CN114262517A - Nylon composite material and preparation method thereof - Google Patents
Nylon composite material and preparation method thereof Download PDFInfo
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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-loaded FeNi alloy, double-grafted ethylene-octene copolymer, benzoic acid, a main antioxidant and an auxiliary antioxidant. The nylon composite material has excellent mechanical property and wave-absorbing property, can be applied to various electronic products such as televisions, LED display screens, sound equipment, microwave ovens and mobile phones, can reduce electromagnetic wave leakage below the national sanitation safety limit value, and ensures 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
Microwave refers to electromagnetic waves with a frequency in the range of 300MHz-300 GHz. Microwaves have now been used in various aspects of human productive life. Among the most important applications are radar and communications. With the development of electronic equipment and communication technology, people increasingly live in a complex electromagnetic environment, and the prevention and treatment of electromagnetic pollution are imperative. In addition, how to escape the radar detection is a major concern in military affairs. Based on the above application requirements, microwave absorbing materials have come into play. The microwave absorption characteristics of a substance mainly depend on its dielectric properties (complex permittivity, ∈ ═ epsilon '-j epsilon "), magnetic properties (complex permeability, μ ═ μ' -j μ"), and the like. Therefore, the wave-absorbing materials can be divided into dielectric wave-absorbing materials and magnetic wave-absorbing materials. At present, a dielectric wave-absorbing material based on carbon series filler has a narrow absorption band, and the wave-absorbing performance of a magnetic wave-absorbing material is limited by high density and a Snoek limit (a phenomenon that the performance of absorbing interference waves is poor when the frequency reaches a GHz frequency band), so that the material cannot be widely applied to military systems. Carbon-based materials such as carbon black, graphite, carbon fiber, carbon nanotube, and the like have been widely studied. As a novel carbon material, graphene has the characteristics of low density, high thermal conductivity, low resistivity, high electron mobility and the like. In the graphene prepared by the oxidation-reduction method, residual defects and radicals not only can improve the impedance matching characteristic of the graphene and enable the graphene to be rapidly converted into a Fermi level state, but also can generate polarization relaxation of the defects and electron dipole relaxation of the radicals, and the defects and the radicals are favorable for scattering and absorbing electromagnetic waves. The expected graphene is a microwave absorbing material with great potential, and is used as an additive to develop a composite wave-absorbing material with more excellent performance, so that the general purpose of thinness, width, lightness and strength of the wave-absorbing material is realized, and the wave-absorbing material has important economic and social benefits for the development of the wave-absorbing material in the military and civil fields.
Currently, some studies on nylon composite materials with wave-absorbing properties are made in the prior art, such as: 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: 9699% of polypropylene nylon 6 composite material, and the balance of chemical foaming agent; the polypropylene nylon 6 composite material comprises the following raw materials in parts by weight: 4080 parts of polypropylene, 530 parts of nylon 6, 210 parts of polycrystalline metal fiber, 115 parts of compatilizer, 0.42 part of antioxidant, 0.51 part of lubricant and 02 parts of other auxiliary agents; chinese patent CN 106046770A discloses a nylon heat-conducting composite material capable of absorbing waves for LED lamps, which is prepared from the following raw materials in parts by weight: nylon 6200 parts, manganese-zinc ferrite 15-20 parts, silicon carbide 15-20 parts, glass fiber 8-10 parts, carbon fiber 15-20 parts, acetone 50-60 parts, 60-70% nitric acid 80-100 parts, silane coupling agent A-1713-4 parts, 1-3% acetic acid aqueous solution 70-80 parts, 1, 6-hexamethylene diisocyanate 15-20 parts, hydroxyethyl (meth) acrylate 20-25 parts, catalyst 0.4-1 part, polymerization inhibitor 0.4-2 parts, tetrahydrofuran 150-170 parts, toluene 80-100 parts, and a proper amount of deionized water.
It can be seen that the nylon composite materials with wave-absorbing properties disclosed in the prior art are all prepared by adding an absorbent, including metal fibers, manganese-zinc ferrite, etc., into a nylon material by a blending method.
Disclosure of Invention
Based on the above, one of the purposes of the present invention is to prepare a nylon composite material with wave absorption performance by performing oxidation treatment on a FeNi alloy to form a thin oxide film on the surface of the FeNi alloy, then loading the thin oxide film on the surface of graphene, and dispersing the graphene in a nylon base material 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 double-grafted ethylene and octene copolymer (HDE-g-POE-g-MGO) is prepared from an amino-containing basic oligomer (HDE), ethylene and octene copolymer grafted maleic anhydride (POE-g-MAH) and Modified Graphene Oxide (MGO); the amino-containing basic oligomer (HDE) is prepared by the reaction of Hexamethylene Diamine (HDA) and Epichlorohydrin (ECH); the Modified Graphene Oxide (MGO) is prepared by organically modifying Graphene Oxide (GO) through 2, 3-epoxypropyltrimethylammonium chloride (GTA).
In some embodiments, the nylon composite material is prepared from the following raw materials in parts by weight:
in some embodiments, the nylon composite material 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 weight portions of FeNi alloy in H2O2Adding an ethanol solution into the solution, carrying out ultrasonic oscillation in an ice-water bath for 2-4 hours, collecting the modified FeNi alloy by using a magnet, and placing the modified FeNi alloy in a forced air drying oven for drying to obtain the modified FeNi alloy; (2) dispersing 100 parts by weight of graphene in a DMF (dimethyl formamide) solution, dispersing 15-35 parts by weight of modified FeNi alloy in a n-hexane solution, then pouring the n-hexane solution into the DMF solution, carrying out ultrasonic oscillation for 1-2 hours, washing with ethanol for 1-3 times, and then drying the obtained product at 50-70 ℃.
