chemical property and is not easily oxidized, reduced, or undergoes other chemical reactions, which can significantly improve the chemical corrosion resistance of the polymer. The ionic liquid monomer is not easy to burn, and after being introduced into the polymer chain, its flame retardant properties can be significantly improved. In addition, the addition of the ionic liquid monomer can increase the interaction force between the polymer chains, such as electrostatic attraction, van der Waals forces, etc., so that the mechanical strength of the polymer is improved. Moreover, the ionic liquid monomer itself has good ionic conductivity and can form ion transmission channels inside the polymer, increase the migration rate of ions, thereby significantly improving the ionic conductivity of the polymer and having good antistatic properties.

[0019] The NH and C=O in the macromolecular chain of the high-temperature resistant long carbon chain bio-based nylon reinforced composite material prepared by the present invention are in a dislocated state. This special dislocated structure has high thermal stability at high temperatures. When the hydrogen bonds of the material dissociate at high temperatures, they may slide toward the macromolecular chain, and the original unsaturated hydrogen bonds will form new high-strength hydrogen bonds, thereby greatly improving the high-temperature resistance of the material. The prepared composite material has good mechanical properties, thermal stability, flame retardancy, dyeing properties, wear resistance and softness.

[0020] The present invention adds a polybranched amine, which is prepared into a branched amine structure and can react with a diacid to form a nylon material with a significantly improved cross-linking degree, so that a three-dimensional network structure is formed between polymer molecular chains, which can significantly enhance the high temperature resistance, mechanical properties and chemical stability of the polymer.

[0021] The present invention also uses ammoniated nanoparticles produced through a sol-gel reaction of aminosilane. These nanoparticles have nanoscale particle sizes and, due to their inherent structural characteristics such as ultra-small size and high surface area, possess higher surface activity. The nanopowders can act as nucleating agents, effectively improving the crystallization properties of nylon polymers and promoting hydrogen bond formation. Furthermore, they can significantly enhance the high-temperature resistance, mechanical properties, and flame retardancy of composite materials. The ammoniated graphene-coated ceramic particles prepared and added by the present invention have the characteristics of high strength, low resistance, high thermal conductivity, etc. due to their graphene structure. The amino group (-NH2), hydroxyl group (-OH) and carboxyl group (-COOH) thereof can form hydrogen bonds with the polymer, which can significantly improve the thermal conductivity and antistatic properties of the composite material. The ceramic particles have excellent thermal conductivity. At the same time, the amino group can also participate in the polymerization of the polymer, thereby improving the dispersibility of the material and will not affect the mechanical properties of the composite material.

[0022] The high-temperature resistant long carbon chain bio-based nylon reinforced composite material prepared by the present invention has good mechanical properties, high-temperature resistance, thermal stability, flame retardancy, dyeing performance, wear resistance and softness, etc., high thermal conductivity, good antistatic performance, significantly improved flame retardancy, and has broad application prospects. DETAILED DESCRIPTION

[0023] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0024] Graphene oxide, average thickness 5nm, oxygen content approximately 35%, average sheet diameter 20μm, brand: Xianfeng Nano.

[0025] The structural formula of diacid ionic liquid is as follows: , where X = H2SO4, CH3SO3H, p-TsOH, CF3SO3H, CF3COOH. Preparation method reference: Xie Jingxue, et al. Synthesis and spectral characterization of dual nucleic acid ionic liquids [J]. Liaoning Chemical Industry, 2024, 53 (9): 1391-1394.

[0026] Preparation Example 1 Preparation of polybranched amines Synthesis route:

[0027] Here’s how: S1. Add 0.1 mol of pentaerythritol to 200 mL of dichloromethane, then add 50 mL of a dichloromethane solution containing 0.4 mol of thionyl chloride. Stir and react for 1 hour. Remove the solvent and excess thionyl chloride under reduced pressure to obtain pentaerythritol. ESI-MS calculated value: C5H9Cl4 (M+H) + 208.94, found: 209.0, yield 90%.

[0028] NMR results: 1 H NMR (300MHz, CDCl3) δ3.32 (s, 8H).

[0029] S2. Add 0.1 mol of pentaerythritol and 0.4 mol of ethylenediamine to 200 mL of acetonitrile, heat under reflux and stir for 4 h, remove the solvent under reduced pressure, recrystallize from methanol, filter, wash, and dry to obtain a multibranched amine. ESI-MS calculated value: C 13 H 37 N8(M+H) +305.31, found: 305.3, yield 85%.

