CN115353677A - Epoxidized natural rubber electromagnetic shielding composite material and preparation method and application thereof - Google Patents

Epoxidized natural rubber electromagnetic shielding composite material and preparation method and application thereof Download PDF

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CN115353677A
CN115353677A CN202210965151.5A CN202210965151A CN115353677A CN 115353677 A CN115353677 A CN 115353677A CN 202210965151 A CN202210965151 A CN 202210965151A CN 115353677 A CN115353677 A CN 115353677A
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composite material
electromagnetic shielding
natural rubber
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张水洞
朱静漪
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South China University of Technology SCUT
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    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • C—CHEMISTRY; METALLURGY
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Abstract

The invention discloses an epoxidized natural rubber electromagnetic shielding composite material and a preparation method and application thereof. The preparation method comprises the following steps: in-situ preparation of ENR/rGO/Fe by one-pot method 3 O 4 And drying and hot pressing to obtain the composite sheet. By the interaction of covalent bond and hydrogen bond interface between the rGO and the ENR, a high-efficiency conductive isolation structure with high interface compatibility is constructed, the flexible ENR electromagnetic shielding composite material with high mechanical property, high conductivity and wave absorption dominance is obtained, the tensile strength of the flexible ENR electromagnetic shielding composite material is as high as 14.3MPa, the flexible ENR electromagnetic shielding composite material is 2310 percent of pure ENR, and the conductivity of the flexible ENR electromagnetic shielding composite material is as high as 50S/Hm, EMI SE reaches up to 40.6dB, and the electromagnetic wave absorption rate reaches up to 99.97%, thereby meeting the requirements of most fields on high-strength flexible electromagnetic shielding materials. And the epoxidized natural rubber electromagnetic shielding composite material has simple and easy processing process and green and environment-friendly raw materials.

Description

Epoxidized natural rubber electromagnetic shielding composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of electromagnetic shielding composite materials, and particularly relates to an epoxidized natural rubber electromagnetic shielding composite material as well as a preparation method and application thereof.
Background
Rubber products are widely used in production and life due to their excellent high elasticity and mechanical properties. The conductive elastomer composite material can be prepared by adding the conductive filler into the flexible rubber, has excellent flexibility and stretchability of the rubber, has conductivity and electromagnetic shielding performance endowed by the conductive filler, and has wide application in the fields of flexible electronic appliances, automobile manufacturing and aerospace.
In the conventional conductive elastomer composite material, the conductive filler is randomly distributed, has poor interface compatibility with a rubber matrix and is difficult to uniformly disperse. Higher filler content is usually required to achieve the required conductivity, resulting in poor mechanical properties, complex processing and high cost of rubber products. An isolation structure is constructed in the rubber matrix, so that the conductive filler is selectively and orderly distributed around the rubber particles to form a high-efficiency conductive path, and the conductivity and the electromagnetic shielding performance of the rubber composite material can be obviously improved. However, the compatibility of the rubber matrix and the interface of conductive fillers such as metal and carbon materials is poor, and the diffusion and entanglement of rubber molecular chains to adjacent particles are limited by the isolation structure formed by the traditional method, so that the mechanical property of the composite material is obviously reduced. Therefore, there is a need in the art for a highly conductive flexible electromagnetic shielding composite material with simple preparation method and excellent mechanical properties.
The chinese patent application CN105086012A mixes the natural rubber latex with Carbon Nanotubes (CNTs), a surfactant CTBA, and a vulcanizing agent DCP, and presses to obtain a flexible CNT/natural rubber composite material with an isolation structure, where when the CNT content is 5.0wt.%, the electromagnetic shielding effectiveness (EMI SE) of the composite material is 44.5dB, the tensile strength is 9.4MPa, and is improved by 276% compared with pure natural rubber. However, this method requires the addition of a surfactant and a vulcanizing agent, and the improvement in tensile strength is not yet significant enough. The Chinese patent application CN107163333A mixes the waste rubber powder with CNT at high speed, hot pressing, the EMI SE of the prepared composite material can reach 66.9dB when the content of CNT is 5.0 wt.%. However, no mechanical properties of the composite material have been reported. In these patent applications, there have been few studies on conductive rubber composites with high mechanical properties; an isolation structure with high interface compatibility is constructed in the rubber matrix through the interaction of covalent bonds and hydrogen bonds between the rubber matrix and the filler, and the flexible epoxidized natural rubber electromagnetic shielding composite material with high mechanical property and high conductivity is prepared.
