Antistatic flame-retardant bio-based nylon, preparation method thereof, antistatic flame-retardant nylon composite material and application

Abstract

The invention provides antistatic flame-retardant bio-based nylon and a preparation method thereof, an antistatic flame-retardant nylon composite material and application wherein the preparation method comprises the following steps: preparing carbon quantum dots in a glacial acetic acid aqueous solution medium by using maleic anhydride and ammonium acetate as raw materials to obtain a glacial acetic acid aqueous solution of the carbon quantum dots; the preparation method comprises the following steps: mixing an aqueous solution of diamine, binary acid, a catalyst, a lubricant, an antioxidant, a flame retardant and a compatilizer with a glacial acetic acid aqueous solution of carbon quantum dots in an inert atmosphere, and carrying out an in-situ polymerization reaction to obtain a carbon quantum dot / polyamide composite prepolymer; wherein the compatilizer is 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, carrying out constant-pressure reaction under a vacuum condition until the system reaches a preset viscosity, and after the reaction is finished, recovering to normal pressure and discharging to obtain the antistatic flame-retardant bio-based nylon. The nylon material provided by the invention has excellent antistatic property, flame retardant property and mechanical property.

Description

Technical Field

[0001] This invention relates to an antistatic and flame-retardant bio-based nylon, its preparation method, antistatic and flame-retardant 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] As an insulating polymer, it has a high resistance, which can easily cause static electricity to accumulate and lead to accidents in some special fields. Therefore, it needs to be modified to resist static electricity. At the same time, its flammable properties can easily cause fires during use, so it needs to be modified to be flame-retardant.

[0004] Currently, the more mature antistatic modification technologies for nylon mainly include blending with inorganic conductive particles, surface coating or oiling, and in-situ preparation of antistatic polymers. Among these, blending with antistatic agents is the most widely used method in the field of engineering plastics; however, the compatibility between antistatic agents and resin matrices is poor, and the introduction of large amounts can lead to a decrease in the mechanical properties of the material. Surface coating technology is mostly used in the fields of fibers and fabrics, but its disadvantage is that it is not wear-resistant. Overall, in-situ preparation technology has a high threshold and is technically difficult, making it difficult to achieve industrialization at present.

[0005] Currently, the most mature flame-retardant technologies for nylon mainly utilize additive or reactive flame retardants. For additive flame retardants, they are typically dispersed in the matrix through blending to prepare flame-retardant nylon. This method is simple, requires low equipment investment, and is widely used, making it the primary method for preparing flame-retardant nylon. However, it can easily affect the mechanical properties of the material, and insufficient blending of the flame retardant can lead to unstable flame-retardant effects. For reactive flame retardants, the flame-retardant functional groups within the flame retardant molecule are usually linked to nylon through copolymerization to prepare flame-retardant nylon. This method yields high flame-retardant efficiency and long-lasting flame-retardant effects, solving the problems of flame retardant exposure and migration. However, the process is complex, requires high equipment investment, and its industrial application is limited.

[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 antistatic and flame-retardant bio-based nylon, its preparation method, antistatic and flame-retardant nylon composite materials, and its applications have become urgent technical problems to be solved in this field. Summary of the Invention

[0011] To address the aforementioned shortcomings and deficiencies, the present invention aims to provide an antistatic and flame-retardant bio-based nylon, its preparation method, antistatic and flame-retardant nylon composite materials, and their applications. The nylon material provided by this invention possesses excellent antistatic, flame-retardant, and mechanical properties, and exhibits stable antistatic and flame-retardant effects, thus solving the technical problem that existing technologies cannot simultaneously achieve excellent antistatic and flame-retardant properties in nylon materials.

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

[0013] Step (1): Carbon quantum dots are prepared in an aqueous glacial acetic acid medium using maleic anhydride and ammonium acetate as raw materials to obtain an aqueous glacial acetic acid solution containing carbon quantum dots;

[0014] Step (2): In an inert atmosphere, an aqueous solution of diamine, diacid, catalyst, lubricant, antioxidant, flame retardant and compatibilizer is mixed with an aqueous solution of glacial acetic acid containing carbon quantum dots and subjected to in-situ polymerization to obtain a carbon quantum dot / polyamide composite prepolymer; wherein the compatibilizer is an 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 conditions until the system reaches the preset viscosity. After the reaction is completed, the system is discharged under normal pressure to obtain the antistatic and flame-retardant bio-based nylon.

[0017] As a specific embodiment of the preparation method described above in this invention, step (1) includes: mixing maleic anhydride and ammonium acetate in equal molar amounts and grinding them evenly, then mixing the resulting uniform mixture with an aqueous solution of glacial acetic acid, and then heating it to 100°C for 60 min under an inert atmosphere and stirring conditions, and cooling it to room temperature after the reaction to obtain an aqueous solution of glacial acetic acid containing carbon quantum dots.

[0018] In one specific embodiment of the preparation method described above in this invention, the concentration of the glacial acetic acid aqueous solution in step (1) is 0.1-0.5 mol / L. This invention does not require a specific amount of glacial acetic acid aqueous solution; it can be adjusted appropriately as needed.

[0019] 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 150r / min-500r / min so that the carbon quantum dots generated by the reaction are uniformly dispersed in the glacial acetic acid aqueous solution to obtain the glacial acetic acid aqueous solution of the carbon quantum dots.

