Flame-retardant reinforced bio-based nylon, preparation method thereof, flame-retardant reinforced nylon composite material and application of flame-retardant reinforced bio-based nylon composite material

Abstract

The invention provides flame-retardant reinforced bio-based nylon and a preparation method thereof, a flame-retardant reinforced nylon composite material and application, and the preparation method comprises the following steps: preparing an aqueous solution of flame-retardant carbon quantum dots by using sodium phosphate, phosphoric acid and urea as raw materials; in an inert atmosphere, mixing an aqueous solution of diamine, binary acid, a catalyst, a compatilizer, a lubricant, an antioxidant and a reinforced fiber with an aqueous solution of the flame-retardant carbon quantum dots, and carrying out an in-situ polymerization reaction to obtain a carbon quantum dot / polyamide composite prepolymer; the compatilizer is an ammoniated derivative of an isobutylene maleic anhydride copolymer; slowly deflating and heating until the system is recovered to normal pressure; and after the system is recovered to normal pressure, vacuumizing and carrying out constant-pressure reaction under a vacuum condition until the system reaches preset viscosity, and after the reaction is finished, recovering to normal pressure and discharging. According to the preparation method disclosed by the invention, a process for preparing the flame-retardant nylon in situ is simplified, large-scale production is easy to realize, and the prepared flame-retardant reinforced bio-based nylon has excellent strength and flame retardance.

Description

Technical Field

[0001] This invention relates to a flame-retardant reinforced bio-based nylon, its preparation method, flame-retardant reinforced nylon composite materials and their applications, belonging to the field of nylon composite material technology. Background Technology

[0002] Nylon materials prepared from renewable biomass resources, such as glucose, cellulose, and vegetable oils (including castor oil, oleic acid, and linoleic acid), through bioengineering methods using nylon raw materials (generally diacids, diamines, or lactams) and ring-opening or condensation polymerization, are collectively referred to as bio-based nylon materials. Common bio-based nylon materials include nylon 56, nylon 510, nylon 5T, nylon 11, nylon 1010, nylon 610, nylon 410, and nylon 1012. Bio-based nylons have numerous applications in clothing fibers, natural gas pipelines, medical protective goggles, metal protective coatings, high-end fire-resistant oil-gas separators and crankshaft end caps, food packaging, automotive fuel lines, LED packaging components, and sporting goods.

[0003] Nylon has advantages such as chemical stability and excellent tensile, flexural and compressive strength, but it also has disadvantages such as high polarity of amide bonds, poor weather resistance and low low-temperature impact strength. In order to further improve the overall performance of nylon and make its application fields wider, it is usually reinforced. At the same time, its flammable properties can easily cause fires during use, so it is also necessary to modify it with flame retardants.

[0004] Currently, the more mature nylon reinforcement technologies mainly include adding reinforcing agents and improving the production process. Adding reinforcing agents is an effective way to increase the strength of nylon. Commonly used reinforcing agents include glass fiber, carbon fiber, and silica powder. These reinforcing agents can fill into nylon, increasing its strength and hardness, but their compatibility and stability are poor, resulting in a limited reinforcing effect. Improving the production process can also effectively enhance nylon strength. Common improvements include increasing melt temperature, pressure, and heating time, but these improvements do not significantly enhance the reinforcing effect of nylon.

[0005] Currently, the most mature flame-retardant technologies for nylon mainly utilize additive or reactive flame retardants. Additive flame retardants are typically dispersed in the matrix through blending to prepare flame-retardant nylon. While this method is simple, requires minimal equipment investment, and is widely used, making it the primary method for preparing flame-retardant nylon, it can easily affect the mechanical properties of the material, and insufficient blending of the flame retardant can lead to unstable flame-retardant performance. Reactive flame retardants are typically prepared by copolymerizing the flame-retardant functional groups within the flame retardant molecule onto nylon. Although this method produces flame-retardant nylon with high flame-retardant efficiency and long-lasting flame-retardant effect, solving the problems of flame retardant exposure and migration, the preparation process is complex, requires significant equipment investment, and limits its industrial application.

[0006] To enable those skilled in the art to further understand the background technology, the following are some prior art works that are closely related to this invention:

[0007] CN114605633A discloses a method for preparing bulk flame-retardant nylon, which involves dissolving aromatic diacid and diamine in water, pre-condensing them to obtain a semi-aromatic polyamide prepolymer, and then melt-polymerizing the semi-aromatic polyamide prepolymer with a flame-retardant monomer and performing solid-phase thickening to obtain the bulk flame-retardant nylon.

[0008] CN115216142A discloses an antistatic halogen-free flame-retardant reinforced nylon composite material. The preparation method is as follows: conductive microencapsulated hypophosphite flame retardant, antioxidant, glass fiber and nylon resin are uniformly mixed according to the required weight parts, and then added to a twin-screw extruder for melt blending, extrusion granulation, and thus obtained an antistatic halogen-free flame-retardant reinforced nylon composite material.

[0009] CN112592583A discloses an alcoholysis-resistant reinforced PA6T material and its preparation method. The alcoholysis-resistant reinforced PA6T material includes, by weight, high-temperature nylon, reinforcing fiber, compatibilizer, heat stabilizer, antioxidant and lubricant. The compatibilizer is a styrene-N-phenylmaleimide copolymer, which can improve the adhesion between glass and matrix resin, giving the material good alcoholysis resistance.

[0010] Therefore, providing a novel flame-retardant reinforced bio-based nylon, its preparation method, flame-retardant reinforced nylon composite materials, and their applications has become a pressing technical problem to be solved in this field. Summary of the Invention

[0011] To address the aforementioned shortcomings and deficiencies, the present invention aims to provide a flame-retardant reinforced bio-based nylon, its preparation method, flame-retardant reinforced nylon composite materials, and their applications. The preparation method provided by this invention simplifies the in-situ preparation process of flame-retardant nylon, facilitates large-scale production, and yields flame-retardant reinforced bio-based nylon with both excellent strength and flame-retardant properties, thus solving the problem that existing nylon materials cannot simultaneously possess both reinforcement and flame-retardant properties.