Disclosure of Invention
Aiming at the defect of poor mechanical property of the existing conductive elastomer composite material, the invention mainly aims to provide a flexible epoxidized natural rubber electromagnetic shielding composite material with high mechanical property and high conductivity.
The invention also aims to provide a preparation method of the flexible epoxidized natural rubber electromagnetic shielding composite material with high mechanical property and high conductivity.
The invention further aims to provide application of the flexible epoxidized natural rubber electromagnetic shielding composite material with high mechanical property and high conductivity.
The purpose of the invention is realized by the following technical scheme.
A preparation method of an epoxidized natural rubber electromagnetic shielding composite material comprises the following steps:
adding epoxidized natural rubber latex into a filler, uniformly mixing, and then adding hydrazine hydrate for reaction; then drying and hot-press molding to obtain the epoxidized natural rubber electromagnetic shielding composite material;
the filler is GO/Fe 3 O 4 I.e. Fe 3 O 4 A mixture uniformly deposited on GO.
Preferably, the epoxidized natural rubber electromagnetic shielding composite material consists of: 50-95 wt.% of epoxidized natural rubber, 1-15 wt.% of reduced graphene oxide and Fe 3 O 4 5～35wt.％。
Preferably, the content of the reduced graphene oxide in the epoxidized natural rubber electromagnetic shielding composite material is 1.8 to 7.7wt.%.
Preferably, said GO/Fe 3 O 4 The preparation method comprises the following steps:
dispersing GO in water, and adding Fe 3+ And Fe 2+ And (2) adding aqueous solution with the molar ratio of 3 3 O 4 。
Preferably, the ratio of the GO to the hydrazine hydrate is 1.
Preferably, the reaction temperature is 50-80 ℃ and the reaction time is 1-6 h.
Preferably, the hot-press molding is carried out for 3-15 min under the pressure of 10-30 MPa and at the temperature of 100-180 ℃.
Preferably, the epoxidized natural rubber latex has a solid content of 20 to 60wt% and an epoxy value of 25 to 75%.
Preferably, the specification of GO is 95-99% of purity, and the diameter is 1-30 μm.
Preferably, said Fe 3+ As FeCl 3 ·6H 2 O,Fe 2+ Is FeCl 2 ·4H 2 O and FeSO 4 ·4H 2 And O is any one of the above.
Preferably, the purity of the hydrazine hydrate is 98-99%.
Preferably, the above preparation method specifically comprises the steps of:
(1) One-pot in-situ preparation of ENR/rGO/Fe 3 O 4 : ultrasonically stirring 0.5-3 parts by mass of GO and deionized water according to the weight ratio of 1 3+ And Fe 2+ Adding ammonia water with the concentration of 25-28% into an aqueous solution with the molar ratio of 3 3 O 4 (ii) a Adding 10-100 parts by mass of ENR latex, uniformly mixing by ultrasonic stirring, adding hydrazine hydrate according to the ratio of GO to hydrazine hydrate of 1-3-1 (g/mL), and continuously stirring for 1-6 h at 50-80 ℃ until the reaction is finished;
(2) And (3) drying: filtering the mixed solution obtained in the step (1), washing the mixed solution for 2 to 5 times by using deionized water, and drying the mixed solution for 12 to 72 hours at the temperature of between 50 ℃ below zero and 25 ℃ below zero in a freeze dryer to obtain ENR/rGO/Fe 3 O 4 Compounding material;
(3) Hot-press molding: and (3) carrying out hot pressing on the composite material obtained in the step (2) for 3-15 min at the pressure of 10-30 MPa and the temperature of 100-180 ℃ to obtain a target sheet product.
And (4) the thickness of the target sheet product in the step (3) is 0.2-5 mm.
The epoxidized natural rubber electromagnetic shielding composite material prepared by the preparation method.
The epoxidized natural rubber electromagnetic shielding composite material is applied to flexible electronic appliances, automobile manufacturing and aerospace.
