CN110699038B - Preparation method of magnetic porous composite material with wide glass-transition temperature range - Google Patents
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Abstract
The invention provides a preparation method of a magnetic porous composite material with a wide glass transition temperature range, which is characterized in that a co-stabilizer of Pickering emulsion is formed by a carbon nano tube-graphene oxide hybrid material and Span80, a monomer with polymerization activity is used as a continuous oil phase, graphene oxide/ferrous ion solution is used as a dispersed water phase, and the magnetic porous composite material with the wide glass transition temperature range is prepared through the steps of oil-in-oil Pickering emulsion preparation, free radical polymerization, magnetic nanoparticle synthesis, freeze drying and the like.
Description
Technical Field
The invention belongs to the field of nano materials, and particularly relates to a preparation method of a magnetic porous composite material with a wide glass-transition temperature range.
Background
Currently, with the rapid development of electronic information technology, various electronic devices are increasingly put into production and life of people, the influence of electromagnetic radiation generated by electronic devices on human health and the operation of instruments and equipment has attracted great attention, and one of effective means for solving the problem of electromagnetic radiation is to develop a low-cost and high-performance electromagnetic wave absorbing material. Generally, when a wave-absorbing material is designed, in order to achieve effective absorption and attenuation of electromagnetic waves, on one hand, reflection of the electromagnetic waves on the surface of the material should be reduced as much as possible, and on the other hand, the absorbed electromagnetic waves should be converted into heat through mechanisms such as conduction loss, dielectric loss and magnetic loss and dissipated. In order to improve the impedance matching characteristic of the wave-absorbing material and improve the electromagnetic absorption efficiency, the development of the structure-function integrated composite wave-absorbing material containing multiple electromagnetic loss processes is a problem to be solved urgently. As is well known, the glass transition temperature is an important index for maintaining the shape precision and the size precision of a polymer material and a composite material thereof in the service process. Therefore, the construction of the magnetic porous composite material with a wide glass transition temperature range is of great significance for the development of light electromagnetic wave absorbing materials.
Carbon nano materials represented by carbon nano tubes and graphene have huge specific surface area, excellent mechanical properties, electric conductivity and heat conductivity, and are attracted by attention in the fields of electronic information, novel energy sources and functional composite materials in recent years. However, carbon nanotubes and graphene, which are currently and widely produced by Chemical Vapor Deposition (CVD), have problems of functional anisotropy and agglomeration caused by one-dimensional and two-dimensional structures, and cannot form a three-dimensional macroscopic ordered structure in a high-viscosity resin matrix, thereby seriously restricting the full exertion of the properties of the carbon nanotube material.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a magnetic porous composite material with a wide glass-transition temperature range, which aims to utilize a carbon nano tube-graphene oxide hybrid material and Span80 as co-stabilizers to form a water-in-oil Pickering emulsion, prepare a hierarchical porous composite material through free radical polymerization, use dispersed water drops in pores as a reaction medium, prepare the magnetic porous composite material with the wide glass-transition temperature range through hydrothermal reaction and freeze drying processes, and has the advantages of controllable pore structure, adjustable magnetism and three-dimensional macroscopic morphology, simple preparation process and low cost.
The technical scheme adopted by the invention for realizing the purpose is as follows: a preparation method of a magnetic porous composite material with a wide glass-transition temperature range comprises the following steps:
(1) ultrasonically dispersing graphene oxide in water to obtain a graphene oxide dispersion liquid;
(2) adding a carbon nano tube into the graphene oxide dispersion liquid obtained in the step (1), after ultrasonic dispersion, adding polyacrylamide, continuing ultrasonic dispersion, then drying to constant weight, heating the obtained dried sample to 240 ℃ under the protection of nitrogen, and preserving heat for 1.5 hours to obtain a hydrophobic carbon nano tube-graphene oxide hybrid material;
(3) adding a monomer serving as an oil phase into a Span80 and a carbon nanotube-graphene oxide hybrid material serving as a co-stabilizer; taking a graphene oxide/ferrous ion water solution as a water phase, wherein the pH value of the water phase is 3-6, then dropwise adding the water phase into the obtained oil phase at a constant speed, and performing ultrasonic dispersion to obtain a water-in-oil Pickering emulsion;
(4) transferring the water-in-oil type Pickering emulsion obtained in the step (3) into a stainless steel polymerization kettle, sealing, heating to 65-75 ℃, and keeping the temperature for 6 hours to obtain a porous polymer framework material;
(5) adding ammonia water into the stainless steel polymerization kettle obtained in the step (4), adjusting the pH value of the system to 11, sealing, heating to 90 ℃, and preserving heat for 8.5 hours;
(6) And (5) carrying out freeze drying treatment on the product obtained in the step (5) for 24 hours to obtain the magnetic porous composite material with a wide glass-transition temperature range.