[0020] As a specific embodiment of the preparation method described above in this invention, step (1) specifically includes the following operational steps:

[0021] Maleic anhydride and ammonium acetate were mixed and ground uniformly at a molar ratio of ammonium acetate to maleic anhydride of 1-1.2:1. The resulting uniform mixture was then added to a high-temperature and high-pressure reactor. A certain amount of 0.1-0.5 mol / L glacial acetic acid aqueous solution was added to the reactor. After closing the reactor lid, the air inside the reactor was replaced with nitrogen. The stirring was started and the stirring speed was set to 150 r / min-500 r / min. The temperature was raised to 90-120℃ and reacted for 60-90 min. After the reaction was completed, the mixture was cooled to room temperature to obtain a glacial acetic acid aqueous solution of carbon quantum dots.

[0022] In step (1) of the preparation method described above in this invention, carbon quantum dots with good conductivity are prepared by the amidation reaction of maleic anhydride and ammonium acetate.

[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: 15-20 parts of ammonium acetate, 20 parts of maleic anhydride, 100 parts of diamine, 90-160 parts of dicarboxylic acid, 0.5-1 part of catalyst, 2-3 parts of lubricant, 2-3 parts of antioxidant, 2-5 parts of compatibilizer, and 50-60 parts of flame retardant.

[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 glacial acetic acid and disodium hydrogen phosphate, etc.; wherein, this invention does not make specific requirements on the ratio of glacial acetic acid to disodium hydrogen phosphate in the mixture of glacial acetic acid and disodium hydrogen phosphate, and can be reasonably adjusted according to the actual needs on site. 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 flame retardant is a nitrogen-based flame retardant, including one or a combination of several of melamine (MA), melamine polyphosphate (MPP), and melamine cyanurate (MCA).

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

[0030]

[0031] The isobutylene maleic anhydride copolymer used in this invention can be commercially available or prepared in-house using conventional methods. When the isobutylene maleic anhydride copolymer is prepared in-house, the preparation method may include, for example:

[0032] Maleic anhydride, azobisisobutyronitrile, and isoamyl acetate were added to a reaction vessel. After nitrogen purging, isobutylene with the same molar amount as maleic anhydride was added. The mixture was then heated 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 dried under vacuum to obtain the isobutylene-maleic anhydride copolymer.

[0033] 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 200-220℃ for 1-3h.

[0034] 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.

[0035] As a specific embodiment of the preparation method described above in this invention, step (2) specifically includes the following operational steps:

[0036] First, dissolve the diamine and diacid in deionized water, then add lubricant, catalyst, antioxidant, flame retardant and compatibilizer. Pour the resulting aqueous solution into a high-temperature and high-pressure reactor containing a carbon quantum dot aqueous solution of glacial acetic acid. Adjust the pH of the system to 7.0-7.5 using the diacid or diamine, replace the air in the reactor with nitrogen, start stirring, slowly raise the temperature to 80-100℃ and hold for 0.5-2 hours, then raise the temperature to 200-220℃ and hold for 1-3 hours. After the in-situ polymerization reaction is completed, a carbon quantum dot / polyamide composite prepolymer is obtained.

[0037] As a specific embodiment of the preparation method described above in this invention, in step (3), the temperature rise is to 240-280℃.

[0038] As a specific embodiment of the preparation method described above in this invention, step (3) specifically includes the following operational steps:

[0039] 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 60-120 minutes. During the slow venting process, the system temperature will slowly rise to 240-280℃ until it returns to normal pressure.

[0040] 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.

[0041] As a specific embodiment of the preparation method described above in this invention, step (4) specifically includes the following operational steps:

[0042] After the system is restored to normal pressure, it is evacuated at a constant temperature (i.e., 240-280℃), and then reacted under constant pressure for 5-20 minutes under the same vacuum conditions. After the reaction is completed, nitrogen is introduced to restore normal pressure, the material is discharged, cast into a strip, cooled, and pelletized to obtain the antistatic and flame-retardant bio-based nylon.

[0043] 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 it reaches -0.099 MPa.

[0044] The method for preparing antistatic and flame-retardant bio-based nylon provided by this invention is simple and easy to scale up for production.

[0045] On the other hand, the present invention also provides an antistatic and flame-retardant bio-based nylon, wherein the antistatic and flame-retardant bio-based nylon is prepared by the above-described method for preparing antistatic and flame-retardant bio-based nylon.

[0046] In another aspect, the present invention also provides an antistatic flame-retardant nylon composite material, wherein the antistatic flame-retardant nylon composite material comprises the above-mentioned antistatic flame-retardant bio-based nylon and nylon resin.

[0047] The present invention does not specify a particular method for preparing the antistatic and flame-retardant nylon composite material, and can be reasonably selected and adjusted according to actual needs. For example, the antistatic and flame-retardant bio-based nylon provided by the present invention can be directly melt-blended with other nylon resins without the use of any processing aids to obtain the antistatic and flame-retardant nylon composite material.

[0048] Furthermore, the present invention does not impose specific requirements on the specific material of the nylon resin, which can be reasonably selected and adjusted according to actual needs. For example, in some embodiments of the present invention, the nylon resin can be any one of nylon 56, nylon 66, nylon 12, and nylon 6.

[0049] Furthermore, this invention also provides the application of the aforementioned antistatic flame-retardant bio-based nylon or the aforementioned antistatic flame-retardant nylon composite material in clothing fabrics or mechanical equipment. The antistatic flame-retardant bio-based nylon or the antistatic flame-retardant nylon composite material can be used as a fabric fiber to improve the flame-retardant and antistatic properties of clothing fabrics.