The invention adopts Epoxidized Natural Rubber (ENR) latex as a matrix and Fe 3 O 4 Depositing in situ on hydrophilic Graphene Oxide (GO) to enable the filler to be fully contacted with ENR particles; carrying out in-situ reduction on GO by using hydrazine hydrate to form a high-efficiency conductive isolation network; hydrazine hydrate reacts with epoxy groups on GO and ENR to realize the interaction of covalent bonds and hydrogen bonds between an ENR matrix and a reduced graphene oxide (rGO) filler, and the flexible epoxidized natural rubber electromagnetic shielding composite material with high mechanical property and high conductivity is prepared.
The principle of the invention is as follows: the hydrophilic oxygen-containing groups on GO make it disperse uniformly in water. Adding Fe to GO dispersion 3+ And Fe 2+ Adjusting the pH to make Fe 3 O 4 Uniformly deposited on GO. GO/Fe after ENR latex addition 3 O 4 Fully contacts with ENR latex particles and is mixed uniformly. After adding hydrazine hydrate, the hydrazine hydrate reduces GO to rGO; meanwhile, hydrazine hydrate reacts with epoxy groups on GO and ENR respectively to serve as a bridge between ENR and rGO/Fe 3 O 4 The interface constructs covalent bond and hydrogen bond interaction. rGO/Fe during hot pressing 3 O 4 The space between the ENR particles is occupied, the ENR particles and the molecular chains on the surfaces of the ENR particles are tightly acted, the interface between the matrix and the filler is improved, an isolation structure with high interface compatibility is constructed in the matrix, a high-efficiency conductive path is formed, high electromagnetic shielding performance taking wave absorption as the leading factor is obtained, and the mechanical property is obviously improved.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The invention utilizes hydrazine hydrate to form in situ GO into rGO in ENR latex. Hydrazine hydrate reacts with epoxy groups on GO and ENR at the same time, covalent bond and hydrogen bond interface interaction are formed between rGO and ENR, an isolation structure with high interface compatibility is constructed, and the mechanical property of the composite material is greatly improved. Conventional conductive composite material with isolation structureBecause of the poor interface compatibility between the conductive filler and the matrix, the mechanical properties are generally much lower than those of the matrix material. The tensile strength of the composite material prepared by the invention is up to 14.3MPa, which is 2310 percent higher than 0.6MPa of pure ENR, and is higher than that of the existing report ENR composite material (ACS Sustainable Chemistry Engineering,2020,8, 1285-1294, 2020, 8; the elongation at break is as high as 440%, and the excellent ductility and elasticity of ENR are maintained. Thus ENR/rGO/Fe prepared by the method of the invention 3 O 4 The composite material has excellent mechanical properties.
(2) In the invention, GO/Fe is made by utilizing the hydrophilicity of GO 3 O 4 Upon sufficient contact with ENR latex particles, GO is reduced in situ to rGO by hydrazine hydrate. In the hot press forming process, rGO/Fe 3 O 4 The filler uniformly wraps the matrix particles, selective distribution is realized, and the construction of a high-efficiency conductive isolation structure can be realized under the condition of lower conductive filler content. ENR/rGO/Fe at a rGO content of only 1.8wt.% 3 O 4 The conductivity of the composite material can reach 0.6S/m; ENR/rGO/Fe at a rGO content of 7.7 wt% 3 O 4 The conductivity of the composite material is as high as 50S/m, which is far superior to the reported rubber composite material. Thus ENR/rGO/Fe prepared by the method of the invention 3 O 4 The composite material can obtain high conductivity at low conductive filler content.
(3) In-situ deposition of Fe on hydrophilic GO 3 O 4 Of Fe 3 O 4 Realizes rGO/Fe without sedimentation along with the uniform dispersion of GO in ENR 3 O 4 Selective distribution, which is beneficial to the absorption of electromagnetic wave. ENR/rGO/Fe at a rGO content of 7.7wt.% 3 O 4 The EMI SE of the composite material is as high as 40.6dB, and the electromagnetic wave absorption rate is as high as 99.97%. Therefore, the method can prepare the high-efficiency electromagnetic shielding material taking wave absorption as the leading factor.
(4) ENR in the invention is green and environment-friendly bio-based rubber, and other raw materials are low in use content and are common and easy to obtain; other auxiliary agents such as vulcanizing agent, surface active agent and the like are not required to be added; the one-pot in-situ preparation process is simple and easy to operate, and the adjustable range of technological parameters in the hot pressing process is large; does not need complex instruments and equipment, and is easy for industrial production.
