CN114262517B - Nylon composite material and preparation method thereof - Google Patents
Nylon composite material and preparation method thereof Download PDFInfo
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- CN114262517B CN114262517B CN202111627742.3A CN202111627742A CN114262517B CN 114262517 B CN114262517 B CN 114262517B CN 202111627742 A CN202111627742 A CN 202111627742A CN 114262517 B CN114262517 B CN 114262517B
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Abstract
The invention discloses a nylon composite material and a preparation method thereof, wherein the nylon composite material is synthesized by the following raw materials: adipic acid, hexamethylenediamine, graphene-supported FeNi alloy, a double-grafted ethylene-octene copolymer, benzoic acid, a main antioxidant and an auxiliary antioxidant. The nylon composite material has excellent mechanical properties and wave absorbing properties, can be applied to various electronic products such as televisions, LED display screens, sound equipment, microwave ovens and mobile phones, and can reduce electromagnetic wave leakage below national sanitary safety limit values and ensure human health.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a nylon composite material and a preparation method thereof.
Background
Microwaves refer to electromagnetic waves having frequencies in the range of 300MHz-300 GHz. Microwaves have now been used in various aspects of human production and life. Among the most important applications are radar and communication. With the development of electronic equipment and communication technology, we increasingly live in a complex electromagnetic environment, and prevention and treatment of electromagnetic pollution are imperative. In addition, in military, how to evade detection of radar has become an important point of attention for various countries. Based on the above application requirements, microwave absorbing materials have been developed. The microwave absorption characteristics of a substance are mainly dependent on its dielectric properties (complex permittivity, epsilon=epsilon ' -j epsilon "), magnetic properties (complex permeability, mu=mu ' -j mu '), and the like. Accordingly, the wave-absorbing material may be classified into a dielectric wave-absorbing material and a magnetic wave-absorbing material. At present, the absorption frequency band of a dielectric wave-absorbing material based on carbon-based filler is narrow, and the wave-absorbing performance of a magnetic wave-absorbing material is limited by the high density and the Snoek limit (the phenomenon that the performance of absorbing interference waves is poor when reaching the GHz frequency band), so that the dielectric wave-absorbing material cannot be widely applied to military systems. Carbon-based materials such as carbon black, graphite, carbon fiber, carbon nanotubes, and the like have been studied extensively. As a novel carbon material, graphene has the characteristics of low density, high thermal conductivity, low resistivity, high electron mobility and the like. In graphene prepared by adopting an oxidation-reduction method, residual defects and groups can not only improve the impedance matching property of the graphene and enable the graphene to be rapidly converted into a fermi level state, but also generate polarization relaxation of the defects and electron dipole relaxation of the groups, and the defects and the groups are favorable for scattering and absorbing electromagnetic waves. It can be expected that graphene is a microwave absorbing material with great potential, and the composite wave absorbing material with more excellent performance is developed by using the graphene as an additive, so that the overall goal of 'thin, wide, light and strong' of the wave absorbing material is realized, and the graphene has important economic and social benefits for the development of the wave absorbing material in the military and civil fields.
At present, some researches are made in the prior art on nylon composite materials with wave absorbing performance, for example: chinese patent CN 111087684a discloses a polypropylene nylon 6 alloy micro-foaming wave-absorbing material, which comprises the following raw materials in percentage by weight: 96% of polypropylene nylon 6 composite material and the balance of chemical foaming agent; wherein, the polypropylene nylon 6 composite material comprises the following raw materials in parts by weight: 40 80 parts of polypropylene, 5 parts of nylon 6,2 parts of polycrystalline metal fiber, 1 part of compatilizer, 0.4 part of antioxidant, 0.5 part of lubricant, 0 2 parts of other auxiliary agents; chinese patent CN 106046770a discloses a nylon heat-conducting composite material for an LED lamp capable of absorbing waves, which is prepared from the following raw materials in parts by weight: 200 parts of nylon 6, 15-20 parts of manganese zinc ferrite, 15-20 parts of silicon carbide, 8-10 parts of glass fiber, 15-20 parts of carbon fiber, 50-60 parts of acetone, 80-100 parts of 60-70% nitric acid, 3-4 parts of silane coupling agent A, 70-80 parts of 1-3% acetic acid aqueous solution, 15-20 parts of 1, 6-hexamethylene diisocyanate, 20-25 parts of hydroxyethyl (meth) acrylate, 0.4-1 part of catalyst, 0.4-2 parts of polymerization inhibitor, 150-170 parts of tetrahydrofuran, 80-100 parts of toluene and a proper amount of deionized water.
It can be seen that the nylon composite materials with wave absorbing performance disclosed in the prior art are all obtained by adding an absorbent into the nylon material by a blending method, wherein the absorbent comprises metal fibers, manganese zinc ferrite and the like.
Disclosure of Invention
Based on the above, one of the purposes of the present invention is to prepare a nylon composite material with wave absorbing property by oxidizing a FeNi alloy to form a thin oxide film on the surface thereof, then loading the thin oxide film on the surface of graphene and dispersing the thin oxide film in a nylon base resin by an in-situ polymerization method.
The specific technical scheme for realizing the aim of the invention is as follows:
the nylon composite material is prepared from the following raw materials in parts by weight:
the dual-grafted ethylene and octene copolymer (HDE-g-POE-g-MGO) is prepared from an ammonia-containing base-based oligomer (HDE), ethylene and octene copolymer grafted maleic anhydride (POE-g-MAH) and Modified Graphene Oxide (MGO); the amino-containing base oligomer (HDE) is prepared by the reaction of Hexamethylenediamine (HDA) and Epichlorohydrin (ECH); the Modified Graphene Oxide (MGO) is prepared by organically modifying Graphene Oxide (GO) through 2, 3-epoxypropyl trimethyl ammonium chloride (GTA).
In some embodiments, the nylon composite is prepared from the following raw materials in parts by weight:
in some embodiments, the nylon composite is prepared from the following raw materials in parts by weight:
In some embodiments, the preparation method of the graphene-supported FeNi alloy (RGO-FeNi) comprises the following steps: (1) Dispersing 100 parts by weight of FeNi alloy in H 2 O 2 Adding ethanol solution into the solution, ultrasonically oscillating in ice water bath for 2-4 hours, collecting the modified FeNi alloy by using a magnet, and placing the magnet into a blast drying oven for drying to obtain the modified FeNi alloy; (2) Dispersing 100 parts by weight of graphene in a DMF solution, dispersing 15-35 parts by weight of modified FeNi alloy in an n-hexane solution, pouring the n-hexane solution into the DMF solution, ultrasonically oscillating for 1-2 hours, washing with ethanol for 1-3 times, and drying the obtained product at 50-70 ℃.