[0050] Compared with the prior art, the beneficial technical effects achieved by the present invention include:

[0051] (1) The method for preparing antistatic and flame-retardant bio-based nylon provided by the present invention firstly prepares antistatic base material, namely carbon quantum dots, in situ, and controls the type and quantity of surface groups of carbon quantum dots by using the raw materials for preparing carbon quantum dots and the reaction temperature in the preparation process. Then, the carbon quantum dots with good conductivity are directly polymerized in situ with nylon monomers to achieve the organic combination of nylon molecular chains and carbon quantum dots.

[0052] (2) In the preparation of antistatic flame-retardant bio-based nylon, the present invention uses isobutylene maleic anhydride copolymer as a compatibilizer. This compatibilizer has good compatibility and can organically combine flame retardant and carbon quantum dots, which perfectly solves the problem of poor compatibility and difficulty in dispersion of carbon quantum dot particles and flame retardant in polyamide resin.

[0053] (3) The antistatic and flame-retardant bio-based nylon provided by this invention has a similar matrix structure to nylon resin. It can be directly melt-blended with other nylon resins to obtain the antistatic and flame-retardant nylon composite material without the use of any processing aids, thereby greatly reducing the difficulty of directly synthesizing antistatic and flame-retardant nylon resin. Furthermore, due to the similar structure between the antistatic and flame-retardant bio-based nylon and nylon resin, carbon quantum dots, flame retardants and nylon resin have good interaction, resulting in good mechanical properties of the antistatic and flame-retardant nylon composite material. In addition, the antistatic and flame-retardant bio-based nylon can also promote the crystallization of other nylon resins and form hydrogen bonds with other nylon resin matrices (hydrogen bonds formed by the misaligned distribution of amide groups during the melt blending process), thereby further improving the mechanical properties of the antistatic and flame-retardant nylon composite material. The carbon quantum dots can also act as physical crosslinking points, realizing in-situ nano-reinforcement and improving the antistatic properties of nylon resin. At the same time, the compatibilizer can perfectly improve the stability and fusion of the flame retardant, thereby improving the flame-retardant properties of nylon resin.

[0054] In summary, the present invention uses a specific compatibilizer in the preparation of antistatic and flame-retardant bio-based nylon. This compatibilizer enables the antistatic agent and flame retardant to exert greater effects, thereby giving the nylon material provided by the present invention excellent antistatic properties, flame retardant properties and mechanical properties, and stable antistatic and flame retardant effects. Detailed Implementation

[0055] 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.

[0056] 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.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] In this invention, unless otherwise specified, the term "two kinds" as used in this specification means "at least two kinds".

[0061] 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.

[0062] 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.

[0063] 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.

[0064] Preparation Example 1

[0065] This preparation example provides an isobutylene-maleic anhydride copolymer, which is prepared by a method including the following specific steps:

[0066] 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 the reaction vessel. After nitrogen purging for 30 min, 6 parts by weight of isobutylene were added. The temperature was then raised to 70°C and reacted for 3 h. After the reaction was completed, the mixture was cooled to room temperature and filtered. The filter cake was washed with ethanol, filtered, and then dried under vacuum to obtain the isobutylene-maleic anhydride copolymer.

[0067] The isobutylene maleic anhydride copolymer has the following structural formula (1) and its number-average molecular weight is 160,000.

[0068]

[0069] Examples and Comparative Examples of Antistatic and Flame-Resistant Bio-Based Nylon

[0070] Example 1

[0071] This embodiment provides an antistatic, flame-retardant bio-based nylon, which is prepared using a method comprising the following specific steps:

[0072] Step (1): First, grind 18.87 parts by weight of ammonium acetate and 20 parts by weight of maleic anhydride thoroughly to make their particle size similar and evenly dispersed; then add the resulting uniform mixture into a high-temperature and high-pressure reactor, and add a certain amount of 0.3 mol / L glacial acetic acid aqueous solution into the high-temperature and high-pressure reactor. Close the reactor, replace the air in the reactor with nitrogen three times, then turn on the stirrer and set the speed to 300 r / min. Heat to 100℃ and react at a constant temperature for 60 min. After the reaction is completed, slowly cool to room temperature. The generated carbon quantum dots are evenly dispersed in the glacial acetic acid aqueous solution to obtain the glacial acetic acid aqueous solution of carbon quantum dots.

[0073] 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 glacial acetic acid and disodium hydrogen phosphate in a mass ratio of 1:1), 2 parts by weight of antioxidant (antioxidant H3322), 50 parts by weight of nylon flame retardant MPP, and 3 parts by weight of compatibilizer (isobutylene maleic anhydride copolymer provided in Preparation Example 1) into a high-temperature and high-pressure reactor containing a glacial acetic acid aqueous solution of carbon quantum dots. Adjust the pH value to 7.2 using pentanediamine, replace the air in the reactor with an inert gas, such as nitrogen, start stirring, set the speed to 80 r / min, slowly raise the temperature to 80°C, hold the temperature for 1 h, and then raise the temperature to 210°C (prepolymerization reaction temperature) and hold the temperature for 3 h. After the in-situ polymerization reaction is completed, carbon quantum dot / polyamide composite prepolymer is obtained.

[0074] Step (3): After the reaction is complete, open the vent valve of the high-pressure reactor to slowly discharge water vapor and unreacted monomers or byproducts, and control the temperature to slowly rise to 260°C until it returns to normal pressure.