Drawings
FIG. 1 shows the high mechanical property and high conductivity flexible ENR/rGO/Fe of the present invention 3 O 4 Schematic diagram of electromagnetic shielding composite material preparation.
FIG. 2 shows the high mechanical property and high conductivity flexible ENR/rGO/Fe of the present invention 3 O 4 A scanning electron microscope image of the electromagnetic shielding composite; where a is comparative example 1, b is comparative example 2, c is example 2, d is example 1, e is example 3.
FIG. 3 shows the high mechanical property and high conductivity flexible ENR/rGO/Fe of the invention 3 O 4 Transmission electron microscopy of the electromagnetic shielding composite; wherein a is example 2, b is example 1, c is example 3.
FIG. 4 shows the high mechanical property and high conductivity flexible ENR/rGO/Fe of the invention 3 O 4 A tensile stress strain plot of the electromagnetically shielded composite.
FIG. 5 shows the high mechanical properties and high conductivity flexible ENR/rGO/Fe of the present invention 3 O 4 Conductivity map of the electromagnetic shielding composite.
FIG. 6 shows the high mechanical properties and high conductivity flexible ENR/rGO/Fe of the present invention 3 O 4 Electromagnetic shielding performance of the electromagnetic shielding composite material.
Detailed Description
The present invention will be described in detail below with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
The process flow for the preparation of the samples according to the invention is shown in FIG. 1. The reagents mentioned in the examples below are all available directly from commercial sources.
GO can be made according to the Journal of the American Chemical Society,1958, 80.
The following parts by mass are in g.
Example 1
(1) One-pot in-situ preparation of ENR/rGO/Fe 3 O 4 : ultrasonically stirring 0.7 part by mass of GO and deionized water according to a weight ratio of 1Cl 3 ·6H 2 O and 1.2 parts by mass of FeCl 2 ·4H 2 Adding 28% ammonia water into the O aqueous solution to adjust the pH to be =10 to obtain GO/Fe 3 O 4 (ii) a Adding 24 parts by mass of ENR latex, uniformly mixing by ultrasonic stirring, adding 5mL of hydrazine hydrate, and continuously stirring at 70 ℃ for 4 hours until the reaction is finished.
(2) And (3) drying: filtering the obtained mixed solution, washing with deionized water for 3 times, and drying in a freeze dryer at-30 deg.C for 48h to obtain ENR/rGO/Fe with rGO content of 4.7 wt% 3 O 4 A composite material.
(3) Hot-press molding: and hot-pressing the obtained composite material at 150 ℃ for 5min under the pressure of 20MPa to obtain a sheet with the thickness of 3 mm.
Example 2
(1) One-pot in-situ preparation of ENR/rGO/Fe 3 O 4 : ultrasonically stirring 0.7 part by mass of GO and deionized water according to a weight ratio of 1 3 ·6H 2 O and 1.2 parts by mass of FeCl 2 ·4H 2 Adding 28% ammonia water into the O aqueous solution to adjust the pH to be =10 to obtain GO/Fe 3 O 4 (ii) a Adding 72 parts by mass of ENR latex, uniformly mixing by ultrasonic stirring, adding 5mL of hydrazine hydrate, and continuously stirring at 70 ℃ for 4 hours until the reaction is finished.
(2) And (3) drying: filtering the obtained mixed solution, washing with deionized water for 3 times, and drying in a freeze dryer at-30 ℃ for 48h to obtain ENR/rGO/Fe with the rGO content of 1.8 wt% 3 O 4 A composite material.
(3) Hot-press molding: and hot-pressing the obtained composite material at 150 ℃ for 5min under the pressure of 20MPa to obtain a sheet with the thickness of 3 mm.
Example 3
(1) One-pot in-situ preparation of ENR/rGO/Fe 3 O 4 : ultrasonically stirring 1.4 parts by mass of GO and deionized water according to a weight ratio of 1 3 ·6H 2 O and 2.4 parts by mass of FeCl 2 ·4H 2 Adding 28% ammonia water into the O aqueous solution to adjust the pH to be =10 to obtain GO/Fe 3 O 4 (ii) a Adding 24 parts by mass of ENR latex, uniformly mixing by ultrasonic stirring, and adding 10mL of waterHydrazine is added and stirring is continued at 70 ℃ for 4h until the reaction is finished.