[0012] To achieve the above objectives, the present invention provides a method for preparing flame-retardant reinforced bio-based nylon, wherein the preparation method includes the following steps:

[0013] Step (1): Prepare an aqueous solution of flame-retardant carbon quantum dots using sodium phosphate, phosphoric acid and urea as raw materials;

[0014] Step (2): In an inert atmosphere, an aqueous solution of diamine, diacid, catalyst, compatibilizer, lubricant, antioxidant and reinforcing fiber is mixed with an aqueous solution of the flame-retardant carbon quantum dots and subjected to an in-situ polymerization reaction to obtain a carbon quantum dot / polyamide composite prepolymer; wherein, the compatibilizer is an aminated derivative of isobutylene maleic anhydride copolymer;

[0015] Step (3): Slowly release the gas and heat up until the system returns to normal pressure;

[0016] Step (4): After the system is restored to normal pressure, a vacuum is drawn and the reaction is carried out under constant pressure under vacuum until the system reaches the preset viscosity. After the reaction is completed, the system is discharged under normal pressure to obtain the flame-retardant reinforced bio-based nylon.

[0017] In the preparation method of flame-retardant reinforced bio-based nylon described above in this invention, the aqueous solution of flame-retardant carbon quantum dots contains sodium phosphate quantum dots and generated carbon quantum dots. Subsequently, sodium phosphate is incorporated into the nylon product in the form of anhydrous sodium phosphate along with crosslinking, in-situ polymerization and other reactions that occur during the preparation of the flame-retardant reinforced bio-based nylon.

[0018] As a specific embodiment of the preparation method described above in this invention, step (1) specifically includes: mixing and grinding phosphoric acid, urea and sodium phosphate evenly, heating to 150-250℃ in an inert atmosphere for 90-150 min, cooling to room temperature after the reaction is completed, adding deionized water to the obtained reaction system and heating to 50-70℃ for 50-70 min to obtain the aqueous solution of the flame-retardant carbon quantum dots.

[0019] In the process of preparing the aqueous solution of flame-retardant carbon quantum dots, phosphoric acid, urea and sodium phosphate are first mixed and ground evenly, and then heated to 150-250°C in an inert atmosphere for reaction. No water solvent is added in this process, and because the melting point of phosphoric acid is 40°C and the melting point of urea is 130°C, both of which are relatively low, they melt and react to form a salt under the condition of 150-250°C. Then, deionized water is added to the obtained reaction system and the temperature is raised to 50-70°C to prepare carbon quantum dots and make them uniformly dispersed in water to obtain an aqueous solution of flame-retardant carbon quantum dots, so as to facilitate better contact and mixing of flame-retardant carbon quantum dots with raw materials during subsequent polymerization reaction.

[0020] In step (1), phosphoric acid and urea react in a molar ratio of 1:1 to generate carbon quantum dots. This application does not specify the amount of sodium phosphate used; it can be adjusted reasonably according to the actual needs of the field operation, as long as the final flame-retardant reinforced bio-based nylon has excellent flame-retardant properties. For example, in some embodiments of this invention, the molar ratio of phosphoric acid, urea, and sodium phosphate is 2:2:1.

[0021] As a specific embodiment of the preparation method described above in this invention, the uniform mixing in step (1) can be achieved by stirring. In order to better mix, the stirring speed can be set to greater than 200 r / min so that the flame-retardant carbon quantum dots are uniformly dispersed in water.

[0022] The present invention does not specify the amount of deionized water added to the resulting reaction system in step (1), and can be reasonably adjusted according to actual needs.

[0023] As a specific embodiment of the preparation method described above in this invention, in steps (1) and (2), the amounts of each component by weight are as follows: 18-22 parts of urea, 30-35 parts of phosphoric acid, 25-30 parts of sodium phosphate, 100 parts of diamine, 90-180 parts of diacid, 0.5-1 part of catalyst, 2-3 parts of lubricant, 0.5-1 part of antioxidant, 50-60 parts of carbon fiber, and 5-7 parts of compatibilizer.

[0024] As a specific embodiment of the preparation method described above in this invention, in step (2), the diamine includes one or a combination of several of the following: pentanediamine, hexanediamine, nonanediamine, decanediamine, and dodecanediamine; and the dicarboxylic acid includes one or a combination of several of the following: succinic acid, adipic acid, sebacic acid, and dodecanediic acid.

[0025] As a specific embodiment of the preparation method described above in this invention, in step (2), the catalyst includes a mixture of ferric oxide and disodium hydrogen phosphate, etc. In this invention, the mass ratio of ferric oxide and disodium hydrogen phosphate in the mixture of ferric oxide and disodium hydrogen phosphate is not specifically required, and can be reasonably adjusted according to the actual needs of on-site operation. For example, in some embodiments of this invention, the mass ratio of the two is 1:1.

[0026] The antioxidants include one or a combination of several of the following: antioxidant 1010, antioxidant H3322, antioxidant H3332, antioxidant 168, and antioxidant SEED.

[0027] The lubricant includes one or two of silicone oil, stearic acid, etc.

[0028] As a specific embodiment of the preparation method described above in this invention, in step (2), the reinforcing fiber includes carbon fiber, etc.

[0029] As a specific embodiment of the preparation method described above in this invention, in step (2), the structural formula of the aminated derivative of the isobutylene maleic anhydride copolymer is shown in Formula 1), and its number-average molecular weight is 160,000-170,000:

[0030]

[0031] As a specific embodiment of the preparation method described above in this invention, the aminated derivative of the isobutylene maleic anhydride copolymer can be obtained commercially, such as ISOBAM-110 purchased from Kuraray Corporation, or it can be prepared by a method including the following steps:

[0032] In an inert atmosphere, maleic anhydride, azobisisobutyronitrile, isoamyl acetate and isobutylene are mixed and heated to 70°C for 3 hours to obtain an isobutylene-maleic anhydride copolymer; wherein the molar ratio of maleic anhydride to isobutylene is 1:1.

[0033] Isobutylene maleic anhydride copolymer was added to an ammonia solution and stirred at 90°C until the pH of the solution was neutral, resulting in a homogeneous mixed solution.

[0034] The homogeneous mixed solution was cooled and crystallized to obtain the aminated derivative of the isobutylene maleic anhydride copolymer.