In some of these embodiments, the process for preparing the dual grafted ethylene and octene copolymer (HDE-g-POE-g-MGO) comprises the steps of:
(1) Adding 100 parts by weight of Hexamethylenediamine (HDA) into a three-mouth bottle filled with deionized water, slowly adding 35-55 parts by weight of Epichlorohydrin (ECH), controlling the system temperature to react for 5-7 hours at 20-30 ℃, heating to 60-80 ℃ to reflux and react for 0.5-1.5 hours, and decompressing, dehydrating and drying to obtain amino-containing polar oligomer (HDE);
(2) Adding 100 parts by weight of Graphene Oxide (GO) into a three-mouth bottle filled with deionized water, dispersing for 0.4-0.8 hour under ultrasonic waves, adding 30-50 parts by weight of 2, 3-epoxypropyl trimethyl ammonium chloride (GTA), controlling the temperature of a system to be 20-30 ℃ and stirring until light brown floccules are not precipitated any more, and finally washing the mixture for 1-3 times by using a centrifuge to obtain Modified Graphene Oxide (MGO);
(3) 100 parts by weight of ethylene, 30-50 parts by weight of POE-g-MAH and 30-50 parts by weight of amino-containing polar oligomer (HDE) are mixed in xylene, then the mixture is added into a reaction kettle, the temperature is raised to 120-140 ℃, after reflux reaction is carried out for 6-8 hours, 5-9 parts by weight of Modified Graphene Oxide (MGO) and 0.5-1.5 parts by weight of tetrabutylammonium bromide are added at normal temperature, after reflux reaction is carried out for 6-8 hours after the temperature is raised to 120-140 ℃, the mixture is cooled to room temperature, ethanol is used for cleaning for 1-3 times, and then the obtained product is dried and ground, thus obtaining the polymer.
In some of these embodiments, the primary antioxidant is N, N' -hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy-phenylpropionamide) and the secondary antioxidant is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite.
Another object of the present invention is to provide a method for preparing the above nylon composite.
The specific technical scheme for realizing the aim of the invention is as follows:
the preparation method of the nylon composite material comprises the following steps:
(1) Adding adipic acid and hexamethylenediamine into a stirring type polymerization reactor, and simultaneously adding graphene-loaded FeNi alloy (RGO-FeNi), a double-grafted ethylene-octene copolymer (HDE-g-POE-g-MGO), benzoic acid, a main antioxidant, an auxiliary antioxidant and a proper amount of water; then vacuumizing for 3-7 min, introducing nitrogen for 3-7 min, and circulating for 4-8 times, wherein the system pressure in the stirring type polymerization reactor is controlled to be 0.1-0.4 MPa;
(2) Heating the stirring type polymerization reactor to 80-100 ℃ in a sealing manner for 0.5-1.5 hours for salifying reaction for 0.5-1.5 hours, regulating the stirring speed of the stirring type polymerization reactor to 30-50 r/min, heating the stirring type polymerization reactor to 265-275 ℃ in a sealing manner, deflating to 1.8MPa when the temperature of the stirring type polymerization reactor reaches 220 ℃, maintaining the pressure at 1.8MPa, deflating to normal pressure after reaction for 1-3 hours (pre-polymerization reaction), continuing to react for 1-3 hours (post-polymerization reaction), continuously vacuumizing at constant temperature for 0.5-1.5 hours (adhesion reaction), and supplementing nitrogen after discharging.
In some of these embodiments, the method of making the nylon composite includes the steps of:
(1) Adding adipic acid and hexamethylenediamine into a stirring type polymerization reactor, and simultaneously adding graphene-loaded FeNi alloy (RGO-FeNi), a double-grafted ethylene-octene copolymer (HDE-g-POE-g-MGO), benzoic acid, a main antioxidant, an auxiliary antioxidant and a proper amount of water; then vacuumizing for 4-6 min, introducing nitrogen for 4-6 min, and circulating for 5-7 times, wherein the system pressure in the stirring type polymerization reactor is controlled to be 0.2-0.3 MPa;
(2) Heating the stirring type polymerization reactor to 85-95 ℃ in a sealing manner for 0.7-1.3 hours for salifying reaction for 0.7-1.3 hours, regulating the stirring speed of the stirring type polymerization reactor to 35-45 r/min, heating the stirring type polymerization reactor to 267-273 ℃ in a sealing manner, deflating to 1.8MPa when the temperature of the stirring type polymerization reactor reaches 220 ℃, maintaining the pressure at 1.8MPa, deflating to normal pressure after reacting for 1.5-2.5 hours (pre-polymerization), continuing to react for 1.5-2.5 hours (post-polymerization), continuously vacuumizing at constant temperature for 0.7-1.3 hours (adhesion reaction), and supplementing nitrogen after discharging.
The nylon composite material has the following functions:
the FeNi alloy has very high saturation magnetization and a knoek limit, but has higher conductivity, and obvious eddy current effect can occur in a high frequency band. The surface treatment is carried out on the FeNi alloy, so that the eddy current loss is reduced, and the reflection of electromagnetic waves is reduced. And taking n-hexane and DMF as organic solvents, and loading the modified FeNi alloy on the surface of the graphene sheet layer to form the magneto-dielectric type wave absorber. The modified FeNi alloy not only plays roles of improving magnetic loss and adjusting impedance, but also reduces the aggregation tendency of graphene due to the steric effect of the modified FeNi alloy. Therefore, graphene and the modified FeNi alloy are compounded, and the wave absorbing performance of the composite material is improved.
The dual-grafted ethylene and octene copolymer (HDE-g-POE-g-MGO) is prepared from an amino-containing base oligomer (HDE), ethylene and octene copolymer grafted maleic anhydride (POE-g-MAH) and Modified Graphene Oxide (MGO). The principle is as follows: firstly, hexamethylenediamine (HDA) and Epichlorohydrin (ECH) are subjected to nucleophilic substitution reaction to prepare an amino-containing polar oligomer (HDE), then, the polar chain HDE containing amino and an ethylene-octene copolymer grafted maleic anhydride (POE-g-MAH) containing maleic anhydride functional groups are subjected to acylation reaction to obtain HDE-g-POE, and finally, the HDE-g-POE is reacted with Modified Graphene Oxide (MGO) to prepare the novel reactive compatibilizer double-grafted ethylene-octene copolymer (HDE-g-POE-g-MGO). Among them, the HDE functions as follows: (1) The polarity portion HDE can balance the non-polarity of POE in the HDE-g-POE-g-MGO; (2) Reactive groups within the HDE may react with the MGO, which is then grafted onto the compatibilizer; (3) The reactive groups in the HDE can form hydrogen bonds with terminal amino groups on the polyamide. The role of the MGO is as follows: (1) The specific surface area of the MGO is large, and the surface and the tail end of the sheet layer contain a large amount of rich oxygen-containing functional groups to provide active sites for reaction; (2) Carboxyl groups on the MGO can form hydrogen bonds with terminal amino groups on the polyamide; (3) The MGO and the graphene-loaded FeNi alloy have stronger interaction, and are favorable for the dispersion of the wave absorber in the nylon resin substrate.