In some of these examples, the process for the preparation of the double-grafted ethylene-octene copolymer (HDE-g-POE-g-MGO) comprises the following steps:
(1) adding 100 parts by weight of Hexamethylenediamine (HDA) into a three-neck flask filled with deionized water, slowly adding 35-55 parts by weight of Epichlorohydrin (ECH), controlling the system temperature at 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 base polar oligomer (HDE);
(2) adding 100 parts by weight of Graphene Oxide (GO) into a three-necked bottle filled with deionized water, dispersing for 0.4-0.8 hour under ultrasonic waves, adding 30-50 parts by weight of 2, 3-epoxypropyltrimethylammonium chloride (GTA), controlling the system temperature at 20-30 ℃, stirring until the light brown floccule does not precipitate, and finally washing the mixture for 1-3 times by using a centrifuge to obtain Modified Graphene Oxide (MGO);
(3) mixing 100 parts by weight of ethylene-octene copolymer grafted maleic anhydride (POE-g-MAH) and 30-50 parts by weight of amino-containing basic oligomer (HDE) in xylene, then adding the mixture into a reaction kettle, heating to 120-140 ℃, carrying out reflux reaction for 6-8 hours, then cooling to normal temperature, adding 5-9 parts by weight of Modified Graphene Oxide (MGO) and 0.5-1.5 parts by weight of tetrabutylammonium bromide, heating to 120-140 ℃, carrying out reflux reaction for 6-8 hours, cooling to room temperature, washing for 1-3 times by using ethanol, and then drying and grinding the obtained product to obtain the catalyst.
In some of these embodiments, the primary antioxidant is N, N' -hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy hydrocinnamamide) and the secondary antioxidant is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite.
The invention also aims to provide a preparation method of the nylon composite material.
The specific technical scheme for realizing the aim of the invention is as follows:
a preparation method of a nylon composite material comprises the following steps:
(1) adding adipic acid and hexamethylenediamine into a stirring type polymerization reactor, and simultaneously adding a 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, circulating for 4-8 times in the way, and controlling the system pressure in the stirring type polymerization reactor to be 0.1-0.4 MPa;
(2) heating the stirring type polymerization reactor to 80-100 ℃ in a closed manner within 0.5-1.5 hours to perform salt forming reaction for 0.5-1.5 hours, adjusting the stirring speed of the stirring type polymerization reactor to 30-50 r/min, then heating the stirring type polymerization reactor to 265-275 ℃ in a closed manner, when the temperature of the stirring type polymerization reactor reaches 220 ℃, discharging to 1.8MPa, maintaining the pressure at 1.8MPa, after reacting for 1-3 hours (pre-polymerization reaction), discharging to normal pressure, after continuing to react for 1-3 hours (post-polymerization reaction), continuously vacuumizing for 0.5-1.5 hours at constant temperature (tackifying reaction), finishing the reaction, and supplementing nitrogen gas during discharging to obtain the catalyst.
In some embodiments, the method for preparing the nylon composite material comprises the following steps:
(1) adding adipic acid and hexamethylenediamine into a stirring type polymerization reactor, and simultaneously adding a 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, circulating for 5-7 times in the way, and controlling the system pressure in the stirring type polymerization reactor to be 0.2-0.3 MPa;
(2) heating the stirring type polymerization reactor to 85-95 ℃ in a closed manner within 0.7-1.3 hours to perform salt forming reaction for 0.7-1.3 hours, adjusting 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 closed 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 reaction), continuously reacting for 1.5-2.5 hours (post-polymerization reaction), continuously vacuumizing for 0.7-1.3 hours at constant temperature (tackifying reaction), finishing the reaction, and supplementing nitrogen during discharging to obtain the catalyst.
The nylon composite material disclosed by the invention has the following functions of raw materials:
the FeNi alloy has high saturation magnetization and snoek limit, but the conductivity is high, and obvious eddy current effect can occur in a high frequency range. The FeNi alloy is subjected to surface treatment, so that the eddy current loss is reduced, and the reflection of electromagnetic waves is reduced. And (3) taking normal hexane and DMF as organic solvents, and loading the modified FeNi alloy on the surface of the graphene sheet layer to form the magnetic dielectric wave absorber. The modified FeNi alloy not only has the functions of improving magnetic loss and adjusting impedance, but also reduces the agglomeration tendency of graphene due to the steric effect of the modified FeNi alloy. Therefore, the graphene and the modified FeNi alloy are compounded, and the wave-absorbing performance of the composite material is improved.
The double-grafted ethylene-octene copolymer (HDE-g-POE-g-MGO) is prepared from amino-containing basic oligomer (HDE), ethylene-octene copolymer grafted maleic anhydride (POE-g-MAH) and Modified Graphene Oxide (MGO). The principle is as follows: firstly, preparing amino-containing base oligomer (HDE) by nucleophilic substitution reaction of Hexamethylenediamine (HDA) and Epoxy Chloropropane (ECH), then performing acylation reaction of the amino-containing polar chain HDE and maleic anhydride functional group-containing ethylene-octene copolymer grafted maleic anhydride (POE-g-MAH) to obtain HDE-g-POE, and finally reacting the HDE-g-POE with Modified Graphene Oxide (MGO) to prepare the novel reactive compatibilizer double-grafted ethylene-octene copolymer (HDE-g-POE-g-MGO). The effect of HDE is as follows: (1) the polar part HDE can balance the non-polarity of POE in HDE-g-POE-g-MGO; (2) the reactive groups within the HDE may react with the MGO, which in turn grafts the MGO to the compatibilizer; (3) the reactive groups in the HDE can form hydrogen bonds with the terminal amino groups on the polyamide. The role of MGO is as follows: (1) the specific surface area of MGO is large, and the surface and the tail end of the lamella layer contain a large amount of and rich oxygen-containing functional groups to provide active sites for reaction; (2) the carboxyl groups on the MGO may form hydrogen bonds with the terminal amino groups on the polyamide; (3) the MGO has strong interaction with the graphene-loaded FeNi alloy, and is beneficial to the dispersion of the wave absorbing agent in the nylon resin base material.