(2) And (3) drying: filtering the obtained mixed solution, washing with deionized water for 3 times, and drying in a freeze dryer at-30 ℃ for 48h to obtain ENR/rGO/Fe with the rGO content of 7.7 wt% 3 O 4 A composite material.
(3) Hot-press molding: and carrying out hot pressing on the obtained composite material for 5min at the pressure of 20MPa and the temperature of 150 ℃ to obtain a sheet with the thickness of 3 mm.
Example 4
(1) One-pot in-situ preparation of ENR/rGO/Fe 3 O 4 : ultrasonically stirring 0.7 part by mass of GO and deionized water according to the weight ratio of 1:400 to prepare a dispersion, and adding FeCl containing 1.7 parts by mass 3 ·6H 2 O and 0.7 part by mass of FeSO 4 ·4H 2 Adding 28% ammonia water into the O aqueous solution to adjust the pH to be =10 to obtain GO/Fe 3 O 4 (ii) a Adding 24 parts by mass of ENR latex, uniformly mixing by ultrasonic stirring, adding 5mL of hydrazine hydrate, and continuously stirring at 70 ℃ for 4 hours until the reaction is finished.
(2) And (3) drying: filtering the obtained mixed solution, washing with deionized water for 3 times, and drying in a freeze dryer at-30 deg.C for 48h to obtain ENR/rGO/Fe with rGO content of 4.7 wt% 3 O 4 A composite material.
(3) Hot-press molding: and hot-pressing the obtained composite material at 150 ℃ for 5min under the pressure of 20MPa to obtain a sheet with the thickness of 3 mm.
Example 5
(1) One-pot in-situ preparation of ENR/rGO/Fe 3 O 4 : ultrasonically stirring 0.7 part by mass of GO and deionized water according to the weight ratio of 1 3 ·6H 2 O and 1.2 parts by mass of FeCl 2 ·4H 2 Adding 28% ammonia water into the O water solution to adjust the pH to be 12 to obtain GO/Fe 3 O 4 (ii) a Adding 24 parts by mass of ENR latex, uniformly mixing by ultrasonic stirring, adding 20mL of hydrazine hydrate, and continuously stirring at 80 ℃ for 1h until the reaction is finished.
(2) And (3) drying: filtering the obtained mixed solution, washing with deionized water for 5 times, and drying in a freeze dryer at-25 deg.C for 72h to obtain ENR/rGO/Fe with rGO content of 4.7 wt% 3 O 4 A composite material.
(3) Hot-press molding: and hot-pressing the obtained composite material at 180 ℃ for 3min under the pressure of 10MPa to obtain a sheet with the thickness of 3 mm.
Example 6
(1) One-pot in-situ preparation of ENR/rGO/Fe 3 O 4 : ultrasonically stirring 0.7 part by mass of GO and deionized water according to a weight ratio of 1 3 ·6H 2 O and 1.2 parts by mass of FeCl 2 ·4H 2 Adding ammonia water with the concentration of 25% into the O water solution to adjust the pH to be =10 to obtain GO/Fe 3 O 4 (ii) a Adding 24 parts by mass of ENR latex, uniformly mixing by ultrasonic stirring, adding 5mL of hydrazine hydrate, and continuously stirring at 50 ℃ for 6 hours until the reaction is finished.
(2) And (3) drying: filtering the obtained mixed solution, washing with deionized water for 3 times, and drying in a freeze dryer at-50 deg.C for 24h to obtain ENR/rGO/Fe with rGO content of 4.7 wt% 3 O 4 A composite material.
(3) Hot-press molding: the resulting composite was hot-pressed at 100 ℃ under a pressure of 30MPa for 10min to give a sheet of 0.5mm thickness.
Comparative example 1
(1) And (3) drying: the ENR latex was dried in a freeze dryer at-30 ℃ for 48h.
(2) Hot-press molding: hot pressing at 150 deg.C under 20MPa for 5min to obtain 3mm sheet.