Benzoic acid is carboxylic acid with a single functional group, and can terminate the chain growth reaction of the nylon material, so that the molecular weight (i.e. the intrinsic viscosity) of the nylon material is regulated, and the nylon material has better mechanical property and processability.
The main antioxidant N, N' -hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy-benzene propionamide) and the auxiliary antioxidant are bis (2, 4-dicumylphenyl) pentaerythritol diphosphite which has higher heat resistance, is suitable for being used in synthetic preparation, and has good compatibility with nylon materials.
Compared with the prior art, the nylon composite material and the preparation method thereof have the following beneficial effects:
1. according to the invention, adipic acid, hexamethylenediamine, graphene-supported FeNi alloy (RGO-FeNi) and double-grafted ethylene-octene copolymer (HDE-g-POE-g-MGO) which are prepared by adopting raw materials in a specific proportion, and simultaneously adding benzoic acid to regulate the intrinsic viscosity of the polymer, the nylon composite material with excellent mechanical properties and wave absorbing performance is prepared, the intrinsic viscosity is 1.12 dL/g-1.64 dL/g (according to GB/T1632-2008 standard test, the solvent is concentrated sulfuric acid), the melting temperature is 263-265 ℃ (according to GB/T19466.3-2004 standard test), the wave absorbing performance is-12 to-32 dB (the operating frequency is 12-20 GHz, according to GJB 5239-2004 standard test), and the nylon composite material can be applied to various electronic products such as televisions, LED display screens, audios, VCD machines, computers, digital cameras, game machines, microwave ovens and mobile phones, and can ensure that electromagnetic waves are leaked below national sanitary safety limit (10 microwatts per square centimeter) and human health.
2. According to the invention, the FeNi alloy is used for loading the graphene sheet to prepare the magneto-dielectric type wave absorber, so that the wave absorber has the effects of improving magnetic loss and adjusting impedance, reduces the aggregation trend of graphene due to the self steric effect, and effectively solves the defects of poor high-frequency wave absorbing performance (Snoek limit), easy aggregation and poor dispersibility of the magnetic wave absorbing material.
3. According to the preparation method of the nylon composite material, nitrogen is introduced before the reaction, so that the probability of occurrence of side reaction is reduced; adding a proper amount of water before the reaction, so as to increase the pressure in the kettle and transfer mass and heat in the heating process; the vacuum is pumped in the reaction process, so that the low-molecular extractables generated in the polymerization reaction process are removed, the forward polymerization reaction is facilitated, the performance of the nylon composite material is not affected by the residual low-molecular extractables, and therefore, additional extraction equipment is not needed to separate the low-molecular extractables, and the time and energy can be saved; the preparation method is simple, all reactions do not need to be carried out in the solvent, and the complex process of removing the solvent subsequently is omitted.
Drawings
FIG. 1 is a flow chart of a preparation process of the nylon composite material of the invention.
Fig. 2 is a transmission electron microscope image of the graphene-supported FeNi alloy prepared by the method.
Detailed Description
In order that the invention may be understood more fully, the invention will be described with reference to the accompanying drawings. This invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The reaction mechanism of the nylon composite material of the invention is as follows (the preparation process flow chart is shown in figure 1):
wherein n=1 to 5, and R is HDE-g-POE-g-MGO.
Reaction mechanism
From the above reaction formula, (1) Hexamethylenediamine (HDA) and Epichlorohydrin (ECH) are reacted to synthesize an amino-containing polar oligomer (HDE); (2) 2, 3-epoxypropyl trimethyl ammonium chloride (GTA) is electrostatically intercalated into Graphene Oxide (GO) sheets, and the method not only ensures that the GO sheets are easier to peel off and improves the dispersity of GO in a polymer matrix, but also provides active epoxy groups for the reaction of GO and HDE-g-POE; (3) Acylating amino-containing polar oligomer (HDE) with nonpolar POE-g-MAH to obtain HDE-g-POE, and then reacting with MGO nano-sheets to obtain double grafting compatilizer HDE-g-POE-g-MGO; (4) The amino-terminated groups of the HDE-g-POE-g-MGO can react with the carboxyl-terminated groups of the PA66, so that the compatibility and interfacial bonding force of the HDE-g-POE-g-MGO and nylon base material resin are improved, and the POE chain segment is excellent in flexibility, so that a large amount of external impact energy is absorbed, the impact performance of the polyamide composite material is improved, and the interaction between the MGO chain segment and graphene-loaded FeNi alloy is improved, so that the dispersion of the graphene-loaded FeNi alloy in the nylon base material resin is improved.
The raw materials used in the embodiment of the invention are as follows:
adipic acid, purchased from the company of China's god horse group, inc.
Hexamethylenediamine, purchased from the company of the chinese god-horse group, ltd.
FeNi alloy, fe 50 Ni 50 Nanometer powder with particle size of 70nm and purchased from Xu Zhoujie innovative materialTechnology limited.
Graphene, purchased from nanjing Jibin nanotechnology limited.
H 2 O 2 Purchased from national pharmaceutical group chemical reagent limited.
Ethanol, available from national pharmaceutical group chemical company, inc.
N-hexane, available from national pharmaceutical groups chemical Co., ltd.
N, N-Dimethylformamide (DMF) was purchased from national pharmaceutical composition chemical reagent Co.
Epichlorohydrin is available from megabang chemical Co., yangzhou.
Graphene oxide, purchased from nanjing Jibin nanotechnology limited.
2, 3-epoxypropyl trimethyl ammonium chloride, available from Hubei Tosoh chemical technology Co., ltd.
The ethylene and octene copolymer was grafted with maleic anhydride, the grafting ratio of maleic anhydride was 1.2%, shenyang Kogyo Plastic Co.
Tetrabutylammonium bromide was purchased from atactic chemical company, inc.
Benzoic acid, available from national pharmaceutical group chemical company, inc.
N, N' -hexamethylenebis (3, 5-di-t-butyl-4-hydroxyphenylpropionamide), available from Zhengzhou Ai Kem chemical Co., ltd.
Bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, available from Shanghai Yao fine chemical Co., ltd.
Polyamide 66, available from the company of the chinese godet group, inc.
The graphene-supported FeNi alloy (RGO-FeNi) used in the following examples was prepared by the following steps:
(1) 100g of FeNi alloy was dispersed in 1L of H 2 O 2 Adding 0.5L of ethanol solution into the solution, ultrasonically oscillating for 3 hours in ice-water bath, collecting the modified FeNi alloy by using a magnet, and drying in a blast drying oven to obtain the modified FeNi alloy;
(2) 100g of graphene is dispersed in 1L of DMF solution, 25g of modified FeNi alloy is dispersed in 0.5L of n-hexane solution, then the n-hexane solution is poured into the DMF solution, ultrasonic oscillation is carried out for 1.5 hours, then ethanol is used for cleaning for 2 times, and the obtained product is dried at 60 ℃.