Benzoic acid is carboxylic acid with a monofunctional group, and can terminate the chain extension reaction of the nylon material, so that the molecular weight (namely the intrinsic viscosity) of the nylon material is adjusted, and the nylon material has better mechanical property and processability.
The main antioxidant N, N' -hexamethylene bis (3, 5-di-tert-butyl-4-hydroxy hydrocinnamamide) and the auxiliary antioxidant are bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, have high heat resistance, are suitable for being used in synthesis and preparation, and have good compatibility with nylon materials.
Compared with the prior art, the nylon composite material and the preparation method thereof provided by the invention have the following beneficial effects:
1. the invention selects raw materials of adipic acid, hexamethylene diamine, graphene-loaded FeNi alloy (RGO-FeNi) and double-grafted ethylene-octene copolymer (HDE-g-POE-g-MGO) with specific proportion, simultaneously adds benzoic acid to adjust the intrinsic viscosity of the polymer, and prepares the nylon composite material with excellent mechanical property and wave absorption property, wherein the intrinsic viscosity is 1.12 dL/g-1.64 dL/g (tested according to GB/T1632-, In digital cameras, game machines, microwave ovens and mobile phones, electromagnetic wave leakage can be reduced to below the national health safety limit (10 microwatts per square centimeter) to ensure human health.
2. The magnetic-dielectric wave absorber is prepared by loading the FeNi alloy on the graphene sheet layer, not only has the functions of improving magnetic loss and adjusting impedance, but also reduces the agglomeration trend of graphene due to the steric effect of the wave absorber, and effectively overcomes the defects of poor high-frequency wave absorbing performance (Snoek limit), easy agglomeration and poor dispersibility of the magnetic wave absorbing material.
3. According to the preparation method of the nylon composite material, nitrogen is introduced before reaction, so that the probability of side reaction is reduced; adding a proper amount of water before reaction, thereby increasing the pressure in the kettle and the mass and heat transfer in the heating process; the reaction process is vacuumized, the low-molecular extractables generated in the polymerization reaction process are removed, the forward progress of the polymerization reaction is facilitated, and the performance of the nylon composite material is not affected by the residual low-molecular extractables, so that the low-molecular extractables are separated without adopting additional extraction equipment, the time can be saved, and the energy can be saved; the preparation method is simple, all reactions do not need to be carried out in a solvent, and the complex process of removing the solvent subsequently is omitted.
Drawings
FIG. 1 is a flow chart of the preparation process of the nylon composite material of the present invention.
Fig. 2 is a transmission electron microscope image of the graphene-loaded FeNi alloy prepared by the present invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. The present 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. As used herein, the term "and/or" 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 (see the preparation process flow chart in figure 1):
wherein n is 1-5, and R is HDE-g-POE-g-MGO.
Mechanism of reaction
From the above reaction formula, (1) Hexamethylenediamine (HDA) reacts with Epichlorohydrin (ECH) to synthesize amino-containing base oligomer (HDE); (2)2, 3-epoxypropyltrimethylammonium chloride (GTA) is electrostatically intercalated into a Graphene Oxide (GO) lamellar, the method not only enables the GO lamellar to be easier to strip, improves the dispersity of GO in a polymer matrix, but also provides an active group epoxy group for the reaction of GO and HDE-g-POE; (3) carrying out acylation reaction on amino-containing basic oligomer (HDE) and a non-polar part POE-g-MAH to obtain HDE-g-POE, and then reacting with MGO nano-sheets to obtain a dual-grafting compatilizer HDE-g-POE-g-MGO; (4) the terminal amino group of the HDE-g-POE-g-MGO can react with the terminal carboxyl group of the PA66, the compatibility and the interface adhesive force of the HDE-g-POE-g-MGO and nylon base material resin are improved, the POE chain segment has excellent flexibility, and the absorption of external impact energy is greatly facilitated, so that the impact performance of the polyamide composite material is improved, the interaction between the MGO chain segment and the graphene loaded FeNi alloy is realized, and the improvement of the dispersion of the graphene loaded FeNi alloy in the nylon base material resin is facilitated.
The raw materials used in the embodiment of the invention are as follows:
adipic acid, available from llc of the samara group, china.
Hexamethylenediamine, available from the national institute of Gong-Ma, Inc.
FeNi alloy, Fe50Ni50The nanometer powder has a particle size of 70nm and is purchased from Xuzhou Jie Innovative materials science and technology Limited.
Graphene, purchased from Nanjing Chikung nanotechnology, Inc.
H2O2From chemical reagents of the national drug group, ltd.
Ethanol, available from national pharmaceutical group chemical agents, ltd.
N-hexane, available from the national pharmaceutical group chemical reagents, ltd.
N, N-Dimethylformamide (DMF) was purchased from Chemicals group, Inc., national pharmaceuticals.
Epichlorohydrin was obtained from Kyoho chemical Co., Ltd.
Graphene oxide, purchased from Nanjing GmbH nanotechnology, Inc.
2, 3-epoxypropyltrimethylammonium chloride, available from Kao chemical technology, Inc., North Hu.
The copolymer of ethylene and octene was grafted with maleic anhydride, the graft ratio of maleic anhydride was 1.2%, Shenyang Ketong plastics Co., Ltd.
Tetrabutylammonium bromide, available from denying chemical ltd.
Benzoic acid, available from national pharmaceutical group chemical reagents, ltd.
N, N' -hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy-hydrocinnamamide) available from Exckm chemical Co., Ltd. of Zheng Zhou.
Bis (2, 4-dicumylphenyl) pentaerythritol diphosphite available from Shanghai Yaozao Fine chemical Co., Ltd.
Polyamide 66, available from the national Gong horse group, LLC.