Comparative example 2
(1) Preparation of rGO/Fe 3 O 4 : ultrasonically stirring 0.7 part by mass of GO and deionized water according to a weight ratio of 1 3 ·6H 2 O and 1.2 parts by mass of FeCl 2 ·4H 2 Adding 28% ammonia water into the O aqueous solution to adjust the pH to be =10 to obtain GO/Fe 3 O 4 (ii) a 5mL of hydrazine hydrate was added and stirring was continued at 70 ℃ for 4h until the reaction was complete. Filtering the obtained mixed solution, washing with deionized water for 3 times, and drying in a freeze dryer at-30 deg.C for 48h to obtain rGO/Fe 3 O 4 。
(2) Preparation of ENR/rGO/Fe 3 O 4 : mixing the obtained rGO/Fe 3 O 4 Adding into 24 parts by mass of ENR latexAfter being stirred and mixed evenly by ultrasonic, the mixture is dried for 48 hours at minus 30 ℃ in a freeze drier to obtain ENR/rGO/Fe 3 O 4 。
(3) Hot-press molding: and hot-pressing the obtained composite material at 150 ℃ for 5min under the pressure of 20MPa to obtain a sheet with the thickness of 3 mm.
For visual evaluation of ENR/rGO/Fe 3 O 4 rGO/Fe in composite material 3 O 4 The invention utilizes a Scanning Electron Microscope (SEM) and a Transmission Electron Microscope (TEM) to observe the microscopic appearances of comparative examples 1-2 and examples 1-3, which are respectively shown in FIG. 2 and FIG. 3.
The tensile stress strain properties (according to GB/T528-2009) of examples 1-4 and comparative examples 1-2 were tested and the results are shown in FIG. 4. The above examples 1 to 4 and comparative examples 1 to 2 were subjected to conductivity measurement using an RST-8 type four-probe tester, and the results are shown in FIG. 5. Examples 1 to 4 and comparative example 2 were tested for electromagnetic shielding performance in the frequency range of 8.2 to 12.4GHz using a vector network analyzer (Agilent N5244A, usa), and the results are shown in fig. 6.
As can be seen from the SEM image of FIG. 2, the brittle section of comparative example 1 is smooth and flat, and the apparent rGO/Fe appears in comparative example 2 3 O 4 Aggregate, whereas in examples 1-3, rGO/Fe 3 O 4 The (bright part) is uniformly distributed around the ENR particles (dark part), the section is smooth, and no holes are formed due to the falling or pulling of the filler, which shows that the ENR/rGO/Fe prepared by the invention 3 O 4 The composite material has high interface compatibility caused by covalent bond and hydrogen bond interaction. As can be seen from the TEM image of FIG. 3, in examples 1-3, rGO/Fe 3 O 4 The filler is dispersed around the ENR particles and is lapped into a continuous filler network structure. With the increase of the content of the filler, the conductive network is clearer and more obvious.
As can be seen from FIG. 4, ENR/rGO/Fe increases with filler content 3 O 4 The tensile strength of the composite material is gradually improved, and the elongation at break is increased and then reduced. Example 1 a composite material with a rGO content of 4.7wt.% with a tensile strength of 12.7MPa and an elongation at break of 253% was prepared, while maintaining comparative example 1The tensile strength is improved by 2050% on the premise of elongation at break of pure ENR rubber; the composite material prepared in example 2, in which the rGO content is 1.8wt.%, has an elongation at break as high as 440%, which is 160% higher than that of the pure ENR rubber of comparative example 1; the composite material prepared in example 3, with a rGO content of 7.7wt.%, has a tensile strength of up to 14.3MPa, which is increased to 2310% compared to pure ENR of comparative example 1, which is higher than the existing reports for ENR composite materials (ACS sustamable Chemistry Engineering,2020, 8. While comparative example 2 ENR/rGO/Fe by direct mixing 3 O 4 Composite material due to rGO/Fe 3 O 4 The filler is seriously agglomerated, and the mechanical property improvement range is small.