[0030] NMR results: 1 H NMR (300MHz, CDCl3) δ2.74-2.85 (m, 16H), 2.35 (s, 8H), 2.3 (br, 4H), 1.85 (br, 8H).

[0031] Preparation Example 2 Preparation of polybranched amines Here’s how: S1. Add 0.1 mol of pentaerythritol to 200 mL of dichloromethane, then add 50 mL of a dichloromethane solution containing 0.42 mol of thionyl chloride. Stir the mixture for 2 hours. Remove the solvent and excess thionyl chloride under reduced pressure to obtain pentaerythritol in a 92% yield.

[0032] S2. 0.1 mol of pentaerythritol and 0.41 mol of ethylenediamine were added to 200 mL of acetonitrile, and the mixture was heated under reflux with stirring for 8 h. The solvent was removed under reduced pressure, and the mixture was recrystallized with methanol, filtered, washed, and dried to obtain a polybranched amine in a yield of 88%.

[0033] Preparation Example 3 Preparation of polybranched amines Here’s how: S1. Add 0.1 mol of pentaerythritol to 200 mL of dichloromethane, then add 50 mL of a dichloromethane solution containing 0.41 mol of thionyl chloride. Stir the mixture for 1.5 hours. Remove the solvent and excess thionyl chloride under reduced pressure to obtain pentaerythritol in a yield of 91%.

[0034] S2. 0.1 mol of pentaerythritol and 0.405 mol of ethylenediamine were added to 200 mL of acetonitrile, and the mixture was heated under reflux with stirring for 6 h. The solvent was removed under reduced pressure, and the mixture was recrystallized with methanol, filtered, washed, and dried to obtain a polybranched amine in a yield of 87%.

[0035] Preparation Example 4 Preparation of Ammoniated Nanoparticles The method is as follows: 8 g of γ-aminopropyltrimethoxysilane is dissolved in 120 g of ethanol, 3 g of concentrated hydrochloric acid and 5 mL of water are added, the mixture is stirred for 8 h, centrifuged, washed, and dried to obtain ammoniated nanoparticles.

[0036] Preparation Example 5 Preparation of Ammoniated Nanoparticles The method is as follows: 12 g of N-β (aminoethyl) -γ-aminopropyltrimethoxysilane is dissolved in 150 g of ethanol, 7 g of concentrated hydrochloric acid and 8 mL of water are added, the mixture is stirred for 12 h, centrifuged, washed, and dried to obtain ammoniated nanoparticles.

[0037] Preparation Example 6 Preparation of Ammoniated Nanoparticles The method is as follows: 10 g of N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane is dissolved in 135 g of ethanol, 5 g of concentrated hydrochloric acid and 7 mL of water are added, stirred for 10 hours, centrifuged, washed, and dried to obtain ammoniated nanoparticles.

[0038] Preparation Example 7 Preparation of Ammoniated Graphene-Coated Ceramic Particles Here’s how: T1. The aluminum nitride ceramic particles were ball-milled and passed through a 100-mesh sieve to obtain aluminum nitride ceramic powder; T2 0.3g of graphene oxide was added to 100mL of water, 0.8g of aluminum nitride ceramic powder was added, stirred and mixed, and spray dried to obtain pleated graphene oxide-coated ceramic powder; T3. Add 10 g of pleated graphene oxide-coated ceramic powder to 200 mL of Tris-HCl solution (pH 8.5), add 3 g of dopamine hydrochloride, heat to 45°C, and stir for 3 h. Filter, wash, and dry to obtain ammoniated graphene-coated ceramic particles.

[0039] Preparation Example 8 Preparation of Ammoniated Graphene-Coated Ceramic Particles Here’s how: T1. The aluminum nitride ceramic particles were ball-milled and passed through a 200-mesh sieve to obtain aluminum nitride ceramic powder; T2 0.5g of graphene oxide was added to 100mL of water, 1g of aluminum nitride ceramic powder was added, stirred and mixed, and spray dried to obtain pleated graphene oxide-coated ceramic powder; T3. Add 10 g of pleated graphene oxide-coated ceramic powder to 200 mL of Tris-HCl solution (pH 9.5), add 4 g of dopamine hydrochloride, heat to 55°C, and stir for 5 h. Filter, wash, and dry to obtain ammoniated graphene-coated ceramic particles.