The graphene-supported FeNi alloy (RGO-FeNi) used in the following examples was prepared by a method comprising the steps of:
(1) 100g of FeNi alloy was dispersed in 1L of H2O2Adding 0.5L of ethanol solution into the solution, carrying out ultrasonic oscillation in an ice water bath for 3 hours, collecting the modified FeNi alloy by using a magnet, and placing the modified FeNi alloy in a forced air drying oven for drying to obtain the modified FeNi alloy;
(2) dispersing 100g of graphene in 1L of DMF (dimethyl formamide) solution, dispersing 25g of modified FeNi alloy in 0.5L of n-hexane solution, then pouring the n-hexane solution into the DMF solution, ultrasonically oscillating for 1.5 hours, washing for 2 times by using ethanol, and then drying the obtained product at 60 ℃.
Fig. 2 is a transmission electron microscope image of the graphene-loaded FeNi alloy prepared by the present invention.
The double-grafted ethylene-octene copolymer (HDE-g-POE-g-MGO) used in the following examples was prepared by a process comprising the following steps:
(1) adding 100g of Hexamethylenediamine (HDA) into a three-neck flask filled with deionized water, slowly adding 45g of Epichlorohydrin (ECH), controlling the temperature of the system to react at 25 ℃ for 6 hours, heating to 70 ℃, carrying out reflux reaction for 1 hour, and carrying out reduced pressure dehydration and drying to obtain amino-containing base linear oligomer (HDE);
(2) adding 100g of Graphene Oxide (GO) into a three-neck flask filled with deionized water, dispersing for 0.6 hour under ultrasonic waves, adding 40g of 2, 3-epoxypropyltrimethylammonium chloride (GTA), controlling the temperature of the system at 25 ℃, stirring until the light brown floccule is not precipitated, and finally washing the mixture for 2 times by using a centrifugal machine to obtain Modified Graphene Oxide (MGO);
(3) mixing 100g of ethylene-octene copolymer grafted maleic anhydride (POE-g-MAH) and 40g of amino-containing basic oligomer (HDE) in xylene, then adding the mixture into a reaction kettle, heating to 130 ℃, carrying out reflux reaction for 7 hours, cooling to normal temperature, adding 7g of Modified Graphene Oxide (MGO) and 1g of tetrabutylammonium bromide, heating to 130 ℃, carrying out reflux reaction for 7 hours, cooling to room temperature, washing for 2 times by using ethanol, and drying and grinding the obtained product to obtain the modified graphene oxide/octylene copolymer grafted maleic anhydride/ammonium bromide composite material.
The present invention will be described in detail with reference to specific examples.
EXAMPLE 1 Nylon composite 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 a graphene-loaded FeNi alloy (RGO-FeNi), a double-grafted ethylene-octene copolymer (HDE-g-POE-g-MGO), benzoic acid, N' -hexamethylene bis (3, 5-di-tert-butyl-4-hydroxy hydrocinnamamide), bis (2, 4-dicumylphenyl) pentaerythritol diphosphite and a proper amount of water; then vacuumizing for 7min, introducing nitrogen for 7min, circulating for 4 times in the way, and controlling the system pressure in the stirring type polymerization reactor to be 0.4 MPa;
(2) heating the stirring type polymerization reactor to 100 ℃ in a closed manner within 1.5 hours to perform salt forming reaction for 1.5 hours, adjusting the stirring speed of the stirring type polymerization reactor to 50r/min, then heating the stirring type polymerization reactor to 275 ℃ in a closed manner, when the temperature of the stirring type polymerization reactor reaches 220 ℃, discharging gas to 1.8MPa, maintaining the pressure at 1.8MPa, discharging gas to normal pressure after 1 hour of reaction (pre-polymerization reaction), continuously reacting for 1 hour (post-polymerization reaction), continuously vacuumizing for 1.5 hours at constant temperature (tackifying reaction), finishing the reaction, and supplementing nitrogen gas during discharging to obtain the catalyst.
Example 2 Nylon composite and method of preparing 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 a graphene-loaded FeNi alloy (RGO-FeNi), a double-grafted ethylene-octene copolymer (HDE-g-POE-g-MGO), benzoic acid, N' -hexamethylene bis (3, 5-di-tert-butyl-4-hydroxy hydrocinnamamide), bis (2, 4-dicumylphenyl) pentaerythritol diphosphite and a proper amount of water; then vacuumizing for 3min, introducing nitrogen for 3min, circulating for 8 times in the way, and controlling the system pressure in the stirring type polymerization reactor to be 0.1 MPa;
(2) heating the stirring type polymerization reactor to 80 ℃ in a closed manner within 0.5 hour to perform salt forming reaction for 0.5 hour, adjusting the stirring speed of the stirring type polymerization reactor to 30r/min, heating the stirring type polymerization reactor to 265 ℃ in a closed manner, discharging gas to 1.8MPa when the temperature of the stirring type polymerization reactor reaches 220 ℃, maintaining the pressure at 1.8MPa, discharging gas to normal pressure after 3 hours of reaction (pre-polymerization reaction), continuously reacting for 3 hours (post-polymerization reaction), continuously vacuumizing for 0.5 hour at constant temperature (tackifying reaction), finishing the reaction, and supplementing nitrogen gas during discharging to obtain the catalyst.
EXAMPLE 3 Nylon composite 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 a graphene-loaded FeNi alloy (RGO-FeNi), a double-grafted ethylene-octene copolymer (HDE-g-POE-g-MGO), benzoic acid, N' -hexamethylene bis (3, 5-di-tert-butyl-4-hydroxy hydrocinnamamide), bis (2, 4-dicumylphenyl) pentaerythritol diphosphite and a proper amount of water; then vacuumizing for 6min, introducing nitrogen for 6min, circulating for 5 times in the way, and controlling the system pressure in the stirring type polymerization reactor to be 0.3 MPa;
(2) heating the stirring type polymerization reactor in a closed manner to 95 ℃ within 1.3 hours to perform salt forming reaction for 1.3 hours, adjusting the stirring speed of the stirring type polymerization reactor to 45r/min, then heating the stirring type polymerization reactor in a closed manner to 273 ℃, when the temperature of the stirring type polymerization reactor reaches 220 ℃, discharging gas to 1.8MPa, maintaining the pressure at 1.8MPa, discharging gas to normal pressure after reacting for 1.5 hours (pre-polymerization reaction), continuously reacting for 1.5 hours (post-polymerization reaction), continuously vacuumizing for 1.3 hours (tackifying reaction) at constant temperature, finishing the reaction, and supplementing nitrogen gas during discharging to obtain the catalyst.