[0075] Step (4): After restoring normal pressure, vacuum is drawn at a constant temperature of 260℃. The vacuum degree increases by 0.020MPa every 10 minutes until it reaches -0.099MPa. After constant pressure reaction for 5 minutes, nitrogen is introduced to restore normal pressure. Then, the material is discharged, cast into a strip, cooled, and pelletized to obtain antistatic and flame-retardant bio-based nylon.

[0076] Example 2

[0077] This embodiment provides an antistatic, flame-retardant 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.

[0078] Example 3

[0079] This embodiment provides an antistatic, flame-retardant 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 160 parts by weight.

[0080] The amount of adipic acid used in Examples 1-3 of this invention, as well as the number-average molecular weight, tensile strength, volume resistivity and limiting oxygen index of the resulting antistatic and flame-retardant bio-based nylon, are shown in Table 1 below.

[0081] Table 1

[0082]

[0083] Note: Tensile strength was measured according to GB / T 1040.1-2018 Determination of Tensile Properties of Plastics; Limiting Oxygen Index was measured according to GB / T 2408-2008 Determination of Burning Performance of Plastics - Horizontal and Vertical Methods; Volume Resistivity was measured according to GB / T 31838.2-2109 Determination of Surface and Volume Resistivity of Insulating Materials.

[0084] As can be seen from Table 1, the number-average molecular weights of the antistatic and flame-retardant bio-based nylons provided in Examples 1-3 of this invention are all above 37,000, the tensile strengths are all above 84 MPa, and the volume resistivity is low, all below 10. 10 The Ω and limiting oxygen index are both 31, indicating that these antistatic and flame-retardant bio-based nylons possess excellent antistatic, flame-retardant, and mechanical properties. Table 1 also shows that the number-average molecular weight and tensile strength of the antistatic and flame-retardant bio-based nylons provided in Examples 1-3 of this invention first increase and then decrease with increasing adipic acid content, while the volume resistivity and limiting oxygen index do not change with the amount of adipic acid.

[0085] Example 4

[0086] This embodiment provides an antistatic, flame-retardant 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.

[0087] Example 5

[0088] This embodiment provides an antistatic, flame-retardant 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.

[0089] The amount of lubricant used in Examples 2 and 4-5 of this invention, as well as the number-average molecular weight, tensile strength, volume resistivity and limiting oxygen index of the resulting antistatic and flame-retardant bio-based nylon, are shown in Table 2 below.

[0090] Table 2

[0091]

[0092] Note: Tensile strength was measured according to GB / T 1040.1-2018 Determination of Tensile Properties of Plastics; Limiting Oxygen Index was measured according to GB / T 2408-2008 Determination of Burning Performance of Plastics - Horizontal and Vertical Methods; Volume Resistivity was measured according to GB / T 31838.2-2109 Determination of Surface and Volume Resistivity of Insulating Materials.

[0093] As can be seen from Table 2, the number-average molecular weight of the antistatic and flame-retardant bio-based nylons provided in Examples 2 and 4-5 of this invention is 38,000, the tensile strength is above 85 MPa, and the volume resistivity is low, all being 10. 10 The Ω and limiting oxygen index are both 31, indicating that these antistatic and flame-retardant bio-based nylons possess excellent antistatic, flame-retardant, and mechanical properties. Table 2 also shows that the tensile strength of the antistatic and flame-retardant bio-based nylons provided in Examples 2 and 4-5 of this invention increases with increasing lubricant dosage, while the number-average molecular weight, volume resistivity, and limiting oxygen index do not change with varying lubricant dosage.

[0094] Example 6

[0095] This embodiment provides an antistatic, flame-retardant 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.

[0096] Example 7

[0097] This embodiment provides an antistatic and flame-retardant 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.

[0098] The amount of catalyst used in Examples 5-7 of this invention, as well as the number-average molecular weight, tensile strength, volume resistivity and limiting oxygen index of the resulting antistatic and flame-retardant bio-based nylon, are shown in Table 3 below.

[0099] Table 3

[0100]

[0101] Note: Tensile strength was measured according to GB / T 1040.1-2018 Determination of Tensile Properties of Plastics; Limiting Oxygen Index was measured according to GB / T 2408-2008 Determination of Burning Performance of Plastics - Horizontal and Vertical Methods; Volume Resistivity was measured according to GB / T 31838.2-2109 Determination of Surface and Volume Resistivity of Insulating Materials.

[0102] As can be seen from Table 3, the number-average molecular weight of the antistatic and flame-retardant bio-based nylons provided in Examples 5-7 of this invention is 38,000, the tensile strength is above 87 MPa, and the volume resistivity is low, all being 10. 10 The Ω and limiting oxygen index are both 31, indicating that these antistatic and flame-retardant bio-based nylons possess excellent antistatic, flame-retardant, and mechanical properties. Table 3 also shows that the tensile strength of the antistatic and flame-retardant bio-based nylons provided in Examples 5-7 of this invention increases with increasing catalyst dosage, while the number-average molecular weight, volume resistivity, and limiting oxygen index do not change with varying catalyst dosage.

[0103] Example 8

[0104] This embodiment provides an antistatic, flame-retardant bio-based nylon, which differs from Embodiment 7 only in the amount of compatibilizer used. In this embodiment, the amount of compatibilizer used is 2 parts by weight.

[0105] Example 9

[0106] This embodiment provides an antistatic, flame-retardant bio-based nylon, which differs from Embodiment 7 only in the amount of compatibilizer used. In this embodiment, the amount of compatibilizer used is 5 parts by weight.