[0035] In this invention, the preparation of the aminated derivative of isobutylene maleic anhydride copolymer can be achieved in a reaction vessel, and the preparation method includes the following specific steps:

[0036] Maleic anhydride, azobisisobutyronitrile and isoamyl acetate were added to the reaction vessel. After replacing the air in the vessel with nitrogen, isobutylene with the same molar amount as maleic anhydride was added to the reaction vessel. The temperature was raised to 70°C and reacted for 3 hours. After the reaction was completed, the mixture was cooled to room temperature and filtered. The filter cake was washed with ethanol, filtered, and then vacuum dried to obtain isobutylene-maleic anhydride copolymer.

[0037] Isobutylene maleic anhydride copolymer was added to an ammonia solution and stirred at 90°C until the pH of the solution was neutral, resulting in a homogeneous mixed solution.

[0038] The homogeneous mixed solution was cooled and crystallized to obtain the aminated derivative of the isobutylene maleic anhydride copolymer.

[0039] As a specific embodiment of the preparation method described above in this invention, in step (2), the in-situ polymerization reaction is carried out at a pH of 7.0-7.5, first at a constant temperature of 80-100℃ for 0.5-2h, and then at a constant temperature of 180-220℃ for 1-3h.

[0040] As a specific embodiment of the preparation method described above in this invention, in step (2), the pH value of the system can be adjusted to 7.0-7.5 using a diacid or a diamine, and the diacid and diamine can be the same as or different from the diacid and diamine used in the preparation of carbon quantum dot / polyamide composite prepolymer, preferably the same.

[0041] As a specific embodiment of the preparation method described above in this invention, in step (3), the temperature rise is to 240-280℃.

[0042] As a specific embodiment of the preparation method described above in this invention, step (3) includes the following operational steps:

[0043] Open the vent valve of the high-temperature and high-pressure reactor and slowly release the water vapor and small molecule volatiles (including unreacted monomers or byproducts obtained after the reaction) from the system within 30-120 minutes. During the slow venting process, the system temperature will slowly rise to 240-280℃ until it returns to normal pressure.

[0044] As a specific embodiment of the preparation method described above in this invention, in step (4), the constant pressure reaction time is 5-20 min.

[0045] As a specific embodiment of the preparation method described above in this invention, step (4) specifically includes: after the system is restored to normal pressure, it is evacuated at a constant temperature (i.e., 240-280℃), and the reaction is carried out under constant pressure for 5-20 minutes under this vacuum condition. After the reaction is completed, the material is discharged under normal pressure to obtain the flame-retardant reinforced bio-based nylon.

[0046] In some embodiments of the present invention, during the vacuuming process in step (4), the vacuum level is increased by 0.020 MPa every 10 minutes until the vacuum level reaches -0.099 MPa.

[0047] In this invention, the preparation of flame-retardant reinforced bio-based nylon can be achieved in a high-temperature and high-pressure reactor. The preparation method includes the following specific steps:

[0048] Step (1): Mix phosphoric acid, urea and sodium phosphate in a molar ratio of 2:2:1 and grind them evenly. Add the resulting uniform mixture to a high-temperature and high-pressure reactor. Replace the air in the reactor with nitrogen and close the reactor lid. Rapidly heat the reactor to 150-250℃ and react for 90-150 min. After the reaction is complete, cool the reactor to room temperature. Add deionized water to the reactor and turn on the stirrer with a speed greater than 200 r / min. Heat the reactor to 50-70℃ and react for 50-70 min to ensure that the system is mixed evenly and obtain an aqueous solution of flame-retardant carbon quantum dots.

[0049] Step (2): Dissolve diamine, diacid, catalyst, compatibilizer, lubricant, antioxidant and carbon fiber in a certain amount of deionized water to obtain an aqueous solution. Then add the aqueous solution to the high temperature and high pressure reactor (the reactor is filled with an aqueous solution of flame-retardant carbon quantum dots). Adjust the pH of the system to 7.0-7.5 using diacid or diamine. Under nitrogen atmosphere protection and stirring conditions (the specific operation can be to first replace the air in the reactor with nitrogen and then start stirring), first slowly raise the temperature to 80-100℃ and keep it at this temperature for 0.5-2h. Then raise the temperature to 180-220℃ and keep it at this temperature for 1-3h. After the reaction is completed, carbon quantum dot / polyamide composite prepolymer is obtained.

[0050] Step (3): Open the vent valve of the high temperature and high pressure reactor and discharge the water vapor and small molecule volatiles (including unreacted monomers or by-products obtained after the reaction) in the system within 30-120 minutes. During the venting process, the temperature slowly rises to 240-280℃ until it returns to normal pressure.

[0051] Step (4): After the system is restored to normal pressure, it is evacuated at a constant temperature (i.e., 240-280℃). During the evacuation process, the vacuum degree is increased by 0.020MPa every 10 minutes until the vacuum degree reaches -0.099MPa. The reaction is carried out under constant pressure for 5-20 minutes under this vacuum condition. After the reaction is completed, nitrogen is introduced into the reactor to restore normal pressure and discharge the material. Then, the flame-retardant reinforced bio-based nylon is obtained through casting, cooling, pelletizing and other operations.

[0052] The present invention does not specify the heating rate in step (1) of the preparation method of flame-retardant reinforced bio-based nylon, or the heating rate in steps (2) and (3) of the rapid heating. The heating rate can be reasonably adjusted according to the actual needs of the field operation, as long as the purpose of the present invention can be achieved.

[0053] On the other hand, the present invention also provides a flame-retardant reinforced bio-based nylon, which is prepared by the above-described method for preparing flame-retardant reinforced bio-based nylon.

[0054] In another aspect, the present invention also provides a flame-retardant reinforced nylon composite material, wherein the flame-retardant reinforced nylon composite material comprises the flame-retardant reinforced bio-based nylon and nylon resin described above.

[0055] This invention does not impose specific requirements on the preparation method of the flame-retardant reinforced nylon composite material, which can be reasonably selected and adjusted according to actual needs. For example, flame-retardant reinforced bio-based nylon and nylon resin can be mixed first, and then melt-blended and extruded using a screw extruder to obtain the flame-retardant reinforced nylon composite material. Furthermore, this invention does not impose specific requirements on the specific material of the nylon resin, which can also be reasonably selected and adjusted according to actual needs. For example, in some embodiments of this invention, the nylon resin can be any one of nylon 56, nylon 66, nylon 12, and nylon 6.

[0056] Furthermore, this invention also provides the application of the aforementioned flame-retardant reinforced bio-based nylon or the aforementioned flame-retardant reinforced nylon composite material in mechanical equipment or building materials. Preferably, the mechanical equipment and building materials are those requiring high-strength use or operation under high-temperature conditions.