Further, the diameter of the graphene oxide in the step (1) is 20-70 μm, and the concentration of the graphene oxide dispersion liquid is 1-8 mg/ml.
Further, the carbon nanotube in the step (2) is a surface carboxyl modified carbon nanotube or a surface amino modified carbon nanotube or a surface hydroxyl modified carbon nanotube, and can be a single-walled carbon nanotube, a double-walled carbon nanotube or a multi-walled carbon nanotube, and the weight ratio of the graphene oxide to the carbon nanotube is 6: 1-2: 1.
Further, the mass of the polyacrylamide in the step (2) is 1% of the total mass of the graphene oxide and the carbon nano tube.
Further, in the step (3), the monomer is a styrene/divinylbenzene mixture with a volume ratio of 4:1, or an acrylonitrile/divinylbenzene mixture with a volume ratio of 4:1, or a methyl methacrylate monomer, and the oil phase also contains an initiator azobisisobutyronitrile, wherein the mass of the initiator is 2% of the total mass of the monomers.
Further, in the step (3), the adding amount of the Span80 is 1% of the mass of the oil phase, and the adding amount of the carbon nanotube-graphene oxide hybrid material is 1.5% of the mass of the oil phase.
Further, the volume ratio of oil to water of the Pickering emulsion in the step (3) is 1: 4.
Further, the ultrasonic dispersion time in the step (1) is 30 minutes, the ultrasonic dispersion time after the carbon nano tube is added in the step (2) is 1-2 hours, the ultrasonic dispersion time is 1 hour after the polyacrylamide is added, the ultrasonic dispersion time in the step (3) is 2-3 hours, the working frequency of an ultrasonic field is 45kHz, and the power is 150W.
Further, the pH value of the water phase in the step (3) is adjusted by hydrochloric acid or nitric acid.
Further, the ferrous ion aqueous solution in the step (3) is ferrous sulfate or ferrous nitrate aqueous solution, and the concentration is 0.2 mg/ml-0.5 mg/ml.
Further, the specific surface area of the composite material prepared in the step (6) is 4.24-4.92 m2In the glass transition temperature range of 80 ℃ and pore diameters in the order of 1 and 100. mu.m.
Compared with the prior art, the invention has the characteristics and beneficial effects that:
(1) according to the invention, a carbon nanotube-graphene oxide hybrid material and Span80 are used as co-stabilizers to prepare a hierarchical porous material containing pore diameters of 1 micron and 100 micron levels;
(2) in the presence of graphene oxide, the carbon nano tubes are uniformly dispersed in the carbon nano hybrid material, and the carbon nano hybrid material is assembled into a three-dimensional macroscopic ordered network structure at an oil-water interface under the action of the tension of the oil-water interface;
(3) According to the invention, pores with different sizes in a polymer framework material are used as microreactors, a water phase is used as a reaction medium, and the magnetic polymer-based porous composite material containing ferroferric oxide nanoparticles is synthesized, wherein the synthesized magnetic porous composite material has a wide glass transition temperature range, and the structure and the performance of the composite material can be regulated and controlled by controlling the using amount of a carbon nano hybrid material, the concentrations of graphene oxide and ferrous ions and the reaction degree;
(4) the magnetic porous composite material with wide glass-transition temperature range prepared by the invention has the advantages of low cost, high performance, environmental friendliness and the like, is easy to prepare composite material components with different shapes, has simple and convenient preparation process, and has wide application prospect in the fields of electromagnetic wave shielding, absorption and the like.
Drawings
FIG. 1 is an optical photograph of a magnetic porous composite prepared in example 1 of the present invention;
FIG. 2 is an SEM photograph of a magnetic porous composite material prepared in example 1 of the present invention;
fig. 3 is a graph of dissipation factor versus temperature for the magnetic porous composite prepared in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
The graphene oxide adopted by the invention is a graphene derivative obtained by a chemical stripping method, and in the preparation process, a large number of polar oxygen-containing groups are introduced on the surface of the graphene through oxidation treatment, particularly on the edge to form partial sp3Sp hybridized to carbon atoms while the unoxidized regions remain hydrophobic2The graphene oxide has a hybrid carbon atom structure, so that the graphene oxide has amphipathy similar to that of a surfactant while a flexible two-dimensional structure of the graphene is kept;
the Pickering emulsion is a thermodynamic heterogeneous system with solid particles spontaneously adsorbed and stabilized on an oil-water two-phase interface, the water-in-oil type Pickering emulsion template method adopted by the invention takes hydrophobic solid particles as a stabilizer and a monomer with polymerization activity as a continuous phase, and a porous polymer matrix composite material with controllable pore types, sizes and distribution can be prepared by the technical processes of emulsion formation, free radical polymerization, dehydration, drying and the like.