[0107] The amount of compatibilizer used in Examples 7-9 of this invention, as well as the number-average molecular weight, tensile strength, volume resistivity and limiting oxygen index of the resulting antistatic and flame-retardant bio-based nylon, are shown in Table 4 below.

[0108] Table 4

[0109]

[0110] Note: Tensile strength was measured according to GB / T 1040.1-2018 Determination of Tensile Properties of Plastics; Limiting Oxygen Index was measured according to GB / T 2408-2008 Determination of Burning Performance of Plastics - Horizontal and Vertical Methods; Volume Resistivity was measured according to GB / T 31838.2-2109 Determination of Surface and Volume Resistivity of Insulating Materials.

[0111] As can be seen from Table 4, the number-average molecular weights of the antistatic and flame-retardant bio-based nylons provided in Examples 7-9 of this invention are all above 37,000, the tensile strengths are all above 88 MPa, and the volume resistivity is low, not exceeding 10. 10Both the Ω and limiting oxygen index are above 28, indicating that these antistatic and flame-retardant bio-based nylons possess excellent antistatic, flame-retardant, and mechanical properties. Table 4 also shows that the number-average molecular weight, tensile strength, and limiting oxygen index of the antistatic and flame-retardant bio-based nylons provided in Examples 7-9 of this invention all increase with increasing compatibilizer dosage. Furthermore, when the compatibilizer dosage is 5 parts by weight, the volume resistivity of the material can be as low as 10. 9 Ω indicates that it has better antistatic properties.

[0112] Example 10

[0113] This embodiment provides an antistatic, flame-retardant bio-based nylon, which differs from Embodiment 9 only in the amount of antioxidant used. In this embodiment, the amount of antioxidant used is 2.5 parts by weight.

[0114] Example 11

[0115] This embodiment provides an antistatic, flame-retardant bio-based nylon, which differs from Embodiment 9 only in the amount of antioxidant used. In this embodiment, the amount of antioxidant used is 3 parts by weight.

[0116] The amount of antioxidant used in Examples 9-11 of this invention, as well as the number-average molecular weight, tensile strength, volume resistivity and limiting oxygen index of the resulting antistatic and flame-retardant bio-based nylon, are shown in Table 5 below.

[0117] Table 5

[0118]

[0119]

[0120] Note: Tensile strength was measured according to GB / T 1040.1-2018 Determination of Tensile Properties of Plastics; Limiting Oxygen Index was measured according to GB / T 2408-2008 Determination of Burning Performance of Plastics - Horizontal and Vertical Methods; Volume Resistivity was measured according to GB / T 31838.2-2109 Determination of Surface and Volume Resistivity of Insulating Materials.

[0121] As can be seen from Table 5, the number-average molecular weight of the antistatic and flame-retardant bio-based nylons provided in Examples 9-11 of this invention is 39,000, the tensile strength is above 92 MPa, and the volume resistivity is low, all being 10. 9Both the Ω and limiting oxygen index are above 32, indicating that these antistatic and flame-retardant bio-based nylons possess excellent antistatic, flame-retardant, and mechanical properties. Table 5 also shows that the tensile strength of the antistatic and flame-retardant bio-based nylons provided in Examples 9-11 of this invention increases with increasing antioxidant dosage, while the number-average molecular weight, limiting oxygen index, and volume resistivity do not change with varying antioxidant dosage.

[0122] Example 12

[0123] This embodiment provides an antistatic flame-retardant bio-based nylon, which differs from Embodiment 11 only in the amount of flame retardant used. In this embodiment, the amount of flame retardant used is 55 parts by weight.

[0124] Example 13

[0125] This embodiment provides an antistatic flame-retardant bio-based nylon, which differs from Embodiment 11 only in the amount of flame retardant used. In this embodiment, the amount of flame retardant used is 60 parts by weight.

[0126] The amount of flame retardant used in Examples 11-13 of this invention, as well as the number-average molecular weight, tensile strength, volume resistivity and limiting oxygen index of the resulting antistatic and flame-retardant bio-based nylon, are shown in Table 6 below.

[0127] Table 6

[0128]

[0129] Note: Tensile strength was measured according to GB / T 1040.1-2018 Determination of Tensile Properties of Plastics; Limiting Oxygen Index was measured according to GB / T 2408-2008 Determination of Burning Performance of Plastics - Horizontal and Vertical Methods; Volume Resistivity was measured according to GB / T 31838.2-2109 Determination of Surface and Volume Resistivity of Insulating Materials.

[0130] As can be seen from Table 6, the number-average molecular weight of the antistatic and flame-retardant bio-based nylons provided in Examples 11-13 of the present invention is 39,000, the tensile strength is above 94 MPa, and the volume resistivity is low, all being 10. 9 Both the Ω and limiting oxygen index are above 32, indicating that these antistatic and flame-retardant bio-based nylons possess excellent antistatic, flame-retardant, and mechanical properties. Table 6 also shows that the tensile strength and limiting oxygen index of the antistatic and flame-retardant bio-based nylons provided in Examples 11-13 of this invention increase with increasing flame retardant dosage, while the number-average molecular weight and volume resistivity do not change with varying flame retardant dosage.

[0131] Example 14

[0132] This embodiment provides an antistatic and flame-retardant bio-based nylon, which differs from Embodiment 2 only in the prepolymerization reaction temperature. In this embodiment, the prepolymerization reaction temperature is 200°C.