[0057] Compared with the prior art, the beneficial technical effects achieved by the present invention include:

[0058] This invention prepares flame-retardant reinforced bio-based nylon by mixing an aqueous solution of flame-retardant carbon quantum dots with raw materials required for preparing flame-retardant reinforced bio-based nylon. During the preparation process, the carbon quantum dots directly polymerize in situ with the nylon monomers, i.e., the raw materials, achieving an organic combination of the nylon molecular chains and carbon dots. Furthermore, the resulting flame-retardant reinforced bio-based nylon contains sodium phosphate, which improves its flame-retardant properties. Specifically, sodium phosphate can oxidize and decompose at high temperatures to produce a large amount of water and phosphoric acid gas. These gases can isolate oxygen and reduce the temperature of the flame, thereby inhibiting the spread of fire. In addition, sodium phosphate can also adsorb the thermal decomposition products on the surface of the fuel, thereby slowing down the decomposition rate of the fuel.

[0059] In preparing flame-retardant reinforced bio-based nylon, this invention uses an ammoniation derivative of isobutylene maleic anhydride copolymer as a compatibilizer. This compatibilizer can organically combine reinforcing fibers and carbon quantum dots, perfectly solving the problem of poor compatibility and difficulty in dispersion of carbon dot particles and reinforcing fibers in polyamide resin.

[0060] The flame-retardant reinforced bio-based nylon and nylon resin provided by this invention are mixed and then melt-blended and extruded to obtain a flame-retardant reinforced nylon composite material. Under the action of the compatibilizer, carbon quantum dots, reinforcing fibers, and nylon resin have good interaction, thereby giving the flame-retardant reinforced nylon composite material good mechanical properties. Furthermore, the carbon quantum dots also act as physical cross-linking points, thus achieving in-situ nano-reinforcement and improving the flame-retardant properties of the nylon resin. Simultaneously, the compatibilizer perfectly improves the stability and fusion of the reinforcing fibers, thereby further enhancing the flame-retardant properties of the nylon resin. Detailed Implementation

[0061] It should be noted that the term "comprising" and any variations thereof in the specification and claims of this invention are intended to cover non-exclusive inclusion. For example, a process, method, system, product, or device that includes a series of steps or units is not necessarily limited to those steps or units that are explicitly listed, but may include other steps or units that are not explicitly listed or that are inherent to such processes, methods, products, or devices.

[0062] The "range" disclosed in this invention is given in the form of a lower limit and an upper limit. It can be one or more lower limits and one or more upper limits, respectively. A given range is defined by selecting a lower limit and an upper limit. The selected lower and upper limits define the boundaries of the particular range. All ranges defined in this way are composable, meaning that any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for specific parameters, it is also expected that ranges of 60-110 and 80-120 are also expected. Furthermore, if the listed minimum range values ​​are 1 and 2, and the listed maximum range values ​​are 3, 4, and 5, then the following ranges are all expected: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5.

[0063] In this invention, unless otherwise specified, the numerical range "ab" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0-5" have been listed in this invention, and "0-5" is simply a shortened representation of these numerical combinations.

[0064] In this invention, unless otherwise specified, all embodiments and preferred embodiments mentioned in this invention can be combined with each other to form new technical solutions.

[0065] In this invention, unless otherwise specified, all technical features and preferred features mentioned in this invention can be combined with each other to form new technical solutions.

[0066] In this invention, unless otherwise specified, the term "two kinds" as used in this specification means "at least two kinds".

[0067] In this invention, unless otherwise specified, all steps mentioned herein may be performed sequentially or randomly, but are preferably performed sequentially. For example, if the method includes steps (a) and (b), it means that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, if the method may also include step (c), it means that step (c) may be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0068] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the appendices and embodiments. The embodiments described below are some, but not all, embodiments of this invention, and are only used to illustrate the invention, and should not be considered as limiting the scope of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0069] The diamines and / or diacids used in the embodiments of this invention are derived from biomass, and the methods for obtaining the corresponding diamines and diacids from biomass are all conventional methods in the art. Since the diamines and / or diacids used in the embodiments of this invention are derived from biomass, the finished products obtained in the embodiments are all bio-based nylon.

[0070] Preparation Example 1

[0071] This preparation example provides an amination derivative of isobutylene maleic anhydride copolymer, which is prepared by a method including the following specific steps:

[0072] 10 parts by weight of maleic anhydride, 0.5 parts by weight of azobisisobutyronitrile, and 30 parts by weight of isoamyl acetate were added to a reaction vessel. After purging the air in the vessel with nitrogen for 30 minutes, 6 parts by weight of isobutylene were added to the reaction vessel. The temperature was raised to 70°C and the reaction was carried out for 3 hours. After the reaction was completed, the mixture was cooled to room temperature and filtered. The filter cake was washed with ethanol, filtered, and then vacuum dried to obtain isobutylene-maleic anhydride copolymer. The number average molecular weight of the isobutylene-maleic anhydride copolymer was 160,000.

[0073] Isobutylene maleic anhydride copolymer was added to an ammonia solution and stirred at 90°C until the pH of the solution was neutral, resulting in a homogeneous mixed solution.

[0074] The homogeneous mixed solution was cooled and crystallized to obtain the aminated derivative of the isobutylene maleic anhydride copolymer;

[0075] The structural formula of the aminated derivative of the isobutylene maleic anhydride copolymer is shown in Formula 1 below:

[0076]

[0077] Examples and comparative examples of flame-retardant reinforced bio-based nylon

[0078] Example 1

[0079] This embodiment provides a flame-retardant reinforced bio-based nylon, which is prepared by a method including the following specific steps:

[0080] Step (1): Grind 20 parts by weight of urea, 32.7 parts by weight of phosphoric acid and 27.4 parts by weight of sodium phosphate thoroughly to make the particles similar in size and evenly dispersed. Add the resulting uniform mixture to a high-temperature and high-pressure reactor, close the reactor, replace the air in the reactor with nitrogen three times, close the reactor lid, rapidly heat to 200℃ and react for 120 min. After the reaction is completed, cool to room temperature, add 50 parts by weight of deionized water to the reactor, turn on the stirrer and set the speed to 400 r / min to make the system uniformly mixed. Heat to 60℃ and react for 60 min to obtain an aqueous solution of flame-retardant carbon quantum dots.