The invention provides a preparation method of a magnetic porous composite material with a wide glass-transition temperature range, which utilizes a co-stabilizer of Pickering emulsion composed of a carbon nano tube-graphene oxide hybrid material and Span80, takes a monomer with polymerization activity as a continuous oil phase, takes graphene oxide/ferrous ion solution as a dispersed water phase, and prepares the magnetic porous composite material with the wide glass-transition temperature range through the steps of oil-in-oil Pickering emulsion preparation, free radical polymerization, magnetic nanoparticle synthesis, freeze drying and the like.
Ferrous sulfate, ferrous nitrate, Span80, styrene, acrylonitrile, divinylbenzene, methyl methacrylate and azobisisobutyronitrile adopted in the embodiment of the invention are commercial products;
the surface carboxyl modified carbon nano tube, the surface amino modified carbon nano tube and the surface hydroxyl modified carbon nano tube adopted in the embodiment of the invention are commercially available products; the diameter of the graphene oxide adopted in the embodiment is 20-70 μm;
the working frequency of the ultrasonic field adopted in the embodiment of the invention is 45kHz, and the power is 150W.
Example 1
The preparation method of the magnetic porous composite material with the wide glass transition temperature range is carried out according to the following steps:
(1) ultrasonically dispersing 2g of graphene oxide in 1000ml of water for 30 minutes to obtain 2mg/ml graphene oxide dispersion liquid;
(2) adding 1g of carboxyl modified multi-walled carbon nanotube into the graphene oxide dispersion liquid obtained in the step (1), after ultrasonic dispersion is carried out for 2 hours, adding 30mg of polyacrylamide, carrying out ultrasonic dispersion for 1 hour to obtain a carbon nanotube-graphene oxide dispersion system, drying to constant weight, heating the obtained dried sample to 240 ℃ under the protection of nitrogen, and carrying out heat preservation for 1.5 hours to obtain a hydrophobic carbon nanotube-graphene oxide hybrid material;
(3) Weighing Span80 and the carbon nanotube-graphene oxide hybrid material as co-stabilizers, adding 10ml of acrylonitrile/divinylbenzene mixed monomer (containing azodiisobutyronitrile accounting for 2% of the monomer mass) with the volume ratio of 4:1 as an oil phase, wherein the adding amount of the Span80 is 1% of the oil phase mass, and the adding amount of the carbon nanotube-graphene oxide hybrid material is 1.5% of the oil phase mass; then weighing 0.015g of ferrous sulfate, adding the ferrous sulfate into 40ml of graphene oxide dispersion liquid (the concentration is 2mg/ml), adjusting the pH value to be 3 by using hydrochloric acid to serve as a water phase, dropwise adding the water phase into the obtained oil phase at a constant speed within 45 minutes, and ultrasonically dispersing for 2.5 hours to obtain a water-in-oil Pickering emulsion;
(4) transferring the water-in-oil type Pickering emulsion obtained in the step (3) into a stainless steel polymerization kettle, sealing, heating to 65 ℃, and preserving heat for 6 hours to obtain a porous polyacrylonitrile/polydivinylbenzene framework material;
(5) adding ammonia water into the stainless steel polymerization kettle obtained in the step (4), adjusting the pH value of the system to 11, sealing, heating to 90 ℃, and preserving heat for 8.5 hours;
(6) and (3) carrying out freeze drying treatment on the product obtained in the step (5) for 24 hours to obtain the magnetic porous composite material (figure 1) with a wide glass transition temperature range, wherein the microstructure of the magnetic porous composite material is shown in figure 2, the magnetic porous composite material has pore structures with different diameters, and the specific surface area of the porous composite material is 4.45m 2In terms of/g, the glass transition temperature range is 80 ℃ as shown in FIG. 3.