[0040] Preparation Example 9 Preparation of Ammoniated Graphene-Coated Ceramic Particles Here’s how: T1. The aluminum nitride ceramic particles were ball-milled and passed through a 150-mesh sieve to obtain aluminum nitride ceramic powder; T2 0.4g of graphene oxide was added to 100mL of water, 0.9g of aluminum nitride ceramic powder was added, stirred and mixed, and spray dried to obtain pleated graphene oxide-coated ceramic powder; T3. Add 10 g of pleated graphene oxide-coated ceramic powder to 200 mL of Tris-HCl solution (pH 9), add 3.5 g of dopamine hydrochloride, heat to 50°C, and stir for 4 h. Filter, wash, and dry to obtain ammoniated graphene-coated ceramic particles.

[0041] Comparative Preparation Example 1 Compared with Preparation Example 9, the difference is that step T2 is not performed.

[0042] The details are as follows: T1. The aluminum nitride ceramic particles were ball-milled and passed through a 150-mesh sieve to obtain aluminum nitride ceramic powder; T2. Add 10 g of aluminum nitride ceramic powder to 200 mL of Tris-HCl solution (pH 9), add 3.5 g of dopamine hydrochloride, heat to 50°C, and stir for 4 h. Filter, wash, and dry to obtain ammoniated ceramic particles.

[0043] Comparative Preparation Example 2 Compared with Preparation Example 9, the difference is that step T3 is not performed.

[0044] The details are as follows: T1. The aluminum nitride ceramic particles were ball-milled and passed through a 150-mesh sieve to obtain aluminum nitride ceramic powder; T2. Add 0.4 g of graphene oxide to 100 mL of water, then add 0.9 g of aluminum nitride ceramic powder. Stir and mix thoroughly. Spray dry to obtain pleated graphene oxide-coated ceramic powder.

[0045] Example 1 This embodiment provides a method for preparing a high-temperature resistant long carbon chain bio-based nylon reinforced composite material, comprising the following steps: (1) 10 g of 1,12-dodecane diacid, 2 g of terephthalic acid, and 1 g of diacid ionic liquid were added to 500 mL of water, the temperature was raised to 60° C., 3 g of the multibranched amine prepared in Preparation Example 1, 2 g of the ammoniated nanoparticles prepared in Preparation Example 4, and 1 g of the ammoniated graphene-coated ceramic particles prepared in Preparation Example 7 were added, the temperature was controlled at 60° C., pentamethylenediamine was supplied, the pH value of the system was detected to be 7.2, and the supply of pentamethylenediamine was stopped to obtain a reaction solution; (2) The air in the reaction liquid was replaced with nitrogen, the temperature was raised to 210 ° C, the pressure was controlled to 2 MPa, the temperature and pressure were kept constant for 2 h, the pressure was reduced and the temperature was continued to be raised to 240 ° C, the reaction was stirred for 2 h, vacuumed, discharged, drawn, and pelletized to obtain a high-temperature resistant long-carbon-chain bio-based nylon reinforced composite material.

[0046] Example 2 This embodiment provides a method for preparing a high-temperature resistant long carbon chain bio-based nylon reinforced composite material, comprising the following steps: (1) 15 g of 1,11-undecyl diacid, 4 g of isophthalic acid, and 3 g of diacid ionic liquid were added to 500 mL of water, the temperature was raised to 65° C., 5 g of the multibranched amine prepared in Preparation Example 2, 3 g of the ammoniated nanoparticles prepared in Preparation Example 5, and 3 g of the ammoniated graphene-coated ceramic particles prepared in Preparation Example 8 were added, the temperature was controlled at 70° C., pentamethylenediamine was supplied, the pH value of the detection system was 7.4, and the supply of pentamethylenediamine was stopped to obtain a reaction solution; (2) The air in the reaction liquid was replaced with nitrogen, the temperature was raised to 230 ° C, the pressure was controlled to 3 MPa, and the reaction was maintained at this temperature and pressure for 4 h. The temperature was further increased to 260 ° C under reduced pressure, and the reaction was stirred for 4 h. The reaction was vacuumed, discharged, drawn, and pelletized to obtain a high-temperature resistant long-carbon-chain bio-based nylon reinforced composite material.