[0081] Step (2): Dissolve 90 parts by weight of adipic acid and 100 parts by weight of pentanediamine in 100 parts by weight of deionized water, then add 2 parts by weight of silicone oil lubricant, 0.5 parts by weight of catalyst (a mixture of iron oxide and disodium hydrogen phosphate in a mass ratio of 1:1), 0.5 parts by weight of antioxidant (antioxidant H3322), 50 parts by weight of carbon fiber (Toray T300), and 5 parts by weight of compatibilizer (ammoniation derivative of isobutylene maleic anhydride copolymer provided in Preparation Example 1) into a high-temperature and high-pressure reactor containing an aqueous solution of flame-retardant carbon quantum dots in step (1). Adjust the pH of the system to 7.2 using pentanediamine, replace the air in the reactor with inert gas, start stirring, set the speed to 80 r / min, slowly raise the temperature to 80°C, hold the temperature for 1 h, raise the temperature to 210°C and hold the temperature for 3 h. After the reaction is completed, carbon quantum dot / polyamide composite prepolymer is obtained.

[0082] Step (3): Open the vent valve of the high-temperature and high-pressure reactor and discharge water vapor and unreacted monomers and / or byproducts within 60 minutes. During the venting process, the temperature slowly rises to 260°C until it returns to normal pressure.

[0083] Step (4): After the system is restored to normal pressure, it is evacuated at a constant temperature of 260℃. The vacuum degree is increased by 0.020MPa every 10 minutes until it reaches -0.099MPa. After reacting under constant pressure for 5 minutes under this vacuum condition, nitrogen is introduced to restore normal pressure and discharge the material. After casting, cooling and pelletizing, flame-retardant reinforced bio-based nylon is obtained.

[0084] Example 2

[0085] This embodiment provides a flame-retardant reinforced bio-based nylon, which differs from Embodiment 1 only in the amount of adipic acid used. In this embodiment, the amount of adipic acid used is 130 parts by weight.

[0086] Example 3

[0087] This embodiment provides a flame-retardant reinforced bio-based nylon, which differs from Embodiment 1 only in the amount of adipic acid used. In this embodiment, the amount of adipic acid used is 180 parts by weight.

[0088] The number-average molecular weight, tensile strength, and limiting oxygen index data of the flame-retardant reinforced bio-based nylons provided in Examples 1-3 are shown in Table 1.

[0089] Table 1

[0090] Adipic acid weight parts Number average molecular weight Tensile strength (MPa) Limiting Oxygen Index (LOI) Example 1 90 37500 105.32 33 Example 2 130 38000 106.42 33 Example 3 180 37000 98.50 33

[0091] Note: Tensile strength was measured according to GB / T 1040.1-2018 Determination of Tensile Properties of Plastics, and Limiting Oxygen Index was measured according to GB / T 2408-2008 Determination of Burning Performance of Plastics - Horizontal and Vertical Methods.

[0092] As shown in Table 1, the flame-retardant reinforced bio-based nylons provided in Examples 1-3 of this invention all have a number-average molecular weight of over 37,000 and a tensile strength of over 98 MPa. Furthermore, the flame-retardant reinforced bio-based nylon provided in Example 2 exhibits an even higher tensile strength of 106.42 MPa and a limiting oxygen index of 33. This indicates that the flame-retardant reinforced bio-based nylons provided in Examples 1-3 of this invention possess high strength and excellent flame-retardant properties. Table 1 also shows that with the increase of adipic acid dosage, the tensile strength and number-average molecular weight of the obtained flame-retardant reinforced bio-based nylons first increase and then decrease, while their flame-retardant properties do not change with the amount of adipic acid used.

[0093] Example 4

[0094] This embodiment provides a flame-retardant reinforced bio-based nylon, which differs from Embodiment 2 only in the amount of lubricant used. In this embodiment, the amount of lubricant used is 2.5 parts by weight.

[0095] Example 5

[0096] This embodiment provides a flame-retardant reinforced bio-based nylon, which differs from Embodiment 2 only in the amount of lubricant used. In this embodiment, the amount of lubricant used is 3 parts by weight.

[0097] The number-average molecular weight, tensile strength, and limiting oxygen index data of the flame-retardant reinforced bio-based nylons provided in Examples 2 and 4-5 are shown in Table 2.

[0098] Table 2

[0099] Lubricant weight parts Number average molecular weight Tensile strength (MPa) Limiting Oxygen Index (LOI) Example 2 2 38000 106.42 33 Example 4 2.5 38000 106.45 33 Example 5 3 38000 106.47 33

[0100] Note: Tensile strength was measured according to GB / T 1040.1-2018 Determination of Tensile Properties of Plastics, and Limiting Oxygen Index was measured according to GB / T 2408-2008 Determination of Burning Performance of Plastics - Horizontal and Vertical Methods.

[0101] As shown in Table 2, the flame-retardant reinforced bio-based nylons provided in Examples 2 and 4-5 of this invention all have a number-average molecular weight of 38,000, a tensile strength of over 106 MPa, and a limiting oxygen index as high as 33. This indicates that the flame-retardant reinforced bio-based nylons provided in Examples 2 and 4-5 of this invention possess high strength and excellent flame-retardant properties. Table 2 also shows that the flame-retardant properties and number-average molecular weight of the flame-retardant reinforced bio-based nylon do not change with the amount of lubricant used, and its tensile strength also remains essentially unchanged with the amount of lubricant used.

[0102] Example 6

[0103] This embodiment provides a flame-retardant reinforced bio-based nylon, which differs from Example 5 only in the amount of catalyst used. In this embodiment, the amount of catalyst used is 0.8 parts by weight.

[0104] Example 7

[0105] This embodiment provides a flame-retardant reinforced bio-based nylon, which differs from Example 5 only in the amount of catalyst used. In this embodiment, the amount of catalyst used is 1 part by weight.

[0106] The number-average molecular weight, tensile strength, and limiting oxygen index data of the flame-retardant reinforced bio-based nylons provided in Examples 5-7 are shown in Table 3.