Fig. 2 is a transmission electron microscope image of the graphene-supported FeNi alloy prepared by the method.
The double grafted ethylene and octene copolymer (HDE-g-POE-g-MGO) used in the following examples was prepared by a process comprising the steps of:
(1) 100g of Hexamethylenediamine (HDA) is added into a three-mouth bottle filled with deionized water, 45g of Epichlorohydrin (ECH) is slowly added, the temperature of the system is controlled to be 25 ℃ for 6 hours, the temperature is increased to 70 ℃ for reflux reaction for 1 hour, and the polar oligomer (HDE) containing amino is obtained after decompression, dehydration and drying;
(2) Adding 100g of Graphene Oxide (GO) into a three-mouth bottle filled with deionized water, dispersing for 0.6 hour under ultrasonic wave, adding 40g of 2, 3-epoxypropyl trimethyl ammonium chloride (GTA), controlling the system temperature at 25 ℃ and stirring until light brown floccules are not precipitated, and finally washing the mixture for 2 times by using a centrifuge to obtain Modified Graphene Oxide (MGO);
(3) 100g of ethylene, octene copolymer grafted maleic anhydride (POE-g-MAH) and 40g of ammonia-containing base-based oligomer (HDE) are mixed in xylene, then the mixture is added into a reaction kettle, the temperature is raised to 130 ℃, reflux reaction is carried out for 7 hours, then 7g of Modified Graphene Oxide (MGO) and 1g of tetrabutylammonium bromide are added at normal temperature, the temperature is raised to 130 ℃, reflux reaction is carried out for 7 hours, the mixture is cooled to the room temperature, the mixture is washed with ethanol for 2 times, and then the obtained product is dried and ground, thus obtaining the catalyst.
The present invention will be described in detail with reference to specific examples.
Example 1 Nylon composite material and method for preparing same
The nylon composite material of the embodiment is prepared from the following raw materials in parts by weight:
the preparation method of the nylon composite material comprises the following steps:
(1) Adding adipic acid and hexamethylenediamine into a stirring type polymerization reactor, and simultaneously adding graphene-supported FeNi alloy (RGO-FeNi), a double-grafted ethylene-octene copolymer (HDE-g-POE-g-MGO), benzoic acid, N' -hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy-phenylpropionamide), bis (2, 4-dicumylphenyl) pentaerythritol diphosphite and a proper amount of water; then vacuumizing for 7min, introducing nitrogen for 7min, circulating for 4 times, and controlling the system pressure in the stirring type polymerization reactor to be 0.4MPa;
(2) And (3) heating the stirring type polymerization reactor to 100 ℃ in a sealing manner for 1.5 hours for salifying reaction, regulating the stirring speed of the stirring type polymerization reactor to 50r/min, heating the stirring type polymerization reactor to 275 ℃ in a sealing manner, deflating to 1.8MPa when the temperature of the stirring type polymerization reactor reaches 220 ℃, maintaining the pressure at 1.8MPa, deflating to normal pressure after reacting for 1 hour (pre-polymerization reaction), continuing reacting for 1 hour (post-polymerization reaction), continuously vacuumizing at constant temperature for 1.5 hours (tackifying reaction), and supplementing nitrogen when discharging to obtain the catalyst.
Example 2 Nylon composite material and method for preparing same
The nylon composite material of the embodiment is prepared from the following raw materials in parts by weight:
the preparation method of the nylon composite material comprises the following steps:
(1) Adding adipic acid and hexamethylenediamine into a stirring type polymerization reactor, and simultaneously adding graphene-supported FeNi alloy (RGO-FeNi), a double-grafted ethylene-octene copolymer (HDE-g-POE-g-MGO), benzoic acid, N' -hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy-phenylpropionamide), bis (2, 4-dicumylphenyl) pentaerythritol diphosphite and a proper amount of water; then vacuumizing for 3min, introducing nitrogen for 3min, circulating for 8 times, and controlling the system pressure in the stirring type polymerization reactor to be 0.1MPa;
(2) And (3) heating the stirring type polymerization reactor to 80 ℃ in a sealing manner for 0.5 hour to carry out salt forming reaction, regulating the stirring speed of the stirring type polymerization reactor to 30r/min, heating the stirring type polymerization reactor to 265 ℃ in a sealing manner, deflating to 1.8MPa when the temperature of the stirring type polymerization reactor reaches 220 ℃, maintaining the pressure at 1.8MPa, deflating to normal pressure after 3 hours (pre-polymerization reaction), continuing to react for 3 hours (post-polymerization reaction), continuously vacuumizing at constant temperature for 0.5 hour (tackifying reaction), and supplementing nitrogen when discharging to obtain the catalyst.
Example 3 Nylon composite material and method of making the same
The nylon composite material of the embodiment is prepared from the following raw materials in parts by weight:
the preparation method of the nylon composite material comprises the following steps:
(1) Adding adipic acid and hexamethylenediamine into a stirring type polymerization reactor, and simultaneously adding graphene-supported FeNi alloy (RGO-FeNi), a double-grafted ethylene-octene copolymer (HDE-g-POE-g-MGO), benzoic acid, N' -hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy-phenylpropionamide), bis (2, 4-dicumylphenyl) pentaerythritol diphosphite and a proper amount of water; then vacuumizing for 6min, introducing nitrogen for 6min, circulating for 5 times, and controlling the system pressure in the stirring type polymerization reactor to be 0.3MPa;
(2) And (3) heating the stirring type polymerization reactor to 95 ℃ in a sealing manner for 1.3 hours to carry out salt forming reaction, regulating the stirring speed of the stirring type polymerization reactor to 45r/min, heating the stirring type polymerization reactor to 273 ℃ in a sealing manner, deflating to 1.8MPa when the temperature of the stirring type polymerization reactor reaches 220 ℃, maintaining the pressure at 1.8MPa, reacting for 1.5 hours (pre-polymerization reaction), deflating to normal pressure, continuing to react for 1.5 hours (post-polymerization reaction), continuously vacuumizing at constant temperature for 1.3 hours (tackifying reaction), finishing the reaction, and supplementing nitrogen when discharging to obtain the catalyst.