EXAMPLE 4 Nylon composite 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 a graphene-loaded FeNi alloy (RGO-FeNi), a double-grafted ethylene-octene copolymer (HDE-g-POE-g-MGO), benzoic acid, N' -hexamethylene bis (3, 5-di-tert-butyl-4-hydroxy hydrocinnamamide), bis (2, 4-dicumylphenyl) pentaerythritol diphosphite and a proper amount of water; then vacuumizing for 4min, introducing nitrogen for 4min, circulating for 7 times in the way, and controlling the system pressure in the stirring type polymerization reactor to be 0.2 MPa;
(2) heating the stirring type polymerization reactor in a closed manner to 85 ℃ within 0.7 hour to perform salt forming reaction for 0.7 hour, adjusting the stirring speed of the stirring type polymerization reactor to 35r/min, then heating the stirring type polymerization reactor in a closed manner to 267 ℃, when the temperature of the stirring type polymerization reactor reaches 220 ℃, discharging gas to 1.8MPa, maintaining the pressure at 1.8MPa, discharging gas to normal pressure after reacting for 2.5 hours (pre-polymerization reaction), continuously reacting for 2.5 hours (post-polymerization reaction), continuously vacuumizing for 0.7 hour (tackifying reaction) at constant temperature, finishing the reaction, and supplementing nitrogen gas during discharging to obtain the catalyst.
EXAMPLE 5 Nylon composite 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 a graphene-loaded FeNi alloy (RGO-FeNi), a double-grafted ethylene-octene copolymer (HDE-g-POE-g-MGO), benzoic acid, N' -hexamethylene bis (3, 5-di-tert-butyl-4-hydroxy hydrocinnamamide), bis (2, 4-dicumylphenyl) pentaerythritol diphosphite and a proper amount of water; then vacuumizing for 5min, introducing nitrogen for 5min, circulating for 6 times in the way, and controlling the system pressure in the stirring type polymerization reactor to be 0.25 MPa;
(2) heating the stirring type polymerization reactor to 90 ℃ in a closed manner within 1 hour to perform salt forming reaction for 1 hour, adjusting the stirring speed of the stirring type polymerization reactor to 40r/min, then heating the stirring type polymerization reactor to 270 ℃ in a closed manner, when the temperature of the stirring type polymerization reactor reaches 220 ℃, discharging gas to 1.8MPa, maintaining the pressure at 1.8MPa, after 2 hours of reaction (pre-polymerization reaction), discharging gas to normal pressure, after 2 hours of reaction (post-polymerization reaction), continuously vacuumizing for 1 hour at constant temperature (tackifying reaction), finishing the reaction, and supplementing nitrogen gas during discharging to obtain the catalyst.
Example 6 Nylon composite 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 a graphene-loaded FeNi alloy (RGO-FeNi), a double-grafted ethylene-octene copolymer (HDE-g-POE-g-MGO), benzoic acid, N' -hexamethylene bis (3, 5-di-tert-butyl-4-hydroxy hydrocinnamamide), bis (2, 4-dicumylphenyl) pentaerythritol diphosphite and a proper amount of water; then vacuumizing for 5min, introducing nitrogen for 5min, circulating for 6 times in the way, and controlling the system pressure in the stirring type polymerization reactor to be 0.25 MPa;
(2) heating the stirring type polymerization reactor to 90 ℃ in a closed manner within 1 hour to perform salt forming reaction for 1 hour, adjusting the stirring speed of the stirring type polymerization reactor to 40r/min, then heating the stirring type polymerization reactor to 270 ℃ in a closed manner, when the temperature of the stirring type polymerization reactor reaches 220 ℃, discharging gas to 1.8MPa, maintaining the pressure at 1.8MPa, after 2 hours of reaction (pre-polymerization reaction), discharging gas to normal pressure, after 2 hours of reaction (post-polymerization reaction), continuously vacuumizing for 1 hour at constant temperature (tackifying reaction), finishing the reaction, and supplementing nitrogen gas during discharging to obtain the catalyst.
EXAMPLE 7 Nylon composite 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 a graphene-loaded FeNi alloy (RGO-FeNi), a double-grafted ethylene-octene copolymer (HDE-g-POE-g-MGO), benzoic acid, N' -hexamethylene bis (3, 5-di-tert-butyl-4-hydroxy hydrocinnamamide), bis (2, 4-dicumylphenyl) pentaerythritol diphosphite and a proper amount of water; then vacuumizing for 5min, introducing nitrogen for 5min, circulating for 6 times in the way, and controlling the system pressure in the stirring type polymerization reactor to be 0.25 MPa;
(2) heating the stirring type polymerization reactor to 90 ℃ in a closed manner within 1 hour to perform salt forming reaction for 1 hour, adjusting the stirring speed of the stirring type polymerization reactor to 40r/min, then heating the stirring type polymerization reactor to 270 ℃ in a closed manner, when the temperature of the stirring type polymerization reactor reaches 220 ℃, discharging gas to 1.8MPa, maintaining the pressure at 1.8MPa, after 2 hours of reaction (pre-polymerization reaction), discharging gas to normal pressure, after 2 hours of reaction (post-polymerization reaction), continuously vacuumizing for 1 hour at constant temperature (tackifying reaction), finishing the reaction, and supplementing nitrogen gas during discharging to obtain the catalyst.