Example 2
The preparation method of the magnetic porous composite material with the wide glass transition temperature range is carried out according to the following steps:
(1) ultrasonically dispersing 2g of graphene oxide in 1000ml of water for 30 minutes to obtain 2mg/ml graphene oxide dispersion liquid;
(2) adding 0.5g of hydroxyl-modified multi-walled carbon nanotube into the graphene oxide dispersion liquid obtained in the step (1), ultrasonically dispersing for 2 hours, adding 0.025g of polyacrylamide, ultrasonically dispersing for 1 hour to obtain a carbon nanotube-graphene oxide dispersion system, and drying to constant weight; under the protection of nitrogen, heating the obtained dry sample to 240 ℃ and preserving heat for 1.5 hours to obtain a hydrophobic carbon nanotube-graphene oxide hybrid material;
(3) weighing Span80 and a carbon nano tube-graphene oxide hybrid material as a co-stabilizer, adding 10ml of styrene/divinylbenzene mixed monomer (containing azodiisobutyronitrile accounting for 2% of the total mass of the monomers) in a volume ratio of 4:1 as an oil phase, wherein the adding amount of Span80 is 1% of the mass of the oil phase, and the adding amount of the carbon nano hybrid material is 1.5% of the mass of the oil phase; weighing 0.015g of ferrous nitrate, adding the ferrous nitrate into 40ml of graphene oxide dispersion liquid (the concentration is 2mg/ml), adjusting the pH value to be 5 by using hydrochloric acid to serve as a water phase, dropwise adding the mixture into the oil phase obtained in the step (2) at a constant speed within 45 minutes, and ultrasonically dispersing for 2.5 hours to obtain a water-in-oil Pickering emulsion;
(4) Transferring the water-in-oil type Pickering emulsion obtained in the step (3) into a stainless steel polymerization kettle, sealing, heating to 70 ℃, and preserving heat for 6 hours to obtain a porous polystyrene/polydivinylbenzene framework material;
(5) adding ammonia water into the stainless steel polymerization kettle obtained in the step (4), adjusting the pH value of the system to 11, sealing, heating to 90 ℃, and preserving heat for 8.5 hours;
(6) freeze-drying the product obtained in the step (5) for 24 hours to obtain the magnetic porous composite material with a wide glass-transition temperature range, wherein the specific surface area of the porous composite material is 4.92m2The glass transition temperature range is 80 ℃.
Example 3
The preparation method of the magnetic porous composite material with the wide glass transition temperature range is carried out according to the following steps:
(1) ultrasonically dispersing 5g of graphene oxide in 1000ml of water for 30 minutes to obtain 5mg/ml graphene oxide dispersion liquid;
(2) adding 1g of amino-modified multi-walled carbon nanotube into the graphene oxide dispersion liquid obtained in the step (1), performing ultrasonic dispersion for 2 hours, adding 60mg of polyacrylamide, performing ultrasonic dispersion for 1 hour to obtain a carbon nanotube-graphene oxide dispersion system, drying to constant weight, heating the obtained dried sample to 240 ℃ under the protection of nitrogen, and keeping the temperature for 1.5 hours to obtain a hydrophobic carbon nanotube-graphene oxide hybrid material;
(3) Weighing Span80 and a carbon nano tube-graphene oxide hybrid material as a co-stabilizer, adding 10ml of methyl methacrylate (containing azodiisobutyronitrile accounting for 2% of the mass of the monomer) as an oil phase, wherein the adding amount of Span80 is 1% of the mass of the oil phase, and the adding amount of the carbon nano hybrid material is 1.5% of the mass of the oil phase; weighing 0.015g of ferrous sulfate, adding the ferrous sulfate into 40ml of graphene oxide dispersion liquid (with the concentration of 5mg/ml), adjusting the pH value to be 4 by using nitric acid to serve as a water phase, dropwise adding the water phase into the oil phase obtained in the step (2) at a constant speed within 45 minutes, and ultrasonically dispersing for 2.5 hours to obtain a water-in-oil Pickering emulsion;
(4) transferring the water-in-oil type Pickering emulsion obtained in the step (3) into a stainless steel polymerization kettle, sealing, heating to 75 ℃, and preserving heat for 6 hours to obtain a porous polymethyl methacrylate framework material;
(5) adding ammonia water into the stainless steel polymerization kettle obtained in the step (4), adjusting the pH value of the system to 11, sealing, heating to 90 ℃, and preserving heat for 8.5 hours;
(6) and (3) carrying out freeze drying treatment on the product obtained in the step (5) for 24 hours to obtain the magnetic porous composite material with a wide glass transition temperature range, wherein the microstructure of the magnetic porous composite material is shown in figure 2, so that the magnetic porous composite material has pore structures with different diameters, and the specific surface area of the magnetic porous composite material is 4.24m 2The glass transition temperature range is 80 ℃.