Example 4 Nylon composite material and method for preparing same
The nylon composite material of the embodiment is prepared from the following raw materials in parts by weight:
the preparation method of the nylon composite material comprises the following steps:
(1) Adding adipic acid and hexamethylenediamine into a stirring type polymerization reactor, and simultaneously adding graphene-supported FeNi alloy (RGO-FeNi), a double-grafted ethylene-octene copolymer (HDE-g-POE-g-MGO), benzoic acid, N' -hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy-phenylpropionamide), bis (2, 4-dicumylphenyl) pentaerythritol diphosphite and a proper amount of water; then vacuumizing for 4min, introducing nitrogen for 4min, circulating for 7 times, and controlling the system pressure in the stirring type polymerization reactor to be 0.2MPa;
(2) And (3) heating the stirring type polymerization reactor to 85 ℃ in a sealing manner for 0.7 hour to carry out salification reaction, regulating the stirring speed of the stirring type polymerization reactor to 35r/min, heating the stirring type polymerization reactor to 267 ℃ in a sealing manner, deflating to 1.8MPa when the temperature of the stirring type polymerization reactor reaches 220 ℃, maintaining the pressure at 1.8MPa, reacting for 2.5 hours (pre-polymerization reaction), deflating to normal pressure, continuing to react for 2.5 hours (post-polymerization reaction), continuously vacuumizing at constant temperature for 0.7 hour (adhesion reaction), finishing the reaction, and supplementing nitrogen when discharging to obtain the catalyst.
Example 5 Nylon composite material and method of making the same
The nylon composite material of the embodiment is prepared from the following raw materials in parts by weight:
the preparation method of the nylon composite material comprises the following steps:
(1) Adding adipic acid and hexamethylenediamine into a stirring type polymerization reactor, and simultaneously adding graphene-supported FeNi alloy (RGO-FeNi), a double-grafted ethylene-octene copolymer (HDE-g-POE-g-MGO), benzoic acid, N' -hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy-phenylpropionamide), bis (2, 4-dicumylphenyl) pentaerythritol diphosphite and a proper amount of water; then vacuumizing for 5min, introducing nitrogen for 5min, circulating for 6 times, and controlling the system pressure in the stirring type polymerization reactor to be 0.25MPa;
(2) And (3) heating the stirring type polymerization reactor to 90 ℃ in a sealing manner for salifying reaction for 1 hour, regulating the stirring speed of the stirring type polymerization reactor to 40r/min, heating the stirring type polymerization reactor to 270 ℃ in a sealing manner, deflating to 1.8MPa when the temperature of the stirring type polymerization reactor reaches 220 ℃, maintaining the pressure at 1.8MPa, deflating to normal pressure after reacting for 2 hours (pre-polymerization reaction), continuing reacting for 2 hours (post-polymerization reaction), continuously vacuumizing at constant temperature for 1 hour (tackifying reaction), and supplementing nitrogen when discharging to obtain the catalyst.
Example 6 Nylon composite material and method for preparing same
The nylon composite material of the embodiment is prepared from the following raw materials in parts by weight:
the preparation method of the nylon composite material comprises the following steps:
(1) Adding adipic acid and hexamethylenediamine into a stirring type polymerization reactor, and simultaneously adding graphene-supported FeNi alloy (RGO-FeNi), a double-grafted ethylene-octene copolymer (HDE-g-POE-g-MGO), benzoic acid, N' -hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy-phenylpropionamide), bis (2, 4-dicumylphenyl) pentaerythritol diphosphite and a proper amount of water; then vacuumizing for 5min, introducing nitrogen for 5min, circulating for 6 times, and controlling the system pressure in the stirring type polymerization reactor to be 0.25MPa;
(2) And (3) heating the stirring type polymerization reactor to 90 ℃ in a sealing manner for salifying reaction for 1 hour, regulating the stirring speed of the stirring type polymerization reactor to 40r/min, heating the stirring type polymerization reactor to 270 ℃ in a sealing manner, deflating to 1.8MPa when the temperature of the stirring type polymerization reactor reaches 220 ℃, maintaining the pressure at 1.8MPa, deflating to normal pressure after reacting for 2 hours (pre-polymerization reaction), continuing reacting for 2 hours (post-polymerization reaction), continuously vacuumizing at constant temperature for 1 hour (tackifying reaction), and supplementing nitrogen when discharging to obtain the catalyst.
Example 7 Nylon composite material and method for preparing same
The nylon composite material of the embodiment is prepared from the following raw materials in parts by weight:
the preparation method of the nylon composite material comprises the following steps:
(1) Adding adipic acid and hexamethylenediamine into a stirring type polymerization reactor, and simultaneously adding graphene-supported FeNi alloy (RGO-FeNi), a double-grafted ethylene-octene copolymer (HDE-g-POE-g-MGO), benzoic acid, N' -hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy-phenylpropionamide), bis (2, 4-dicumylphenyl) pentaerythritol diphosphite and a proper amount of water; then vacuumizing for 5min, introducing nitrogen for 5min, circulating for 6 times, and controlling the system pressure in the stirring type polymerization reactor to be 0.25MPa;
(2) And (3) heating the stirring type polymerization reactor to 90 ℃ in a sealing manner for salifying reaction for 1 hour, regulating the stirring speed of the stirring type polymerization reactor to 40r/min, heating the stirring type polymerization reactor to 270 ℃ in a sealing manner, deflating to 1.8MPa when the temperature of the stirring type polymerization reactor reaches 220 ℃, maintaining the pressure at 1.8MPa, deflating to normal pressure after reacting for 2 hours (pre-polymerization reaction), continuing reacting for 2 hours (post-polymerization reaction), continuously vacuumizing at constant temperature for 1 hour (tackifying reaction), and supplementing nitrogen when discharging to obtain the catalyst.
Comparative example 1
The nylon composite material of the comparative example is prepared from the following raw materials in parts by weight:
the preparation method of the nylon composite material comprises the following steps:
(1) Adding adipic acid and hexamethylenediamine into a stirring type polymerization reactor, and simultaneously adding a double-grafted ethylene-octene copolymer (HDE-g-POE-g-MGO), benzoic acid, N' -hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy-phenyl-propionamide), bis (2, 4-dicumylphenyl) pentaerythritol diphosphite and a proper amount of water; then vacuumizing for 5min, introducing nitrogen for 5min, circulating for 6 times, and controlling the system pressure in the stirring type polymerization reactor to be 0.25MPa;
(2) And (3) heating the stirring type polymerization reactor to 90 ℃ in a sealing manner for salifying reaction for 1 hour, regulating the stirring speed of the stirring type polymerization reactor to 40r/min, heating the stirring type polymerization reactor to 270 ℃ in a sealing manner, deflating to 1.8MPa when the temperature of the stirring type polymerization reactor reaches 220 ℃, maintaining the pressure at 1.8MPa, deflating to normal pressure after reacting for 2 hours (pre-polymerization reaction), continuing reacting for 2 hours (post-polymerization reaction), continuously vacuumizing at constant temperature for 1 hour (tackifying reaction), and supplementing nitrogen when discharging to obtain the catalyst.