[0133] Example 15

[0134] This embodiment provides an antistatic and flame-retardant bio-based nylon, which differs from Embodiment 2 only in the prepolymerization reaction temperature. In this embodiment, the prepolymerization reaction temperature is 220°C.

[0135] The prepolymerization reaction temperature and the number-average molecular weight, tensile strength, volume resistivity and limiting oxygen index of the obtained antistatic and flame-retardant bio-based nylon in Examples 2 and 14-15 of this invention are shown in Table 7 below.

[0136] Table 7

[0137]

[0138] Note: Tensile strength was measured according to GB / T 1040.1-2018 Determination of Tensile Properties of Plastics; Limiting Oxygen Index was measured according to GB / T 2408-2008 Determination of Burning Performance of Plastics - Horizontal and Vertical Methods; Volume Resistivity was measured according to GB / T 31838.2-2109 Determination of Surface and Volume Resistivity of Insulating Materials.

[0139] As can be seen from Table 7, the number-average molecular weight of the antistatic and flame-retardant bio-based nylons provided in Examples 2 and 14-15 of the present invention is above 37,000, the tensile strength is above 81 MPa, and the volume resistivity is above 10. 10 The limiting oxygen index (Ω) and the limiting oxygen index (LOI) are both 31, indicating that these antistatic and flame-retardant bio-based nylons possess excellent antistatic, flame-retardant, and mechanical properties. Table 7 also shows that the tensile strength and number-average molecular weight of the antistatic and flame-retardant bio-based nylons provided in Examples 2 and 14-15 of this invention increase with increasing prepolymerization temperature, while the limiting oxygen index and volume resistivity do not change with the prepolymerization temperature.

[0140] Example 16

[0141] This embodiment provides an antistatic and flame-retardant bio-based nylon, which differs from Embodiment 2 only in the prepolymerization reaction time. In this embodiment, the prepolymerization reaction time is 1 hour.

[0142] Example 17

[0143] This embodiment provides an antistatic and flame-retardant bio-based nylon, which differs from Embodiment 2 only in the prepolymerization reaction time. In this embodiment, the prepolymerization reaction time is 2 hours.

[0144] The prepolymerization reaction time in Examples 2 and 16-17 of this invention, as well as the number-average molecular weight, tensile strength, volume resistivity and limiting oxygen index of the resulting antistatic and flame-retardant bio-based nylon, are shown in Table 8 below.

[0145] Table 8

[0146]

[0147] Note: Tensile strength was measured according to GB / T 1040.1-2018 Determination of Tensile Properties of Plastics; Limiting Oxygen Index was measured according to GB / T 2408-2008 Determination of Burning Performance of Plastics - Horizontal and Vertical Methods; Volume Resistivity was measured according to GB / T 31838.2-2109 Determination of Surface and Volume Resistivity of Insulating Materials.

[0148] As can be seen from Table 7, the number-average molecular weight of the antistatic and flame-retardant bio-based nylons provided in Examples 2 and 16-17 of the present invention is above 37,000, the tensile strength is above 81 MPa, and the volume resistivity is above 10. 10 Both the limiting oxygen index (Ω) and the limiting oxygen index (LOI) are 31, indicating that these antistatic and flame-retardant bio-based nylons possess excellent antistatic, flame-retardant, and mechanical properties. Table 8 also shows that the tensile strength of the antistatic and flame-retardant bio-based nylons provided in Examples 2 and 16-17 of this invention increases with increasing prepolymerization time, while the limiting oxygen index and volume resistivity do not change with prepolymerization temperature. Regarding the number-average molecular weight, when the prepolymerization time is 1 h and 2 h, the number-average molecular weight of the obtained antistatic and flame-retardant bio-based nylons remains unchanged, indicating that when the prepolymerization time is less than 2 h, the prepolymerization time has little effect on the number-average molecular weight of the antistatic and flame-retardant bio-based nylons. However, when the prepolymerization time is 3 h, the number-average molecular weight of the obtained antistatic and flame-retardant bio-based nylons increases, reaching 38,000.

[0149] Comparative Example 1

[0150] This comparative example provides a bio-based nylon, which differs from Example 2 only in that the carbon quantum dot generation process in this comparative example is not heated.

[0151] The heating conditions during the generation process of carbon quantum dots in Example 2 and Comparative Example 1 of the present invention, as well as the number-average molecular weight, tensile strength, volume resistivity and limiting oxygen index of the resulting bio-based nylon, are shown in Table 9 below.

[0152] Table 9

[0153]

[0154] Note: Tensile strength was measured according to GB / T 1040.1-2018 Determination of Tensile Properties of Plastics; Limiting Oxygen Index was measured according to GB / T 2408-2008 Determination of Burning Performance of Plastics - Horizontal and Vertical Methods; Volume Resistivity was measured according to GB / T 31838.2-2109 Determination of Surface and Volume Resistivity of Insulating Materials.

[0155] As can be seen from Table 9 above, compared with Example 2 of the present invention, Comparative Example 1 did not perform heat treatment on the carbon quantum dot generation process, and the resulting bio-based nylon had a volume resistivity as high as 10. 13 The antistatic properties were significantly reduced, indicating that, under the same conditions, the formation of carbon quantum dots requires heating and uniform dispersion of the carbon quantum dots in the solvent to achieve the antistatic effect. Furthermore, Table 9 shows that, compared to Example 2 of this invention, Comparative Example 1 did not involve heating during the formation of carbon quantum dots, resulting in a decrease in the tensile strength of the obtained bio-based nylon.