Comparative example 1
The nylon composite material 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' -hexamethylene bis (3, 5-di-tert-butyl-4-hydroxy hydrocinnamamide) 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 in the way, and controlling the system pressure in the stirring type polymerization reactor to be 0.25 MPa;
(2) heating the stirring type polymerization reactor to 90 ℃ in a closed manner within 1 hour to perform salt forming reaction for 1 hour, adjusting the stirring speed of the stirring type polymerization reactor to 40r/min, then heating the stirring type polymerization reactor to 270 ℃ in a closed manner, when the temperature of the stirring type polymerization reactor reaches 220 ℃, discharging gas to 1.8MPa, maintaining the pressure at 1.8MPa, after 2 hours of reaction (pre-polymerization reaction), discharging gas to normal pressure, after 2 hours of reaction (post-polymerization reaction), continuously vacuumizing for 1 hour at constant temperature (tackifying reaction), finishing the reaction, and supplementing nitrogen gas during discharging to obtain the catalyst.
Comparative example 2
The nylon composite material 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 FeNi alloy, a double-grafted ethylene-octene copolymer (HDE-g-POE-g-MGO), benzoic acid, N' -hexamethylene bis (3, 5-di-tert-butyl-4-hydroxy hydrocinnamamide) 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 in the way, and controlling the system pressure in the stirring type polymerization reactor to be 0.25 MPa;
(2) heating the stirring type polymerization reactor to 90 ℃ in a closed manner within 1 hour to perform salt forming reaction for 1 hour, adjusting the stirring speed of the stirring type polymerization reactor to 40r/min, then heating the stirring type polymerization reactor to 270 ℃ in a closed manner, when the temperature of the stirring type polymerization reactor reaches 220 ℃, discharging gas to 1.8MPa, maintaining the pressure at 1.8MPa, after 2 hours of reaction (pre-polymerization reaction), discharging gas to normal pressure, after 2 hours of reaction (post-polymerization reaction), continuously vacuumizing for 1 hour at constant temperature (tackifying reaction), finishing the reaction, and supplementing nitrogen gas during discharging to obtain the catalyst.
Comparative example 3
The nylon composite material 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-loaded FeNi alloy (RGO-FeNi), benzoic acid, N' -hexamethylene bis (3, 5-di-tert-butyl-4-hydroxy hydrocinnamamide), bis (2, 4-dicumylphenyl) pentaerythritol diphosphite and a proper amount of water; then vacuumizing for 5min, introducing nitrogen for 5min, circulating for 6 times in the way, and controlling the system pressure in the stirring type polymerization reactor to be 0.25 MPa;
(2) heating the stirring type polymerization reactor to 90 ℃ in a closed manner within 1 hour to perform salt forming reaction for 1 hour, adjusting the stirring speed of the stirring type polymerization reactor to 40r/min, then heating the stirring type polymerization reactor to 270 ℃ in a closed manner, when the temperature of the stirring type polymerization reactor reaches 220 ℃, discharging gas to 1.8MPa, maintaining the pressure at 1.8MPa, after 2 hours of reaction (pre-polymerization reaction), discharging gas to normal pressure, after 2 hours of reaction (post-polymerization reaction), continuously vacuumizing for 1 hour at constant temperature (tackifying reaction), finishing the reaction, and supplementing nitrogen gas during discharging to obtain the catalyst.
Comparative example 4
The nylon composite material 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-loaded FeNi alloy (RGO-FeNi), double-grafted ethylene-octene copolymer (HDE-g-POE-g-MGO), N' -hexamethylene bis (3, 5-di-tert-butyl-4-hydroxy hydrocinnamamide) 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 in the way, and controlling the system pressure in the stirring type polymerization reactor to be 0.25 MPa;
(2) heating the stirring type polymerization reactor to 90 ℃ in a closed manner within 1 hour to perform salt forming reaction for 1 hour, adjusting the stirring speed of the stirring type polymerization reactor to 40r/min, then heating the stirring type polymerization reactor to 270 ℃ in a closed manner, when the temperature of the stirring type polymerization reactor reaches 220 ℃, discharging gas to 1.8MPa, maintaining the pressure at 1.8MPa, after 2 hours of reaction (pre-polymerization reaction), discharging gas to normal pressure, after 2 hours of reaction (post-polymerization reaction), continuously vacuumizing for 1 hour at constant temperature (tackifying reaction), finishing the reaction, and supplementing nitrogen gas during discharging to obtain the catalyst.
Comparative example 5
The nylon composite material 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 the temperature of 110 ℃ for 3 hours, cooling, and placing the cooled polyamide 66 for later use;
(2) adding the graphene-loaded FeNi alloy (RGO-FeNi), the double-grafted ethylene-octene copolymer (HDE-g-POE-g-MGO), N' -hexamethylene bis (3, 5-di-tert-butyl-4-hydroxy hydrocinnamamide) and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into another high-speed stirrer (the rotating speed is 1000 rpm) for mixing;
(3) adding the polyamide 66 dried in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into the parallel double-screw extruder (totally eight zones) in the lateral direction (fourth zone), performing melt extrusion, and granulating, wherein the process parameters are as follows: the temperature in the first zone was 210 ℃, the temperature in the second zone was 220 ℃, the temperature in the third zone was 225 ℃, the temperature in the fourth zone was 230 ℃, the temperature in the fifth zone was 230 ℃, the temperature in the sixth zone was 230 ℃, the temperature in the seventh zone was 230 ℃, the temperature in the eighth zone was 230 ℃, the temperature in the die head was 225 ℃ and the screw speed was 400 rpm.
The following is a summary of the raw material compositions of examples 1-7 and comparative examples 1-5.
TABLE 1 summary of the raw material compositions of examples 1-7 and comparative examples 1-5
Remarking: replacing a graphene-loaded FeNi alloy with a FeNi alloy; b, adipic acid is replaced by polyamide 66.
Wherein, the main antioxidant of the above examples and comparative examples is N, N' -hexamethylene-bis (3, 5-di-tert-butyl-4-hydroxy-hydrocinnamamide), and the auxiliary antioxidant is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite.