Comparative example 2
The nylon composite material of the comparative example is prepared from the following raw materials in parts by weight:
the preparation method of the nylon composite material comprises the following steps:
(1) Adding adipic acid and hexamethylenediamine into a stirring type polymerization reactor, and simultaneously adding FeNi alloy, a double-grafted ethylene-octene copolymer (HDE-g-POE-g-MGO), benzoic acid, N' -hexamethylenebis (3, 5-di-tert-butyl-4-hydroxyphenylpropionamide) and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite and a proper amount of water; then vacuumizing for 5min, introducing nitrogen for 5min, circulating for 6 times, and controlling the system pressure in the stirring type polymerization reactor to be 0.25MPa;
(2) And (3) heating the stirring type polymerization reactor to 90 ℃ in a sealing manner for salifying reaction for 1 hour, regulating the stirring speed of the stirring type polymerization reactor to 40r/min, heating the stirring type polymerization reactor to 270 ℃ in a sealing manner, deflating to 1.8MPa when the temperature of the stirring type polymerization reactor reaches 220 ℃, maintaining the pressure at 1.8MPa, deflating to normal pressure after reacting for 2 hours (pre-polymerization reaction), continuing reacting for 2 hours (post-polymerization reaction), continuously vacuumizing at constant temperature for 1 hour (tackifying reaction), and supplementing nitrogen when discharging to obtain the catalyst.
Comparative example 3
The nylon composite material of the comparative example is prepared from the following raw materials in parts by weight:
the preparation method of the nylon composite material comprises the following steps:
(1) Adding adipic acid and hexamethylenediamine into a stirring type polymerization reactor, and simultaneously adding graphene-supported FeNi alloy (RGO-FeNi), benzoic acid, N' -hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy-phenyl-propionamide) and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite and a proper amount of water; then vacuumizing for 5min, introducing nitrogen for 5min, circulating for 6 times, and controlling the system pressure in the stirring type polymerization reactor to be 0.25MPa;
(2) And (3) heating the stirring type polymerization reactor to 90 ℃ in a sealing manner for salifying reaction for 1 hour, regulating the stirring speed of the stirring type polymerization reactor to 40r/min, heating the stirring type polymerization reactor to 270 ℃ in a sealing manner, deflating to 1.8MPa when the temperature of the stirring type polymerization reactor reaches 220 ℃, maintaining the pressure at 1.8MPa, deflating to normal pressure after reacting for 2 hours (pre-polymerization reaction), continuing reacting for 2 hours (post-polymerization reaction), continuously vacuumizing at constant temperature for 1 hour (tackifying reaction), and supplementing nitrogen when discharging to obtain the catalyst.
Comparative example 4
The nylon composite material of the comparative example is prepared from the following raw materials in parts by weight:
the preparation method of the nylon composite material comprises the following steps:
(1) Adding adipic acid and hexamethylenediamine into a stirring type polymerization reactor, and simultaneously adding graphene-supported FeNi alloy (RGO-FeNi), a double-grafted ethylene-octene copolymer (HDE-g-POE-g-MGO), N' -hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy-phenyl-propionamide), bis (2, 4-dicumylphenyl) pentaerythritol diphosphite and a proper amount of water; then vacuumizing for 5min, introducing nitrogen for 5min, circulating for 6 times, and controlling the system pressure in the stirring type polymerization reactor to be 0.25MPa;
(2) And (3) heating the stirring type polymerization reactor to 90 ℃ in a sealing manner for salifying reaction for 1 hour, regulating the stirring speed of the stirring type polymerization reactor to 40r/min, heating the stirring type polymerization reactor to 270 ℃ in a sealing manner, deflating to 1.8MPa when the temperature of the stirring type polymerization reactor reaches 220 ℃, maintaining the pressure at 1.8MPa, deflating to normal pressure after reacting for 2 hours (pre-polymerization reaction), continuing reacting for 2 hours (post-polymerization reaction), continuously vacuumizing at constant temperature for 1 hour (tackifying reaction), and supplementing nitrogen when discharging to obtain the catalyst.
Comparative example 5
The nylon composite material of the comparative example is prepared from the following raw materials in parts by weight:
the preparation method of the nylon composite material comprises the following steps:
(1) Drying the polyamide 66 at 110 ℃ for 3 hours, cooling, and placing the cooled polyamide 66 for later use;
(2) Adding the graphene-supported FeNi alloy (RGO-FeNi), a double-grafted ethylene and octene copolymer (HDE-g-POE-g-MGO), N' -hexamethylene bis (3, 5-di-tert-butyl-4-hydroxy-phenyl-propionamide) and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into another high-speed stirrer (with the rotating speed of 1000 revolutions per minute) for mixing;
(3) Feeding the polyamide 66 dried in the step (1) into a parallel double-screw extruder through a feeder, and adding the mixture mixed in the step (2) in the lateral direction (fourth zone) of the parallel double-screw extruder (total eight zones) for melt extrusion and granulation, wherein the technological parameters are as follows: the first zone temperature is 210 ℃, the second zone temperature is 220 ℃, the third zone temperature is 225 ℃, the fourth zone temperature is 230 ℃, the fifth zone temperature is 230 ℃, the sixth zone temperature is 230 ℃, the seventh zone temperature is 230 ℃, the eighth zone temperature is 230 ℃, the die temperature is 225 ℃, and the screw rotating speed is 400rpm.
The following is a list of the raw material compositions of examples 1-7 and comparative examples 1-5.
Table 1 list of raw material compositions of examples 1 to 7 and comparative examples 1 to 5
Remarks: a, replacing the graphene-loaded FeNi alloy with FeNi alloy; b, adipic acid is replaced by polyamide 66.
Wherein the primary antioxidant in the above examples and comparative examples is N, N' -hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy-phenyl-propionamide), and the secondary antioxidant is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite.
Examples 1 to 7 were nylon composite materials prepared by adjusting the addition amounts of adipic acid, hexamethylenediamine, graphene-supported FeNi alloy (RGO-FeNi), double-grafted ethylene and octene copolymer (HDE-g-POE-g-MGO), and benzoic acid, comparative examples 1 to 5 were nylon composite materials prepared on the basis of the raw materials of example 7, comparative example 1 was not added with graphene-supported FeNi alloy, comparative example 2 was replaced with FeNi alloy, comparative example 3 was not added with double-grafted ethylene and octene copolymer (HDE-g-POE-g-MGO), comparative example 4 was not added with benzoic acid, and comparative example 5 was prepared with polyamide 66 resin. The nylon composite materials prepared in the above examples and comparative examples were subjected to the following performance tests:
Tensile properties: the stretching rate was 50mm/min as tested according to GB/T1040-2006 standard.
Notched impact properties: tested according to GB/T1843-2008 standard.