[0156] Comparative Example 2

[0157] This comparative example provides a bio-based nylon, which differs from Example 2 only in the reaction temperature of the carbon quantum dot generation process. The reaction temperature in this comparative example is 150°C.

[0158] The reaction temperature during the generation process of carbon quantum dots in Example 2 and Comparative Example 2 of the present invention, as well as the number-average molecular weight, tensile strength, volume resistivity and limiting oxygen index of the resulting bio-based nylon, are shown in Table 10 below.

[0159] Table 10

[0160]

[0161] Note: Tensile strength was measured according to GB / T 1040.1-2018 Determination of Tensile Properties of Plastics; Limiting Oxygen Index was measured according to GB / T 2408-2008 Determination of Burning Performance of Plastics - Horizontal and Vertical Methods; Volume Resistivity was measured according to GB / T 31838.2-2109 Determination of Surface and Volume Resistivity of Insulating Materials.

[0162] As can be seen from Table 10 above, compared with Example 2 of the present invention, the reaction temperature in the carbon quantum dot generation process of Comparative Example 2 is higher, reaching 150°C. At this temperature, the volume resistivity of the resulting bio-based nylon is as high as 10 Ω·cm. 14The antistatic properties were significantly reduced, indicating that under the same conditions, excessively high heating temperatures during the formation of carbon quantum dots would destroy their formation, and solvent evaporation would also occur, which is detrimental to improving the antistatic effect of nylon. Furthermore, Table 10 shows that compared to Example 2 of this invention, the reaction temperature during the formation of carbon quantum dots in Comparative Example 2 was higher, and the tensile strength of the resulting bio-based nylon was also slightly lower.

[0163] Comparative Example 3

[0164] This comparative example provides a bio-based nylon, which differs from Example 2 only in the reaction time of the carbon quantum dot generation process. The reaction time in this comparative example is 30 min.

[0165] Comparative Example 4

[0166] This comparative example provides a bio-based nylon, which differs from Example 2 only in the reaction time of the carbon quantum dot generation process. The reaction time in this comparative example is 120 min.

[0167] The reaction time during the generation of carbon quantum dots in Example 2 and Comparative Examples 3-4 of the present invention, as well as the number-average molecular weight, tensile strength, volume resistivity and limiting oxygen index of the resulting bio-based nylon, are shown in Table 11 below.

[0168] Table 11

[0169]

[0170] Note: Tensile strength was measured according to GB / T 1040.1-2018 Determination of Tensile Properties of Plastics; Limiting Oxygen Index was measured according to GB / T 2408-2008 Determination of Burning Performance of Plastics - Horizontal and Vertical Methods; Volume Resistivity was measured according to GB / T 31838.2-2109 Determination of Surface and Volume Resistivity of Insulating Materials.

[0171] As can be seen from Table 11 above, compared with Example 2 of the present invention, the reaction time in the carbon quantum dot generation process in Comparative Example 3 is shorter, only 30 min, and the volume resistivity of the resulting bio-based nylon is as high as 10. 13 The antistatic properties were significantly reduced, and the reaction time during the formation of carbon quantum dots in Comparative Example 4 was too long, only 120 min. At this time, the volume resistivity of the resulting bio-based nylon was as high as 10 Ω. 14The value Ω indicates a significant decrease in antistatic properties. This suggests that, under the same conditions, a reaction time that is too short for the formation of carbon quantum dots affects their formation and is detrimental to improving the antistatic effect of nylon. Conversely, a reaction time that is too long affects the quality of the carbon quantum dots and is also detrimental to improving the antistatic effect of nylon. Furthermore, compared to Example 2 of this invention, Table 11 also shows that the shorter reaction time in the carbon quantum dot formation process in Comparative Example 3 and the excessively long reaction time in the carbon quantum dot formation process in Comparative Example 4 resulted in a significant decrease in the tensile strength of the resulting bio-based nylon.

[0172] Based on the antistatic 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 carbon dots are not fully formed, resulting in a large number of unreacted monomers in the subsequent polymerization system. This causes some of the nylon polymerization reactions to stop, which weakens the interaction between carbon quantum dots and nylon resin, reduces the number of carbon quantum dots, and decreases the antistatic performance. On the other hand, if the temperature is too high or the reaction time is too long, some carbon dots will completely carbonize and lose their reactivity, making it difficult to react with nylon and resulting in poor dispersibility. The deactivated carbon dots have a weaker impact on the nylon polymerization reaction.

[0173] Comparative Example 5

[0174] This comparative example provides a bio-based nylon, which differs from Example 2 only in that no compatibilizer was used in this comparative example.

[0175] Comparative Example 6

[0176] 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 POE grafted with maleic anhydride.

[0177] The compatibilizer usage in Example 2 and Comparative Examples 5-6 of this invention, as well as the number-average molecular weight, tensile strength, volume resistivity, and limiting oxygen index of the resulting bio-based nylon, are shown in Table 12 below.

[0178] Table 12

[0179]

[0180] Note: Tensile strength was measured according to GB / T 1040.1-2018 Determination of Tensile Properties of Plastics; Limiting Oxygen Index was measured according to GB / T 2408-2008 Determination of Burning Performance of Plastics - Horizontal and Vertical Methods; Volume Resistivity was measured according to GB / T 31838.2-2109 Determination of Surface and Volume Resistivity of Insulating Materials.