Examples 1 to 7 were conducted to prepare nylon composite materials by adjusting the addition amounts of adipic acid, hexamethylenediamine, graphene-supported FeNi alloy (RGO-FeNi), double-grafted ethylene-octene copolymer (HDE-g-POE-g-MGO), and benzoic acid, comparative examples 1 to 5 were conducted to prepare nylon composite materials based on the raw materials of example 7, comparative example 1 was conducted without adding graphene-supported FeNi alloy, comparative example 2 was conducted by replacing graphene-supported FeNi alloy with the FeNi alloy, comparative example 3 was conducted without adding double-grafted ethylene-octene copolymer (HDE-g-POE-g-MGO), comparative example 4 was conducted without adding benzoic acid, and comparative example 5 was conducted by using polyamide 66 resin to prepare nylon composite materials. The nylon composite materials prepared in the above examples and comparative examples were subjected to the following performance tests:
tensile property: the tensile rate is 50mm/min according to the test of GB/T1040-2006 standard.
Notched impact strength: testing according to GB/T1843-2008 standard.
Melt index: the test temperature is 275 ℃ and the load is 2.16kg according to the test of GB/T3682-2000-plus-2000 standard.
Wave-absorbing property: according to the GJB 5239-. The wider the width of the microwave frequency is, the better the coverage area is, and the higher the microwave frequency is, the better the coverage area is; the wave-absorbing performance reflects the wave-absorbing capacity of the material to electromagnetic waves, and the larger the absolute value of the wave-absorbing performance is, the more the electromagnetic waves passing through the material are attenuated, the better the wave-absorbing performance is.
Intrinsic viscosity: tested according to GB/T1632-2008 standard, the solvent is concentrated sulfuric acid.
Melting temperature: testing according to GB/T19466.3-2004 standard.
The results of the performance tests are shown in table 2.
TABLE 2 Performance Table of the Nylon composites of examples 1-7 and comparative examples 1-5
As can be seen from table 2:
with the addition of the graphene-loaded FeNi alloy (RGO-FeNi), the double-grafted ethylene-octene copolymer (HDE-g-POE-g-MGO) and the benzoic acid being reduced, the tensile strength of the nylon composite material shows a change trend of increasing firstly and then reducing. This is mainly influenced by multiple factors: (1) the graphene-loaded FeNi alloy plays a role in reinforcement, and when the composite material is stretched by an external force, the relative slippage of 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 per se 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 less benzoic acid, the higher the intrinsic viscosity, and the greater the tensile strength of the polyamide composite material.
The change trend that the notch impact strength of the nylon composite material is increased firstly and then reduced along with the reduction of the addition of the double-grafted ethylene-octene copolymer (HDE-g-POE-g-MGO) and the graphene loaded FeNi alloy (RGO-FeNi). The method is mainly influenced by double factors, the intervention of octene in a POE molecular chain damages the crystallization of partial polyethylene, an elastic soft segment is formed by an octene chain segment and a polyethylene chain segment damaged by the crystallization, a hard segment is formed by a polyethylene crystallization part and plays a role of a physical cross-linking point, so that the POE has the property of an elastomer, and the addition amount of HDE-g-POE-g-MGO is reduced, so that the capability of absorbing external impact is reduced when the composite material is impacted by external force, and the notch impact performance is reduced; the graphene-loaded FeNi alloy is dispersed in nylon base material resin, so that stress concentration points are easily formed, 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 amounts of the double-grafted ethylene-octene copolymer and the graphene-loaded FeNi alloy are large, the graphene-loaded FeNi alloy plays a leading role; when the addition amounts of the double-grafted ethylene-octene copolymer and the graphene-loaded FeNi alloy are small, the double-grafted ethylene-octene copolymer plays a leading role.
With the addition of the benzoic acid being reduced, the intrinsic viscosity of the nylon composite material is gradually increased, and the relative slippage of polymer molecular chains of the nylon composite material is more difficult, so that the melt index of the nylon composite material is reduced. The single-functional-group 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 influenced when the intrinsic viscosity of the nylon composite material is too high, and the mechanical property is influenced when the intrinsic viscosity of the nylon composite material is too low, so that the nylon composite material with excellent mechanical property and processability can be obtained only by proper intrinsic viscosity.
With the decrease of the addition of the graphene-loaded FeNi alloy (RGO-FeNi), the wave-absorbing performance of the nylon composite material is reduced. This is because the modified FeNi alloy is supported on the surface of the graphene sheet layer, and forms a magnetic dielectric wave absorber. The modified FeNi alloy not only has the functions of improving magnetic loss and adjusting impedance, but also reduces the agglomeration tendency of graphene due to the steric effect of the modified FeNi alloy. Therefore, the graphene and the modified FeNi alloy are compounded, and the wave-absorbing performance of the composite material is improved.
In summary, the nylon composite material with excellent mechanical properties and wave absorption properties of the present invention can be obtained 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 under the synergistic coordination of the additives, wherein the nylon composite material prepared in example 7 has the best combination properties.
Compared with the comparative example 1, the comparative example 1 does not add the graphene-loaded FeNi alloy, and the wave absorbing performance of the graphene-loaded FeNi alloy is lower than that of the example 7. This is because comparative example 1 does not contain a wave absorbing agent.
Example 7 compared with comparative example 2, in comparative example 2, the graphene-supported FeNi alloy is replaced by the FeNi alloy, and the wave absorbing performance is lower than that of example 7. The FeNi alloy has very high saturation magnetization and snoek limit, but the conductivity is high, so that obvious eddy current effect can occur in a high-frequency band, and the wave absorbing capacity is reduced; and loading the modified FeNi alloy on the surface of the graphene sheet layer to form the magnetic dielectric wave absorber. The modified FeNi alloy not only has the functions of improving magnetic loss and adjusting impedance, but also reduces the agglomeration 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 the double-grafted ethylene-octene copolymer (HDE-g-POE-g-MGO), has notched impact properties lower than those of example 7. The reason is that the intervention of octene in the molecular chain of POE destroys part of polyethylene crystal, the octene chain segment and the polyethylene chain segment destroyed by crystal form an elastic soft segment, the crystal part of polyethylene forms a hard segment, which plays the role of physical cross-linking point, so that POE has the property of elastomer.