Melt index: the test is carried out according to GB/T3682-2000 standard, the test temperature is 275 ℃, and the load is 2.16kg.
Wave absorbing performance: the test is carried out according to GJB 5239-2004 standard by adopting a vector network analyzer of Agilent company in China, and the sample is a coaxial circular ring sample with the thickness of 2mm, the outer diameter of 7mm and the inner diameter of 3 mm. The wider the width of the microwave frequency, the better the coverage of the microwave frequency is, and the higher the microwave frequency is, the better the microwave frequency is; the wave absorbing performance reflects the wave absorbing capability of the material to electromagnetic waves, and the larger the absolute value of the value is, the more the electromagnetic waves are attenuated after passing through the material, and the better the wave absorbing performance is.
Intrinsic viscosity: according to GB/T1632-2008 standard test, the solvent is concentrated sulfuric acid.
Melting temperature: tested according to GB/T19466.3-2004 standard.
The results of the performance test are shown in Table 2.
Table 2 performance tables for nylon composites of examples 1-7 and comparative examples 1-5
As can be seen from table 2:
along with the decrease of the addition amount of graphene-loaded FeNi alloy (RGO-FeNi), double-grafted ethylene-octene copolymer (HDE-g-POE-g-MGO) and benzoic acid, the tensile strength of the nylon composite material shows a change trend of increasing first and then decreasing. This is mainly affected by multiple factors: (1) The graphene loaded FeNi alloy plays a role in enhancing, and when the composite material is stretched by external force, the relative sliding of the molecular chains of the composite material is hindered, so that the tensile strength is improved; (2) The tensile strength of the HDE-g-POE-g-MGO is reduced, so that the tensile strength of the composite material is reduced; (3) Benzoic acid affects the intrinsic viscosity of the polyamide composite material, and the lower the benzoic acid is, the higher the intrinsic viscosity is, and the higher the tensile strength of the polyamide composite material is.
With the decrease of the addition amount of the double-grafted ethylene-octene copolymer (HDE-g-POE-g-MGO) and the graphene-supported FeNi alloy (RGO-FeNi), the change trend of the notch impact strength of the nylon composite material is that the notch impact strength is increased first and then decreased. The method is mainly influenced by double factors, the intervention of octene in a POE molecular chain damages the crystallization of part of polyethylene, an octene chain segment and a polyethylene chain segment with the damaged crystallization form an elastic soft segment together, and the crystallization part of the polyethylene forms a hard segment to play a role of a physical crosslinking point, so that the POE has the property of an elastomer, the addition amount of HDE-g-POE-g-MGO is reduced, and when the composite material is impacted by external force, the capability of absorbing external impact is reduced, and the notch impact performance of the composite material is reduced; the graphene-loaded FeNi alloy is dispersed in the nylon base material resin, so that stress concentration points are easy to form, the impact performance is reduced, and the impact performance is improved along with the reduction of the addition amount of the graphene-loaded FeNi alloy. Therefore, when the addition amount of the double-grafted ethylene-octene copolymer and the graphene-loaded FeNi alloy is more, the graphene-loaded FeNi alloy plays a dominant role; when the addition amount of the double-grafted ethylene and octene copolymer and the graphene loaded FeNi alloy is small, the double-grafted ethylene and octene copolymer plays a leading role.
As the addition amount of benzoic acid is reduced, the intrinsic viscosity of the nylon composite material is gradually increased, and the relative sliding of polymer molecular chains is more and more difficult, so that the melt index of the nylon composite material is reduced. The method is characterized in that the monofunctional benzoic acid plays a role of a polymerization inhibitor, so that the intrinsic viscosity of the nylon composite material is effectively adjusted, the processability is affected when the intrinsic viscosity of the nylon composite material is too high, the mechanical properties are affected when the intrinsic viscosity of the nylon composite material is too low, and the nylon composite material with good mechanical properties and processability can be obtained when the intrinsic viscosity of the nylon composite material is too low.
As the addition amount of the graphene-supported FeNi alloy (RGO-FeNi) decreases, the wave absorbing performance of the nylon composite material decreases. This is because the modified FeNi alloy is supported on the surface of the graphene sheet to form the magneto-dielectric type wave absorber. The modified FeNi alloy not only plays roles of improving magnetic loss and adjusting impedance, but also reduces the aggregation tendency of graphene due to the steric effect of the modified FeNi alloy. Therefore, graphene and the modified FeNi alloy are compounded, and the wave absorbing performance of the composite material is improved.
In summary, by adjusting the addition amounts of the graphene-supported FeNi alloy (RGO-FeNi), the double-grafted ethylene-octene copolymer (HDE-g-POE-g-MGO) and the benzoic acid, the nylon composite material with excellent mechanical properties and wave absorbing properties can be obtained under the synergistic cooperation of the auxiliary agents, wherein the nylon composite material prepared in the embodiment 7 has the best comprehensive properties.
Example 7 compared to comparative example 1, in which graphene-supported FeNi alloy was not added, had lower wave-absorbing performance than example 7. This is because the wave absorber was not added in comparative example 1.
Example 7 compared to comparative example 2, comparative example 2 replaced the graphene-supported FeNi alloy with a FeNi alloy having lower wave-absorbing properties than example 7. The FeNi alloy has high saturation magnetization and a knoek limit, but has high conductivity, and obvious eddy current effect can occur in a high frequency band, so that the wave absorbing capacity is reduced; and loading the modified FeNi alloy on the surface of the graphene sheet layer to form the magneto-dielectric type wave absorber. The modified FeNi alloy not only plays roles of improving magnetic loss and adjusting impedance, but also reduces the aggregation tendency of graphene due to the steric effect of the modified FeNi alloy.
Example 7 in comparison with comparative example 3, without the addition of a dual grafted ethylene and octene copolymer (HDE-g-POE-g-MGO), has lower notched impact properties than example 7. The intervention of octene in POE molecular chain damages the crystallization of partial polyethylene, the octene chain segment and the polyethylene chain segment with damaged crystallization form elastic soft segment together, and the crystallized part of the polyethylene forms hard segment to act as physical crosslinking point, so that the POE has the property of elastomer.
Example 7 in comparison with comparative example 4, in which no benzoic acid was added, had a melt index much lower than that of example 7. This is because the monofunctional benzoic acid acts as a polymerization inhibitor, thereby effectively adjusting the intrinsic viscosity of the nylon composite, which affects the processability, and thus the melt index of comparative example 4 is much lower than that of example 7.