As can be seen from FIG. 5, ENR/rGO/Fe as the rGO content increases 3 O 4 The electrical conductivity of the composite material gradually increases. The composite material prepared in example 1, with a rGO content of 4.7wt.%, has a conductivity of up to 10S/m; example 2a composite with a rGO content of 1.8wt.% was prepared with a conductivity of up to 0.6S/m; example 3 produced a composite with a rGO content of 7.7wt.% with a conductivity of up to 50S/m. Example 4a composite material with a rGO content of 4.7wt.% was produced due to Fe 3 O 4 The content is low, direct contact of conductive rGO is facilitated, and the conductivity can reach 25S/m. While comparative example 2 is due to rGO/Fe 3 O 4 The filler is seriously agglomerated and the conductivity is only 8.5 multiplied by 10 -7 S/m。
As can be seen from FIG. 6, ENR/rGO/Fe as the rGO content increases 3 O 4 The electromagnetic shielding performance of the composite material is gradually improved. The composite material prepared in example 3, which has a rGO content of 7.7wt.%, has an EMI SE of 40.6dB and an electromagnetic wave absorption rate as high as 99.97%. While comparative example 2 is due to rGO/Fe 3 O 4 The filler agglomeration is severe and the conductivity is low, resulting in a low EMI SE.
Therefore, the invention utilizes the simple and feasible one-pot preparation process of the ENR composite material isolation structure to construct the high-efficiency conductive network with high interface compatibility in the rubber matrix, and obtains the flexible epoxidized natural rubber electromagnetic shielding composite material with high mechanical property and high conductivity.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. The preparation method of the epoxidized natural rubber electromagnetic shielding composite material is characterized by comprising the following steps of:
adding epoxidized natural rubber latex into a filler, uniformly mixing, and then adding hydrazine hydrate for reaction; then drying and hot-press molding to obtain the epoxidized natural rubber electromagnetic shielding composite material;
the filler is GO/Fe 3 O 4 I.e. Fe 3 O 4 A mixture uniformly deposited on GO.
2. The method for preparing the epoxidized natural rubber electromagnetic shielding composite material according to claim 1, wherein the epoxidized natural rubber electromagnetic shielding composite material is prepared from the following substances: 50-95 wt.% of epoxidized natural rubber, 1-15 wt.% of reduced graphene oxide and Fe 3 O 4 5～35wt.％。
3. The method for preparing the epoxidized natural rubber electromagnetic shielding composite material according to claim 2, wherein the content of the reduced graphene oxide in the epoxidized natural rubber electromagnetic shielding composite material is 1.8 to 7.7wt.%.
4. The method for preparing the epoxidized natural rubber electromagnetic shielding composite material according to any one of claims 1 to 3, wherein the GO/Fe is 3 O 4 The preparation method comprises the following steps:
dispersing GO in water, and adding Fe 3+ And Fe 2+ And (2) adding aqueous solution with the molar ratio of 3 3 O 4 。
5. The method for preparing the epoxidized natural rubber electromagnetic shielding composite material according to any one of claims 1 to 3, wherein the ratio of the GO to the hydrazine hydrate is 1.
6. The method for preparing an epoxidized natural rubber electromagnetic shielding composite material according to any of claims 1-3, wherein the reaction temperature is 50-80 ℃ and the reaction time is 1-6 hours.
7. The method for preparing an epoxidized natural rubber electromagnetic shielding composite material according to any one of claims 1 to 3, wherein the hot press molding is performed under a pressure of 10 to 30MPa at a temperature of 100 to 180 ℃ for 3 to 15min.
8. The method for preparing an epoxidized natural rubber electromagnetic shielding composite material according to any one of claims 1-3, wherein the epoxidized natural rubber latex has a solid content of 20-60 wt% and an epoxy value of 25-75 wt%.
9. An epoxidized natural rubber electromagnetic shielding composite material produced by the production method according to any one of claims 1 to 8.
10. The epoxidized natural rubber electromagnetic shielding composite material of claim 9, which is used in flexible electronic appliances, automobile manufacturing and aerospace.
CN202210965151.5A 2022-08-12 2022-08-12 Epoxidized natural rubber electromagnetic shielding composite material and preparation method and application thereof Pending CN115353677A (en)

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CN110527159A (en) * 2019-08-30 2019-12-03 北京化工大学 A kind of original position hydrorubber graphene elastomer and preparation method
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CN106608991A (en) * 2015-10-21 2017-05-03 中国石油化工股份有限公司 Conductive rubber composition, and conductive rubber and preparation method thereof
CN110678055A (en) * 2018-07-02 2020-01-10 南开大学 Graphene/ferroferric oxide composite material, preparation method and application thereof
CN110527159A (en) * 2019-08-30 2019-12-03 北京化工大学 A kind of original position hydrorubber graphene elastomer and preparation method

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