[0107] Table 3

[0108] Catalyst weight parts Number average molecular weight Tensile strength (MPa) Limiting Oxygen Index (LOI) Example 5 0.5 38000 106.47 33 Example 6 0.8 38000 106.62 33 Example 7 1 38500 107.21 33

[0109] Note: Tensile strength was measured according to GB / T 1040.1-2018 Determination of Tensile Properties of Plastics, and Limiting Oxygen Index was measured according to GB / T 2408-2008 Determination of Burning Performance of Plastics - Horizontal and Vertical Methods.

[0110] As can be seen from Table 3, the flame-retardant reinforced bio-based nylons provided in Examples 5-7 of this invention all have a number-average molecular weight of over 38,000, a tensile strength of over 106 MPa, and a limiting oxygen index as high as 33. This indicates that the flame-retardant reinforced bio-based nylons provided in Examples 5-7 of this invention all possess high strength and excellent flame-retardant properties. Table 3 also shows that the flame-retardant properties of the flame-retardant reinforced bio-based nylons do not change with the amount of catalyst, while their tensile strength and number-average molecular weight change slightly with the amount of catalyst; for example, the tensile strength increases slightly with increasing catalyst dosage.

[0111] Example 8

[0112] This embodiment provides a flame-retardant reinforced bio-based nylon, which differs from Embodiment 7 only in the amount of compatibilizer used. In this embodiment, the amount of compatibilizer used is 6 parts by weight.

[0113] Example 9

[0114] This embodiment provides a flame-retardant reinforced bio-based nylon, which differs from Embodiment 7 only in the amount of compatibilizer used. In this embodiment, the amount of compatibilizer used is 7 parts by weight.

[0115] The number-average molecular weight, tensile strength, and limiting oxygen index data of the flame-retardant reinforced bio-based nylons provided in Examples 7-9 are shown in Table 4.

[0116] Table 4

[0117] Compatibilizer weight parts Number average molecular weight Tensile strength (MPa) Limiting Oxygen Index (LOI) Example 7 5 38500 107.21 33 Example 8 6 38900 107.34 34 Example 9 7 39000 107.75 35

[0118] Note: Tensile strength was measured according to GB / T 1040.1-2018 Determination of Tensile Properties of Plastics, and Limiting Oxygen Index was measured according to GB / T 2408-2008 Determination of Burning Performance of Plastics - Horizontal and Vertical Methods.

[0119] As shown in Table 4, the flame-retardant reinforced bio-based nylons provided in Examples 7-9 of this invention all have a number-average molecular weight of over 38,500, a tensile strength of over 107 MPa, and a limiting oxygen index of over 33. This indicates that the flame-retardant reinforced bio-based nylons provided in Examples 7-9 of this invention all possess high strength and excellent flame-retardant properties. Table 4 also shows that the number-average molecular weight, tensile strength, and flame-retardant properties of the flame-retardant reinforced bio-based nylons all increase slightly with the increase of compatibilizer.

[0120] Example 10

[0121] This embodiment provides a flame-retardant reinforced bio-based nylon, which differs from Embodiment 9 only in the amount of antioxidant used. In this embodiment, the amount of antioxidant used is 0.8 parts by weight.

[0122] Example 11

[0123] This embodiment provides a flame-retardant reinforced bio-based nylon, which differs from Embodiment 9 only in the amount of antioxidant used. In this embodiment, the amount of antioxidant used is 1 part by weight.

[0124] The number-average molecular weight, tensile strength, and limiting oxygen index data of the flame-retardant reinforced bio-based nylons provided in Examples 9-11 are shown in Table 5.

[0125] Table 5

[0126] antioxidant parts by weight Number average molecular weight Tensile strength (MPa) Limiting Oxygen Index (LOI) Example 9 0.5 39000 107.75 35 Example 10 0.8 39000 108.01 35 Example 11 1 39000 108.18 35

[0127] Note: Tensile strength was measured according to GB / T 1040.1-2018 Determination of Tensile Properties of Plastics, and Limiting Oxygen Index was measured according to GB / T 2408-2008 Determination of Burning Performance of Plastics - Horizontal and Vertical Methods.

[0128] As shown in Table 5, the flame-retardant reinforced bio-based nylons provided in Examples 9-11 of this invention all have a number-average molecular weight of 39,000, a tensile strength of over 107 MPa, and a limiting oxygen index as high as 35. This indicates that the flame-retardant reinforced bio-based nylons provided in Examples 9-11 of this invention all possess high strength and excellent flame-retardant properties. Table 5 also shows that the number-average molecular weight and flame-retardant properties of the flame-retardant reinforced bio-based nylons do not change with the amount of antioxidant, while their tensile strength increases slightly with the increase of compatibilizer.

[0129] Example 12

[0130] This embodiment provides a flame-retardant reinforced bio-based nylon, which differs from Embodiment 11 only in the amount of carbon fiber (Toray T300). In this embodiment, the amount of carbon fiber is 55 parts by weight.

[0131] Example 13

[0132] This embodiment provides a flame-retardant reinforced bio-based nylon, which differs from Embodiment 11 only in the amount of carbon fiber (Toray T300). In this embodiment, the amount of carbon fiber is 60 parts by weight.

[0133] The number-average molecular weight, tensile strength, and limiting oxygen index data of the flame-retardant reinforced bio-based nylons provided in Examples 11-13 are shown in Table 6.

[0134] Table 6

[0135] carbon fiber weight parts Number average molecular weight Tensile strength (MPa) Limiting Oxygen Index (LOI) Example 11 50 39000 108.18 35 Example 12 55 39000 108.17 37 Example 13 60 39000 108.30 40

[0136] Note: Tensile strength was measured according to GB / T 1040.1-2018 Determination of Tensile Properties of Plastics, and Limiting Oxygen Index was measured according to GB / T 2408-2008 Determination of Burning Performance of Plastics - Horizontal and Vertical Methods.

[0137] As shown in Table 6, the flame-retardant reinforced bio-based nylons provided in Examples 11-13 of this invention all have a number-average molecular weight of 39,000, a tensile strength of over 108 MPa, and a limiting oxygen index of over 35. This indicates that the flame-retardant reinforced bio-based nylons provided in Examples 11-13 of this invention all possess high strength and excellent flame-retardant properties. Table 6 also shows that the number-average molecular weight of the flame-retardant reinforced bio-based nylon does not change with the amount of carbon fiber used, while its tensile strength and flame-retardant properties increase slightly with the increase of carbon fiber content.