Example 7 in comparison with comparative example 5, comparative example 5 uses polyamide 66 resin to prepare nylon composite material, which has lower tensile strength, notched impact strength and wave-absorbing properties than example 7. The dispersibility of the graphene-loaded FeNi alloy in the nylon composite material prepared by in-situ polymerization in a resin base material is better than that of the graphene-loaded FeNi alloy prepared by ordinary blending, so that the tensile strength, notch impact strength and wave absorbing performance of the nylon composite material are improved.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (6)
1. The nylon composite material is characterized by being prepared from the following raw materials in parts by weight:
146 parts of adipic acid,
116 parts of hexamethylenediamine, which is used for preparing the components,
10 to 30 parts of graphene-supported FeNi alloy,
2 to 8 parts of double grafted ethylene and octene copolymer,
0.2 to 2 parts of benzoic acid,
0.1 to 0.6 part of main antioxidant,
0.1 to 0.6 part of auxiliary antioxidant;
the dual-grafted ethylene and octene copolymer is prepared from an ammonia-containing base polar oligomer, ethylene and octene copolymer grafted maleic anhydride and modified graphene oxide; the amino-containing base oligomer is prepared by the reaction of hexamethylenediamine and epichlorohydrin; the modified graphene oxide is prepared by organically modifying graphene oxide through 2, 3-epoxypropyl trimethyl ammonium chloride;
the preparation method of the graphene-loaded FeNi alloy comprises the following steps:
(1) Dispersing 100 parts by weight of FeNi alloy in H 2 O 2 Adding ethanol solution into the solution, ultrasonically oscillating in ice water bath for 2-4 hours, collecting the modified FeNi alloy by using a magnet, and placing the magnet into a blast drying oven for drying to obtain the modified FeNi alloy;
(2) Dispersing 100 parts by weight of graphene in a DMF solution, dispersing 15-35 parts by weight of modified FeNi alloy in an n-hexane solution, pouring the n-hexane solution into the DMF solution, ultrasonically oscillating for 1-2 hours, washing with ethanol for 1-3 times, and drying the obtained product at 50-70 ℃;
the preparation method of the double-grafted ethylene-octene copolymer comprises the following steps:
(1) Adding 100 parts by weight of hexamethylenediamine into a bottle filled with deionized water, slowly adding 35-55 parts by weight of epichlorohydrin, controlling the system temperature to be 20-30 ℃ for reaction for 5-7 hours, heating to 60-80 ℃ for reflux reaction for 0.5-1.5 hours, and carrying out reduced pressure dehydration and drying to obtain an amino-containing polar oligomer;
(2) Adding 100 parts by weight of graphene oxide into a bottle filled with deionized water, dispersing for 0.4-0.8 hour under ultrasonic wave, adding 30-50 parts by weight of 2, 3-epoxypropyl trimethyl ammonium chloride, controlling the system temperature at 20-30 ℃ and stirring until light brown floccules are not precipitated, and centrifugally washing for 1-3 times to obtain modified graphene oxide;
(3) Mixing 100 parts by weight of ethylene and octene copolymer grafted maleic anhydride and 30-50 parts by weight of amino-containing polar oligomer in dimethylbenzene, then adding the mixture into a reaction kettle, heating to 120-140 ℃, carrying out reflux reaction for 6-8 hours, cooling to normal temperature, adding 5-9 parts by weight of modified graphene oxide and 0.5-1.5 parts by weight of tetrabutylammonium bromide, heating to 120-140 ℃ for reflux reaction for 6-8 hours, cooling to room temperature, washing with ethanol for 1-3 times, drying, and grinding to obtain the double-grafted ethylene and octene copolymer;
The preparation method of the nylon composite material comprises the following steps:
(1) Adding adipic acid and hexamethylenediamine into a stirring type polymerization reactor, and simultaneously adding graphene-loaded FeNi alloy, a double-grafted ethylene-octene copolymer, benzoic acid, a main antioxidant, an auxiliary antioxidant and a proper amount of water; then vacuumizing for 3-7 min, introducing nitrogen for 3-7 min, and circulating for 4-8 times, wherein the system pressure in the stirring type polymerization reactor is controlled to be 0.1-0.4 MPa;
(2) Heating the stirring type polymerization reactor to 80-100 ℃ in a sealing manner for 0.5-1.5 hours for salifying reaction for 0.5-1.5 hours, regulating the stirring speed of the stirring type polymerization reactor to 30-50 r/min, heating the stirring type polymerization reactor to 265-275 ℃ in a sealing manner, deflating to 1.8MPa when the temperature of the stirring type polymerization reactor reaches 220 ℃, maintaining the pressure at 1.8MPa, deflating to normal pressure after reacting for 1-3 hours, continuing reacting for 1-3 hours, continuously vacuumizing at constant temperature for 0.5-1.5 hours, and supplementing nitrogen when discharging to obtain the catalyst.
2. The nylon composite of claim 1, wherein the nylon composite is prepared from the following raw materials in parts by weight:
146 parts of adipic acid,
116 parts of hexamethylenediamine, which is used for preparing the components,
14 to 26 parts of graphene-supported FeNi alloy,
3 to 7 parts of double grafted ethylene and octene copolymer,
0.5 to 1.5 portions of benzoic acid,
0.2 to 0.5 part of main antioxidant,
0.2 to 0.5 portion of auxiliary antioxidant.
3. The nylon composite of claim 2, wherein the nylon composite is prepared from the following raw materials in parts by weight:
146 parts of adipic acid,
116 parts of hexamethylenediamine, which is used for preparing the components,
18 to 22 portions of graphene-loaded FeNi alloy,
4 to 6 parts of double grafted ethylene and octene copolymer,
0.7 to 1.3 portions of benzoic acid,
0.3 to 0.4 part of main antioxidant,
0.3 to 0.4 portion of auxiliary antioxidant.
4. The nylon composite of any one of claims 1-3, wherein the primary antioxidant is N, N' -hexamethylenebis (3, 5-di-tert-butyl-4-hydroxyphenylpropionamide) and the secondary antioxidant is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite.
5. The nylon composite according to claim 1, wherein in the preparation method of the nylon composite, the vacuum is pumped for 4min to 6min, nitrogen is introduced for 4min to 6min, the process is circulated for 5 times to 7 times, and the system pressure in the stirring type polymerization reactor is controlled to be 0.2MPa to 0.3MPa.
6. The method for producing a nylon composite according to claim 1, wherein in the step (2), the stirring polymerization reactor is heated to 85 to 95 ℃ in a sealed manner for 0.7 to 1.3 hours, the salt formation reaction is carried out for 0.7 to 1.3 hours, the stirring speed of the stirring polymerization reactor is adjusted to 35 to 45r/min, then the stirring polymerization reactor is heated to 267 to 273 ℃ in a sealed manner, when the temperature of the stirring polymerization reactor reaches 220 ℃, the pressure is maintained at 1.8MPa, the pressure is maintained at 1.5 to 2.5 hours, the pressure is released to normal pressure, the reaction is continued for 1.5 to 2.5 hours, the constant temperature is continuously evacuated for 0.7 to 1.3 hours, the reaction is completed, and nitrogen is supplemented at the time of discharging.
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