Example 7 in comparison to comparative example 4, which did not add benzoic acid, had a much lower melt index than example 7. This is because monofunctional benzoic acid acts as a polymerization inhibitor to effectively adjust the intrinsic viscosity of the nylon composite, and too high an intrinsic viscosity of the nylon composite affects processability, so the melt index of comparative example 4 is much lower than that of example 7.
Compared with the comparative example 5, the tensile strength, the notch impact strength and the wave absorbing performance of the nylon composite material prepared by the comparative example 5 by adopting the polyamide 66 resin are lower than those of the nylon composite material prepared by the example 7. The dispersibility of the graphene-loaded FeNi alloy in the nylon composite material prepared by in-situ polymerization in the resin base material is better than that of the common blend, so that the tensile strength, the notch impact strength and the wave-absorbing performance of the graphene-loaded FeNi alloy are improved.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. The nylon composite material is characterized by being prepared from the following raw materials in parts by weight:
the double-grafted ethylene-octene copolymer is prepared by grafting maleic anhydride and modified graphene oxide on an amino-containing basic oligomer and an ethylene-octene copolymer; the amino-containing basic oligomer is prepared by the reaction of hexamethylene diamine and epichlorohydrin; the modified graphene oxide is prepared by organically modifying graphene oxide with 2, 3-epoxypropyltrimethylammonium chloride.
2. The nylon composite material as claimed in claim 1, which is prepared from the following raw materials in parts by weight:
3. the nylon composite material as claimed in claim 2, which is prepared from the following raw materials in parts by weight:
4. the nylon composite material as claimed in any one of claims 1 to 3, wherein the preparation method of the graphene-loaded FeNi alloy comprises the following steps:
(1) dispersing 100 weight portions of FeNi alloy in H2O2Adding an ethanol solution into the solution, carrying out ultrasonic oscillation in an ice-water bath for 2-4 hours, collecting the modified FeNi alloy by using a magnet, and placing the modified FeNi alloy in a forced air drying oven for drying to obtain the modified FeNi alloy;
(2) dispersing 100 parts by weight of graphene in a DMF (dimethyl formamide) solution, dispersing 15-35 parts by weight of modified FeNi alloy in a n-hexane solution, then pouring the n-hexane solution into the DMF solution, carrying out ultrasonic oscillation for 1-2 hours, washing with ethanol for 1-3 times, and then drying the obtained product at 50-70 ℃.
5. The nylon composite material according to any one of claims 1 to 3, wherein 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 epoxy chloropropane, controlling the temperature of the system to be 20-30 ℃, reacting for 5-7 hours, heating to 60-80 ℃, performing reflux reaction for 0.5-1.5 hours, and performing reduced pressure dehydration and drying to obtain an amino-containing basic 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 waves, adding 30-50 parts by weight of 2, 3-epoxypropyltrimethylammonium chloride, controlling the temperature of the system at 20-30 ℃, stirring until the light brown floccule does not precipitate, and centrifugally washing for 1-3 times to obtain modified graphene oxide;
(3) mixing 100 parts by weight of ethylene-octene copolymer grafted maleic anhydride and 30-50 parts by weight of amino-containing basic oligomer in xylene, adding the mixture into a reaction kettle, heating to 120-140 ℃, performing 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 ℃, performing 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-octene copolymer.
6. The nylon composite material according to any one of claims 1 to 3, wherein the primary antioxidant is N, N' -hexamethylene bis (3, 5-di-tert-butyl-4-hydroxy hydrocinnamamide) and the secondary antioxidant is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite.
7. A method for preparing a nylon composite material according to any one of claims 1 to 6, comprising the steps of:
(1) adding adipic acid and hexamethylenediamine into a stirring type polymerization reactor, and simultaneously adding a 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, circulating for 4-8 times in the way, and controlling the system pressure in the stirring type polymerization reactor to be 0.1-0.4 MPa;
(2) heating the stirring type polymerization reactor to 80-100 ℃ in a closed manner within 0.5-1.5 hours to perform salt forming reaction for 0.5-1.5 hours, adjusting the stirring speed of the stirring type polymerization reactor to 30-50 r/min, then heating the stirring type polymerization reactor to 265-275 ℃ in a closed manner, when the temperature of the stirring type polymerization reactor reaches 220 ℃, discharging gas to 1.8MPa, maintaining the pressure at 1.8MPa, after reacting for 1-3 hours, discharging gas to normal pressure, after continuing to react for 1-3 hours, continuously vacuumizing for 0.5-1.5 hours at constant temperature, finishing the reaction, and supplementing nitrogen gas during discharging to obtain the product.
8. The preparation method of the nylon composite material according to claim 7, wherein in the step (1), the vacuum pumping is performed for 4min to 6min, the nitrogen gas is introduced for 4min to 6min, the cycle is performed for 5 to 7 times, and the system pressure in the stirring type polymerization reactor is controlled to be 0.2MPa to 0.3 MPa.
9. The preparation method of the nylon composite material according to claim 7, wherein in the step (2), the stirring type polymerization reactor is heated in a sealing manner to 85-95 ℃ within 0.7-1.3 hours to carry out salt forming reaction for 0.7-1.3 hours, the stirring speed of the stirring type polymerization reactor is adjusted to 35-45 r/min, then the stirring type polymerization reactor is heated in a sealing manner to 267-273 ℃, when the temperature of the stirring type polymerization reactor reaches 220 ℃, the gas is released to 1.8MPa, the pressure is maintained at 1.8MPa, the reaction is carried out for 1.5-2.5 hours, the gas is released to normal pressure, the reaction is continued for 1.5-2.5 hours, the constant temperature vacuum pumping is carried out for 0.7-1.3 hours, the reaction is finished, and nitrogen is supplemented during discharging, so as to obtain the nylon composite material.
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