[0181] As can be seen from Table 12 above, compared with Example 2 of the present invention, the limiting oxygen index of the bio-based nylon obtained in Comparative Example 5 without using a compatibilizer is only 25, and the flame retardant performance is significantly reduced. In Comparative Example 6, POE grafted maleic anhydride is used as a compatibilizer, and the limiting oxygen index of the bio-based nylon obtained is also only 27, and the flame retardant performance is significantly reduced. This indicates that the present invention uses a specific isobutylene-maleic anhydride copolymer as a compatibilizer, which can effectively integrate the flame retardant into the nylon material and achieve a stable flame retardant effect. In addition, as can be seen from Table 12, compared with Example 2 of the present invention, the tensile strength of the bio-based nylon obtained in Comparative Example 5 without using a compatibilizer and in Comparative Example 6 using POE grafted maleic anhydride as a compatibilizer is significantly reduced.

[0182] Comparative Example 7

[0183] This comparative example provides an antistatic, flame-retardant bio-based nylon, which differs from Example 9 only in the amount of compatibilizer used. In this example, the amount of compatibilizer used is 7 parts by weight.

[0184] The amount of compatibilizer used in Example 9 and Comparative Example 7 of this invention, as well as the number-average molecular weight, tensile strength, volume resistivity and limiting oxygen index of the resulting antistatic and flame-retardant bio-based nylon, are shown in Table 13 below.

[0185] Table 13

[0186]

[0187] Note: Tensile strength was measured according to GB / T 1040.1-2018 Determination of Tensile Properties of Plastics; Limiting Oxygen Index was measured according to GB / T 2408-2008 Determination of Burning Performance of Plastics - Horizontal and Vertical Methods; Volume Resistivity was measured according to GB / T 31838.2-2109 Determination of Surface and Volume Resistivity of Insulating Materials.

[0188] As can be seen from Table 13, compared to Example 9, in Comparative Example 7, increasing the amount of compatibilizer to 7 parts by weight did not change the number-average molecular weight, volume resistivity, and limiting oxygen index of the resulting antistatic and flame-retardant bio-based nylon, but the tensile strength decreased slightly. Therefore, considering the mechanical strength and production cost of the antistatic and flame-retardant bio-based nylon, this application sets the upper limit of the compatibilizer amount at 5 parts by weight.

[0189] Examples of antistatic and flame-retardant nylon 56 composite materials

[0190] Example 18

[0191] This embodiment provides an antistatic and flame-retardant nylon 56 composite material, which is prepared by a method including the following specific steps:

[0192] The antistatic and flame-retardant 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 the dried antistatic and flame-retardant 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 antistatic and flame-retardant nylon 56 composite material was obtained after extrusion and pelletizing.

[0193] 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 antistatic, flame-retardant bio-based nylon, characterized in that, The preparation method includes the following steps: Step (1): Carbon quantum dots are prepared in an aqueous glacial acetic acid medium using maleic anhydride and ammonium acetate as raw materials to obtain an aqueous glacial acetic acid solution containing carbon quantum dots; Step (2): In an inert atmosphere, an aqueous solution of diamine, diacid, catalyst, lubricant, antioxidant, flame retardant and compatibilizer is mixed with an aqueous solution of glacial acetic acid containing carbon quantum dots and subjected to in-situ polymerization to obtain a carbon quantum dot / polyamide composite prepolymer; wherein the compatibilizer is an 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 conditions until the system reaches the preset viscosity. After the reaction is completed, the system is discharged under normal pressure to obtain the antistatic and flame-retardant bio-based nylon.

2. The preparation method according to claim 1, characterized in that, Step (1) includes: mixing maleic anhydride and ammonium acetate in a molar ratio of 1-1.2:1 and grinding them evenly. Then, the resulting uniform mixture is mixed evenly with an aqueous solution of glacial acetic acid. The mixture is then heated to 90-120℃ under an inert atmosphere and stirring for 60-90 minutes. After the reaction is completed, the mixture is cooled to room temperature to obtain an aqueous solution of glacial acetic acid containing 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: 15-20 parts of ammonium acetate, 20 parts of maleic anhydride, 100 parts of diamine, 90-160 parts of dicarboxylic acid, 0.5-1 part of catalyst, 2-3 parts of lubricant, 2-3 parts of antioxidant, 2-5 parts of compatibilizer and 50-60 parts of flame retardant.

4. The preparation method according to any one of claims 1-3, characterized in that, In step (1), the concentration of the glacial acetic acid aqueous solution is 0.1-0.5 mol / L.

5. 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.

6. The preparation method according to any one of claims 1-3, characterized in that, In step (2), the catalyst comprises a mixture of glacial acetic acid 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.

7. The preparation method according to any one of claims 1-3, characterized in that, In step (2), the flame retardant is a nitrogen-based flame retardant, including one or a combination of melamine, melamine polyphosphate and melamine cyanurate.

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

9. 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 200-220℃ for 1-3h.

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

11. 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.

12. A bio-based nylon with antistatic and flame-retardant properties, characterized in that, The antistatic and flame-retardant bio-based nylon is prepared by the method for preparing antistatic and flame-retardant bio-based nylon according to any one of claims 1-11.

13. A static-resistant, flame-retardant nylon composite material, characterized in that, The antistatic and flame-retardant nylon composite material comprises the antistatic and flame-retardant bio-based nylon and nylon resin as described in claim 12.

14. The application of the antistatic and flame-retardant bio-based nylon of claim 12 or the antistatic and flame-retardant nylon composite material of claim 13 in clothing fabrics or mechanical equipment.

Images