[0047] Example 3 This embodiment provides a method for preparing a high-temperature resistant long carbon chain bio-based nylon reinforced composite material, comprising the following steps: (1) 12 g of 1,10-decanedioic acid, 3 g of phthalic acid, and 2 g of diacid ionic liquid were added to 500 mL of water, the temperature was raised to 62° C., 4 g of the multibranched amine prepared in Preparation Example 3, 2.5 g of the ammoniated nanoparticles prepared in Preparation Example 6, and 2 g of the ammoniated graphene-coated ceramic particles prepared in Preparation Example 9 were added, the temperature was controlled at 65° C., pentamethylenediamine was supplied, the pH value of the detection system was 7.3, and the supply of pentamethylenediamine was stopped to obtain a reaction solution; (2) The air in the reaction liquid was replaced with nitrogen, the temperature was raised to 220°C, the pressure was controlled at 2.5 MPa, and the reaction was carried out under heat and pressure for 3 hours. The temperature was further raised to 250°C under reduced pressure, and the reaction was stirred for 3 hours. The reaction was then vacuumed, discharged, drawn, and pelletized to obtain a high-temperature resistant long-carbon-chain bio-based nylon reinforced composite material.

[0048] Comparative Example 1 Compared with Example 3, the difference is that no diacid ionic liquid is added.

[0049] The details are as follows: (1) 14 g of 1,10-decanedioic acid and 3 g of phthalic acid were added to 500 mL of water, the temperature was raised to 62° C., 4 g of the multibranched amine prepared in Preparation Example 3, 2.5 g of the ammoniated nanoparticles prepared in Preparation Example 6, and 2 g of the ammoniated graphene-coated ceramic particles prepared in Preparation Example 9 were added, the temperature was controlled at 65° C., pentamethylenediamine was supplied, the pH value of the system was detected to be 7.3, the supply of pentamethylenediamine was stopped, and a reaction solution was obtained; (2) The air in the reaction liquid was replaced with nitrogen, the temperature was raised to 220°C, the pressure was controlled at 2.5 MPa, and the reaction was carried out under heat and pressure for 3 hours. The temperature was further raised to 250°C under reduced pressure, and the reaction was stirred for 3 hours. The reaction was then vacuumed, discharged, drawn, and pelletized to obtain a high-temperature resistant long-carbon-chain bio-based nylon reinforced composite material.

[0050] Comparative Example 2 The difference compared with Example 3 is that phthalic acid is not added.

[0051] The details are as follows: (1) 15 g of 1,10-decanedioic acid and 2 g of diacid ionic liquid were added to 500 mL of water, the temperature was raised to 62° C., 4 g of the multibranched amine prepared in Preparation Example 3, 2.5 g of the ammoniated nanoparticles prepared in Preparation Example 6, and 2 g of the ammoniated graphene-coated ceramic particles prepared in Preparation Example 9 were added, the temperature was controlled at 65° C., pentamethylenediamine was supplied, the pH value of the system was detected to be 7.3, and the supply of pentamethylenediamine was stopped to obtain a reaction solution; (2) The air in the reaction liquid was replaced with nitrogen, the temperature was raised to 220°C, the pressure was controlled at 2.5 MPa, and the reaction was carried out under heat and pressure for 3 hours. The temperature was further raised to 250°C under reduced pressure, and the reaction was stirred for 3 hours. The reaction was then vacuumed, discharged, drawn, and pelletized to obtain a high-temperature resistant long-carbon-chain bio-based nylon reinforced composite material.

[0052] Comparative Example 3 Compared with Example 3, the difference is that no polybranched amine is added.

[0053] The details are as follows: (1) 12 g of 1,10-decanedioic acid, 3 g of phthalic acid, and 2 g of diacid ionic liquid were added to 500 mL of water, the temperature was raised to 62° C., 2.5 g of the aminated nanoparticles prepared in Preparation Example 6 and 2 g of the aminated graphene-coated ceramic particles prepared in Preparation Example 9 were added, the temperature was controlled at 65° C., pentamethylenediamine was supplied, the pH value of the system was detected to be 7.3, and the supply of pentamethylenediamine was stopped to obtain a reaction solution; (2) The air in the reaction liquid was replaced with nitrogen, the temperature was raised to 220°C, the pressure was controlled at 2.5 MPa, and the reaction was carried out under heat and pressure for 3 hours. The temperature was further raised to 250°C under reduced pressure, and the reaction was stirred for 3 hours. The reaction was then vacuumed, discharged, drawn, and pelletized to obtain a high-temperature resistant long-carbon-chain bio-based nylon reinforced composite material.