The technical idea of the present invention is described in the above technical solutions, and the protection scope of the present invention is not limited thereto, and any changes and modifications made to the above technical solutions according to the technical essence of the present invention belong to the protection scope of the technical solutions of the present invention.
Claims (7)
1. A preparation method of a magnetic porous composite material with a wide glass-transition temperature range is characterized by comprising the following steps:
(1) ultrasonically dispersing graphene oxide in water to obtain a graphene oxide dispersion liquid;
(2) adding a carbon nano tube into the graphene oxide dispersion liquid obtained in the step (1), after ultrasonic dispersion, adding polyacrylamide, continuing ultrasonic dispersion, then drying to constant weight, heating the obtained dried sample to 240 ℃ under the protection of nitrogen, and preserving heat for 1.5 hours to obtain a hydrophobic carbon nano tube-graphene oxide hybrid material; the mass of the polyacrylamide is 1% of the total mass of the graphene oxide and the carbon nano tube;
(3) adding a monomer serving as an oil phase into a Span80 and a carbon nanotube-graphene oxide hybrid material serving as a co-stabilizer; taking a graphene oxide/ferrous ion water solution as a water phase, wherein the pH value of the water phase is 3-6, then dropwise adding the water phase into the oil phase, and performing ultrasonic dispersion to obtain a water-in-oil Pickering emulsion; the monomer is a styrene/divinylbenzene mixed monomer with the volume ratio of 4:1, or an acrylonitrile/divinylbenzene mixed monomer with the volume ratio of 4:1, or a methyl methacrylate monomer; the adding amount of the Span80 is 1% of the mass of the oil phase, and the adding amount of the carbon nano tube-graphene oxide hybrid material is 1.5% of the mass of the oil phase; the volume ratio of the Pickering emulsion oil to the water is 1: 4;
(4) Transferring the water-in-oil type Pickering emulsion obtained in the step (3) into a stainless steel polymerization kettle, sealing, heating to 65-75 ℃, and preserving heat for 6 hours to obtain a porous polymer framework material;
(5) adding ammonia water into the stainless steel polymerization kettle obtained in the step (4), adjusting the pH value of the system to 11, sealing, heating to 90 ℃, and preserving heat for 8.5 hours;
(6) and (5) carrying out freeze drying treatment on the product obtained in the step (5) for 24 hours to obtain the magnetic porous composite material with a wide glass-transition temperature range.
2. The preparation method of the magnetic porous composite material with the wide glass transition temperature range according to claim 1, wherein the graphene oxide diameter in the step (1) is 20-70 μm, and the concentration of the graphene oxide dispersion is 1-8 mg/ml.
3. The preparation method of the magnetic porous composite material with the wide glass transition temperature range according to claim 1, wherein the carbon nanotubes in the step (2) are surface carboxyl modified carbon nanotubes, surface amino modified carbon nanotubes or surface hydroxyl modified carbon nanotubes, and can be single-walled carbon nanotubes, double-walled carbon nanotubes or multi-walled carbon nanotubes, and the weight ratio of graphene oxide to the carbon nanotubes is 6: 1-2: 1.
4. The preparation method of the magnetic porous composite material with the wide glass transition temperature range according to claim 1, wherein the oil phase in the step (3) further contains an initiator azobisisobutyronitrile, and the mass of the initiator is 2% of the total mass of the monomers.
5. The preparation method of the magnetic porous composite material with the wide glass transition temperature range according to claim 1, wherein the ultrasonic dispersion time in the step (1) is 30 minutes, the ultrasonic dispersion time after the carbon nanotubes are added in the step (2) is 1-2 hours, the ultrasonic dispersion time after the polyacrylamide is added is 1 hour, the ultrasonic dispersion time in the step (3) is 2-3 hours, the working frequency of an ultrasonic field is 45kHz, and the power is 150W.
6. The preparation method of the magnetic porous composite material with the wide glass transition temperature range according to claim 1, wherein the pH value of the aqueous phase in the step (3) is adjusted by hydrochloric acid or nitric acid, and the ferrous ion aqueous solution in the step (3) is ferrous sulfate or ferrous nitrate aqueous solution.
7. The preparation method of the magnetic porous composite material with the wide glass transition temperature range according to claim 1, wherein the specific surface area of the composite material prepared in the step (6) is 4.24-4.92 m2In terms of/g, the glass transition temperature range is 80 ℃ and the pore diameters are in the order of 1 and 100. mu.m.
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