[0138] Comparative Example 1

[0139] This comparative example provides a bio-based nylon, which differs from Example 2 only in that the reaction temperature for generating carbon quantum dots is lowered; in this comparative example, the reaction temperature is 100°C.

[0140] Comparative Example 2

[0141] This comparative example provides a bio-based nylon, which differs from Example 2 only in that the reaction temperature for generating carbon quantum dots is increased; in this comparative example, the reaction temperature is 300°C.

[0142] Comparative Example 3

[0143] This comparative example provides a bio-based nylon, which differs from Example 2 only in that the reaction time for generating carbon quantum dots is reduced; in this comparative example, the reaction time is 60 min.

[0144] Comparative Example 4

[0145] This comparative example provides a bio-based nylon, which differs from Example 2 only in that the reaction time for generating carbon quantum dots is increased; in this comparative example, the reaction time is 180 min.

[0146] The limiting oxygen index data of the flame-retardant reinforced bio-based nylon provided in Example 2 of the present invention and the bio-based nylon provided in Comparative Examples 1-4 are shown in Table 7.

[0147] Table 7

[0148]

[0149] Note: Tensile strength was measured according to GB / T 1040.1-2018 Determination of Tensile Properties of Plastics, and Limiting Oxygen Index was measured according to GB / T 2408-2008 Determination of Burning Performance of Plastics - Horizontal and Vertical Methods.

[0150] As can be seen from Table 7, compared with Example 2, Comparative Example 1 lowered the reaction temperature for carbon quantum dot generation to 100°C, resulting in a limiting oxygen index of only 29 for the final product, which is significantly lower than that of Example 2. This indicates that, under the same conditions, the generation of carbon quantum dots requires a sufficiently high reaction temperature so that the carbon quantum dots can react fully and disperse evenly in water, thereby achieving a better flame retardant effect in bio-based nylon products.

[0151] As can be seen from Table 7, compared with Example 2, Comparative Example 2 increased the reaction temperature for carbon quantum dot generation to 250°C, resulting in a limiting oxygen index of only 30 for the final product, which is significantly lower than that of Example 2. This indicates that under the same conditions, excessively high carbon quantum dot generation temperature can also destroy the generation of carbon quantum dots, which is not conducive to their better flame retardant effect in bio-based nylon products.

[0152] As can also be seen from Table 7, compared with Example 2, Comparative Example 3 reduced the reaction time for carbon quantum dot generation to 60 min, resulting in a limiting oxygen index of only 30 for the final product, which is significantly lower than that of Example 2. This indicates that under the same conditions, a short reaction time for carbon quantum dot generation will affect the generation of carbon quantum dots and is not conducive to their better flame retardant effect in bio-based nylon products.

[0153] As can also be seen from Table 7, compared with Example 2, Comparative Example 4 increased the reaction time for carbon quantum dot generation to 180 min, resulting in a limiting oxygen index of only 31 for the final product, which is significantly lower than that of Example 4. This indicates that under the same conditions, if the reaction time for carbon quantum dot generation is too long, it will affect the quality of carbon quantum dots and will not be conducive to their better flame retardant effect in bio-based nylon products.

[0154] Based on the flame retardant effects of the bio-based nylon products obtained in Example 2 and Comparative Examples 1-4, it can be seen that reaction temperature and time are key parameters for preparing activated carbon quantum dots in a high-temperature and high-pressure reactor. When the reaction temperature is too low or the time is too short, the reaction between phosphoric acid and urea is incomplete, resulting in incomplete carbon dot formation. This leads to a large number of unreacted monomers in the subsequent polymerization system, causing some of the nylon polymerization to stop. This weakens the interaction between carbon quantum dots and nylon resin, and reduces the number of carbon quantum dots, thus decreasing the flame retardant performance. On the other hand, if the temperature is too high or the reaction time is too long, some carbon dots become completely charred and lose their reactivity, making it difficult for them to react with nylon and resulting in poor dispersibility. The deactivated carbon dots have a weaker impact on the nylon polymerization reaction.

[0155] Comparative Example 5

[0156] This comparative example provides a bio-based nylon, which differs from Example 2 only in that no compatibilizer is used.

[0157] The tensile strength and limiting oxygen index data of the flame-retardant reinforced bio-based nylon provided in Example 2 and the bio-based nylon provided in Comparative Example 5 are shown in Table 8.

[0158] Table 8

[0159]

[0160] Note: Tensile strength was measured according to GB / T 1040.1-2018 Determination of Tensile Properties of Plastics, and Limiting Oxygen Index was measured according to GB / T 2408-2008 Determination of Burning Performance of Plastics - Horizontal and Vertical Methods.

[0161] As can be seen from Table 8, compared with Comparative Example 5, Example 2 of the present invention uses an amination derivative of isobutylene maleic anhydride copolymer as a compatibilizer, which can effectively integrate carbon quantum dots and carbon fibers into the nylon material and achieve better and more stable flame retardant effect and tensile strength.

[0162] Comparative Example 6

[0163] This comparative example provides a bio-based nylon, which differs from Example 2 only in that sodium phosphate is not added in step (1).

[0164] The limiting oxygen index data of the flame-retardant reinforced bio-based nylon provided in Example 2 of the present invention and the bio-based nylon provided in Comparative Example 6 are shown in Table 9.

[0165] Table 9

[0166]

[0167] Note: Tensile strength was measured according to GB / T 1040.1-2018 Determination of Tensile Properties of Plastics, and Limiting Oxygen Index was measured according to GB / T 2408-2008 Determination of Burning Performance of Plastics - Horizontal and Vertical Methods.

[0168] As can be seen from Table 9, sodium phosphate was added in step (1) of Example 2 of the present invention. Compared with the bio-based nylon provided in Comparative Example 6, the flame-retardant reinforced bio-based nylon provided in Example 2 has superior flame-retardant properties. This indicates that, under the same conditions, phosphates, such as sodium phosphate, can promote the flame-retardant effect of nylon materials. Specifically, phosphates can oxidize and decompose at high temperatures to produce a large amount of water and phosphoric acid gas. These gases can isolate oxygen and reduce the temperature of the flame, thereby inhibiting the spread of fire. In addition, phosphates can also adsorb the thermal decomposition products on the surface of fuel to slow down the decomposition rate of fuel. In summary, the role of phosphates is to inhibit the temperature and oxygen of the fire source when an object is burning, thereby improving the flame-retardant properties of the material.