[0054] Comparative Example 4 Compared with Example 3, the difference is that no ammoniated nanoparticles are added.

[0055] The details are as follows: (1) 12 g of 1,10-decanedioic acid, 3 g of phthalic acid, and 2 g of diacid ionic liquid were added to 500 mL of water, the temperature was raised to 62° C., 4 g of the multibranched amine prepared in Preparation Example 3 and 2 g of the ammoniated graphene-coated ceramic particles prepared in Preparation Example 9 were added, the temperature was controlled at 65° C., pentamethylenediamine was supplied, the pH value of the detection system was 7.3, and the supply of pentamethylenediamine was stopped to obtain a reaction solution; (2) The air in the reaction liquid was replaced with nitrogen, the temperature was raised to 220°C, the pressure was controlled at 2.5 MPa, and the reaction was carried out under heat and pressure for 3 hours. The temperature was further raised to 250°C under reduced pressure, and the reaction was stirred for 3 hours. The reaction was then vacuumed, discharged, drawn, and pelletized to obtain a high-temperature resistant long-carbon-chain bio-based nylon reinforced composite material.

[0056] Comparative Example 5 Compared with Example 3, the difference is that no ammoniated graphene-coated ceramic particles are added.

[0057] The details are as follows: (1) 12 g of 1,10-decanedioic acid, 3 g of phthalic acid, and 2 g of diacid ionic liquid were added to 500 mL of water, the temperature was raised to 62° C., 4 g of the multibranched amine prepared in Preparation Example 3 and 2.5 g of the aminated nanoparticles prepared in Preparation Example 6 were added, the temperature was controlled at 65° C., pentamethylenediamine was supplied, the pH value of the system was detected to be 7.3, and the supply of pentamethylenediamine was stopped to obtain a reaction solution; (2) The air in the reaction liquid was replaced with nitrogen, the temperature was raised to 220°C, the pressure was controlled at 2.5 MPa, and the reaction was carried out under heat and pressure for 3 hours. The temperature was further raised to 250°C under reduced pressure, and the reaction was stirred for 3 hours. The reaction was then vacuumed, discharged, drawn, and pelletized to obtain a high-temperature resistant long-carbon-chain bio-based nylon reinforced composite material.

[0058] Comparative Example 6 Compared with Example 3, the difference is that no ammoniated graphene-coated ceramic particles are added and replaced by the product prepared in Comparative Preparation Example 1 of equal mass.

[0059] Comparative Example 7 Compared with Example 3, the difference is that no ammoniated graphene-coated ceramic particles are added and replaced by the product prepared in Comparative Preparation Example 2 of equal mass.

[0060] Sufficient test samples were prepared according to the methods in the Examples or Comparative Examples for testing.

[0061] Test Example 1 The performance of the high-temperature resistant long carbon chain bio-based nylon reinforced composite materials prepared in Examples 1-3 and Comparative Examples 1-7 was tested. The results are shown in Table 1.

[0062] The tensile properties were tested according to ISO 527 at a tensile rate of 5 mm / min.

[0063] Bending strength is tested according to ISO178, speed 2.0mm / min; Izod notched impact strength is tested according to ISO179; The flame retardant performance is carried out according to UL-94, and the flame retardant grades are HB, V2, V1, and V0 respectively.

[0064] HDT (Heat Deflection Temperature): Conducted on an HDT apparatus (EDIT). Method A (1.8 MPa) was used. The specimen (4 mm thick) was placed flat on a substrate (distance between supports = 64 mm). The heating rate was 120°C / h. Surface resistivity: Tested according to ASTM D257 at a temperature of 23°C and a relative humidity of 50 ± 5%. Table 1

[0065] It can be seen from the above table that the high-temperature resistant long carbon chain bio-based nylon reinforced composite materials prepared in Examples 1-3 of the present invention have good comprehensive properties.

[0066] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing a high-temperature resistant long carbon chain bio-based nylon reinforced composite material, characterized in that: The following steps are involved: (1) adding a long-chain diacid, an aromatic diacid, and a diacid ionic liquid to water, raising the temperature, adding a multi-branched amine, aminated nanoparticles, and aminated graphene-coated ceramic particles, controlling the temperature, feeding pentamethylenediamine, detecting the pH value of the system, stopping feeding pentamethylenediamine, and obtaining a reaction solution; (2) The air in the reaction liquid is replaced with an inert gas, the temperature is increased, the pressure is controlled, the reaction is carried out under heat and pressure, the temperature is further increased under reduced pressure, the reaction is stirred, vacuumed, discharged, drawn, and pelletized to obtain a high-temperature resistant long-carbon-chain bio-based nylon reinforced composite material.