[0169] Comparative Example 7

[0170] This comparative example provides a bio-based nylon, which differs from Example 2 only in the compatibilizer used. The compatibilizer used in this comparative example is the isobutylene-maleic anhydride copolymer with a number average molecular weight of 160,000 provided in Preparation Example 1.

[0171] The tensile strength and limiting oxygen index data of the flame-retardant reinforced bio-based nylon provided in Example 2 of the present invention and the bio-based nylon provided in Comparative Example 7 are shown in Table 10.

[0172] Table 10

[0173]

[0174]

[0175] Note: Tensile strength was measured according to GB / T 1040.1-2018 Determination of Tensile Properties of Plastics, and Limiting Oxygen Index was measured according to GB / T 2408-2008 Determination of Burning Performance of Plastics - Horizontal and Vertical Methods.

[0176] As can be seen from Table 10, compared with the bio-based nylon prepared by using isobutylene maleic anhydride copolymer as a compatibilizer in Comparative Example 7, the flame-retardant reinforced bio-based nylon prepared by using an aminated derivative of isobutylene maleic anhydride copolymer as a compatibilizer in Example 2 of this invention has superior tensile strength and flame retardant properties. This indicates that compared with using isobutylene maleic anhydride copolymer (unaminated copolymer) as a compatibilizer, the use of an aminated derivative of isobutylene maleic anhydride copolymer as a compatibilizer in this invention is more conducive to improving the mechanical strength and flame retardant properties of the obtained bio-based nylon product.

[0177] Example 14

[0178] This embodiment provides a flame-retardant reinforced nylon 56 composite material, which is prepared by a method including the following specific steps:

[0179] The flame-retardant reinforced bio-based nylon provided in Example 1 was placed in a vacuum oven and dried at 90°C for 6 hours. Then, it was blended and modified with nylon 56. Specifically, 100 parts by weight of nylon 56 and 25 parts by weight of dried flame-retardant reinforced bio-based nylon were mixed evenly and then melt-blended in a twin-screw extruder. The twin-screw temperature was 270°C and the rotation speed was 50 r / min. Finally, the flame-retardant reinforced nylon 56 composite material was prepared after extrusion and pelletizing.

[0180] The above description is merely a specific embodiment of the present invention and should not be construed as limiting the scope of the invention. Therefore, any substitution of equivalent components or equivalent changes and modifications made within the scope of protection of this patent should still fall within the scope of this patent. Furthermore, the technical features, technical features and technical inventions, and technical inventions in this invention can be freely combined and used.

Claims

1. A method for preparing flame-retardant reinforced bio-based nylon, characterized in that, The preparation method includes the following steps: Step (1): Prepare an aqueous solution of flame-retardant carbon quantum dots using sodium phosphate, phosphoric acid and urea as raw materials; Step (2): In an inert atmosphere, an aqueous solution of diamine, diacid, catalyst, compatibilizer, lubricant, antioxidant and reinforcing fiber is mixed with an aqueous solution of flame-retardant carbon quantum dots and subjected to in-situ polymerization to obtain a carbon quantum dot / polyamide composite prepolymer; wherein, the compatibilizer is an aminated derivative of isobutylene maleic anhydride copolymer. Step (3): Slowly release the gas and heat up until the system returns to normal pressure; Step (4): After the system is restored to normal pressure, a vacuum is drawn and the reaction is carried out under constant pressure under vacuum until the system reaches the preset viscosity. After the reaction is completed, the system is discharged under normal pressure to obtain the flame-retardant reinforced bio-based nylon.

2. The preparation method according to claim 1, characterized in that, Step (1) specifically includes: mixing and grinding phosphoric acid, urea and sodium phosphate evenly, heating to 150-250℃ in an inert atmosphere and reacting for 90-150 min, cooling to room temperature after the reaction is completed, adding deionized water to the obtained reaction system and heating to 50-70℃ and reacting for 50-70 min to obtain the aqueous solution of the flame-retardant carbon quantum dots.

3. The preparation method according to claim 1, characterized in that, In steps (1) and (2), the amounts of each component by weight are as follows: 18-22 parts urea, 30-35 parts phosphoric acid, 25-30 parts sodium phosphate, 100 parts diamine, 90-180 parts diacid, 0.5-1 part catalyst, 2-3 parts lubricant, 0.5-1 part antioxidant, 50-60 parts reinforcing fiber, and 5-7 parts compatibilizer.

4. The preparation method according to any one of claims 1-3, characterized in that, In step (2), the diamine includes one or a combination of several of pentanediamine, hexanediamine, nonanediamine, decanediamine and dodecanediamine, and the dicarboxylic acid includes one or a combination of several of succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid.

5. The preparation method according to any one of claims 1-3, characterized in that, In step (2), the catalyst comprises a mixture of iron(III) oxide and disodium hydrogen phosphate; The antioxidants include one or a combination of antioxidants 1010, H3322, H3332, 168, and SEED. The lubricant includes one or both of silicone oil and stearic acid.

6. The preparation method according to any one of claims 1-3, characterized in that, In step (2), the reinforcing fiber includes carbon fiber.

7. The preparation method according to any one of claims 1-3, characterized in that, In step (2), the structural formula of the aminated derivative of the isobutylene maleic anhydride copolymer is shown in Formula 1), and its number-average molecular weight is 160,000-170,000:

8. The preparation method according to any one of claims 1-3, characterized in that, In step (2), the in-situ polymerization reaction is carried out under the condition of pH 7.0-7.5, first at 80-100℃ for 0.5-2h, and then at 180-220℃ for 1-3h.

9. The preparation method according to any one of claims 1-3, characterized in that, In step (3), the temperature rise is to 240-280℃.

10. The preparation method according to any one of claims 1-3, characterized in that, In step (4), the constant pressure reaction takes 5-20 minutes.

11. A flame-retardant reinforced bio-based nylon, characterized in that, The flame-retardant reinforced bio-based nylon is prepared by the method of any one of claims 1-10.

12. A flame-retardant reinforced nylon composite material, characterized in that, The flame-retardant reinforced nylon composite material comprises the flame-retardant reinforced bio-based nylon and nylon resin as described in claim 11.

13. The application of the flame-retardant reinforced bio-based nylon of claim 11 or the flame-retardant reinforced nylon composite of claim 12 in mechanical equipment or building materials.

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