2. The preparation method according to claim 1, characterized in that The mass ratio of the long-chain diacid, aromatic diacid, diacid ionic liquid, multi-branched amine, aminated nanoparticles, and aminated graphene-coated ceramic particles in step (1) is 10-15:2-4:1-3:3-5:2-3:1-3, the pH value of the system is 7.2-7.4, the temperature is increased to 60-65°C, and the controlled temperature is 60-70°C; the long-chain diacid is selected from at least one of 1,10-decanedioic acid, 1,11-undecanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, and 1,18-octadecanediol, and the aromatic diacid is selected from at least one of terephthalic acid, phthalic acid, isophthalic acid, and pyromellitic acid.

3. The preparation method according to claim 1, characterized in that The preparation method of the polybranched amine is as follows: S1. Pentaerythritol was added to dichloromethane, followed by thionyl chloride. The reaction was stirred and the solvent and excess thionyl chloride were removed under reduced pressure to produce pentaerythritol tetrachloride, which has the following structure: ; S2. Pentaerythritol and ethylenediamine were added to acetonitrile, heated to reflux with stirring, and the solvent was removed under reduced pressure. The product was recrystallized from methanol, filtered, washed, and dried to obtain a polybranched amine having the following structure: .

4. The preparation method according to claim 3, characterized in that In step S1, the molar ratio of pentaerythritol to thionyl chloride is 1:4-4.2, and the stirring reaction time is 1-2 hours; in step S2, the molar ratio of pentaerythritol to ethylenediamine is 1:4-4.1, and the heating reflux stirring reaction time is 4-8 hours.

5. The preparation method according to claim 1, characterized in that The preparation method of the ammoniated nanoparticles is as follows: 8-12 parts by weight of aminosilane is dissolved in 120-150 parts by weight of ethanol, 3-7 parts by weight of concentrated hydrochloric acid and 5-8 parts by weight of water are added, stirred for reaction for 8-12 hours, centrifuged, washed, and dried to obtain the ammoniated nanoparticles; The aminosilane is selected from at least one of γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane, N-β (aminoethyl)-γ-aminopropyltriethoxysilane, N-β (aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl)-γ-aminopropylmethyldiethoxysilane, and diethylenetriaminopropyltrimethoxysilane.

6. The preparation method according to claim 1, characterized in that The structural formula of the diacid ionic liquid is shown in Formula I: Formula I; Wherein, X = H2SO4, CH3SO3H, p-TsOH, CF3SO3H, CF3COOH.

7. The preparation method according to claim 1, characterized in that The preparation method of the ammoniated graphene-coated ceramic particles is as follows: T1. Ball-mill the ceramic particles and sieve them to obtain ceramic powder; T2 graphene oxide was added to water, ceramic powder was added, stirred and mixed, and spray dried to obtain pleated graphene oxide-coated ceramic powder; T3. Add the pleated graphene oxide-coated ceramic powder to a Tris-HCl solution, add dopamine hydrochloride, heat and stir to react, filter, wash, and dry to obtain ammoniated graphene-coated ceramic particles.

8. The preparation method according to claim 7, characterized in that The mesh size of the sieve in step T1 is 100-200 mesh; the mass ratio of graphene oxide to ceramic powder in step T2 is 3-5:8-10; the pH value of the Tris-HCl solution in step T3 is 8.5-9.5, the mass ratio of the pleated graphene oxide-coated ceramic powder to dopamine hydrochloride is 10:3-4, and the heating and stirring reaction temperature is 45-55°C and the time is 3-5h.

9. The preparation method according to claim 1, characterized in that In step (2), the temperature of the heating is 210-230°C, the controlled pressure is 2-3 MPa, the heat and pressure maintaining reaction time is 2-4 hours, the temperature of the continued temperature increase is 240-260°C, and the stirring reaction time is 2-4 hours.

10. A high-temperature resistant long carbon chain bio-based nylon reinforced composite material prepared by the preparation method according to any one of claims 1 to 9.

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