CN108250728B - Polymer/graphene aerogel composite foam material and preparation method thereof - Google Patents
Polymer/graphene aerogel composite foam material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a polymer/graphene aerogel composite foam material, which consists of graphene aerogel and a thermoplastic polymer, wherein the graphene aerogel is used as a framework, the thermoplastic polymer is attached to a three-dimensional network structure of the graphene aerogel, the thermoplastic polymer is provided with closed-cell-structure cells, the composite foam material is provided with mutually communicated three-dimensional network structures, and the content of the graphene aerogel in the composite foam material is 0.5-10%. The invention also provides a preparation method of the composite foam material. The invention provides a new idea for solving the problem of agglomeration of graphene in a polymer matrix material.
Description
Technical Field
The invention belongs to the field of polymer composite foam materials, and relates to a polymer/graphene aerogel composite foam material and a preparation method thereof.
Background
Polymer foam materials have low density, excellent properties such as sound absorption, vibration damping, and heat preservation, and have received much attention from the scientific and industrial fields. Foaming by using supercritical fluid is a newly developed foaming technology, which is green and environment-friendly, and has the most important advantage that the mechanical property of the foam material can be hardly lost while the weight of the foam material is reduced. In the process of preparing the polymer foaming material, inorganic nano particles are added as heterogeneous nucleating agents, and the method is an important means for reducing the size of cells, improving the density of the cells and improving the cell structure of the material.
Graphene is one of the ideal fillers for improving polymer foams due to its unique structure and excellent physicochemical properties. When the polymer foam material is prepared, graphene is used as a heterogeneous nucleating agent, and the graphene and a polymer matrix are blended and then foamed, so that the cell size and the cell structure can be optimized, and the electrical property of the polymer matrix can be improved. The dispersibility of graphene in a polymer is crucial to the formation of a conductive network, and the biggest problem at present is that graphene is very easy to agglomerate in the polymer, and the agglomeration of graphene can not only hinder the formation of the conductive network, but also cause poor cell quality during foaming, for example, the cell distribution is not uniform and cell combination occurs, and the cell combination can cause the cell size distribution to be wider, which easily causes the stress of a foam material to be non-uniform in the using process and the stress concentration phenomenon to be damaged. Aiming at the problem of graphene agglomeration, a common improvement method in the prior art is to functionalize graphene, but the functionalization can damage the lattice structure of graphene to a certain extent and affect the performance of the polymer composite foam material. Therefore, how to achieve uniform dispersion of graphene in a polymer remains an important research direction in the field of polymer/graphene composite foam materials. According to the existing thinking of preparing polymer/graphene composite foam materials, graphene and a polymer matrix are blended and foamed to form the composite foam material, and because the relative position between the graphene is continuously changed along with the formation of foam pores in the foaming process, the position of the graphene is difficult to be effectively controlled to form a complete graphene network, so that the graphene cannot be ensured to form a highly-through three-dimensional conductive network in the polymer even if the dispersity of the graphene in the blend is improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a polymer/graphene aerogel composite foam material, so that a three-dimensional graphene network with high connectivity is formed in the polymer composite foam material, the electrical property and the mechanical property of the composite foam material are effectively improved, and a new idea different from the prior art is provided for solving the problem of agglomeration of graphene in a polymer matrix material.
The polymer/graphene aerogel composite foam material provided by the invention is composed of graphene aerogel and a thermoplastic polymer, the graphene aerogel is used as a framework, the thermoplastic polymer is attached to a three-dimensional network structure of the graphene aerogel, the thermoplastic polymer is provided with closed-cell-structure cells, the composite foam material is provided with mutually communicated three-dimensional network structures, and the content of the graphene aerogel in the composite foam material is 0.5-10 wt%.
The pore size of the three-dimensional network structure of the polymer/graphene aerogel composite foam material is 10-120 mu m, and the pore diameter of the closed pore structure attached to the thermoplastic polymer on the three-dimensional network structure of the graphene aerogel is 5-30 mu m.
In the polymer/graphene aerogel composite foam material, the thermoplastic polymer is preferably polystyrene, polylactic acid, polypropylene or thermoplastic polyurethane, and the like, and preferably, the content of the graphene aerogel in the composite foam material is 2wt% to 6 wt%.
According to the requirements of practical application, the conductivity of the composite foam material can be adjusted by adjusting the content and the three-dimensional network structure of the graphene aerogel in the polymer/graphene aerogel composite foam material, and when thermoplastic polyurethane is selected as the polymer, the conductivity of the composite foam material can be adjusted within the range of 0.12-0.6S/cm.
The invention also provides a preparation method of the polymer/graphene aerogel composite foam material, which comprises the following steps:
(1) preparation of graphene aerogel
Adding a reducing agent into a graphene oxide solution, uniformly mixing, reducing for 1-24 hours at 35-90 ℃ to obtain partially reduced graphene oxide hydrogel, soaking the obtained hydrogel in water or an ethanol-water solution for 2-7 days, freezing for 6-24 hours at-20 to-10 ℃, then placing the hydrogel in a freeze dryer for freeze drying for 36-72 hours, and performing thermal reduction for 2-3 hours at 200-300 ℃ to obtain graphene aerogel; the mass ratio of the graphene oxide to the reducing agent is 1 (1-10);
or
Adding a solution of a water-based polymer into a graphene oxide solution, uniformly mixing, standing at room temperature until the graphene oxide is gelatinized, freezing the obtained graphene oxide hydrogel at-20 to-10 ℃ for 6 to 24 hours, then placing the graphene oxide hydrogel in a freeze dryer for freeze drying for 36 to 72 hours, and then performing thermal reduction at 400 to 1000 ℃ for 0.2 to 2 hours to obtain graphene aerogel; the mass ratio of the graphene oxide to the water-based polymer is 1 (0.1-10);
in the graphene oxide solution, the concentration of graphene oxide is 3-10 mg/mL, the carbon-oxygen ratio of the graphene oxide is (1.4-3): 1, and the size of the graphene oxide is 5-30 μm.
(2) Preparation of Polymer/graphene aerogel composite
Vacuumizing the graphene aerogel to fully remove air in the graphene aerogel, then placing the vacuumized graphene aerogel into a thermoplastic polymer solution with the concentration of 0.05-0.5 g/mL, standing in vacuum to fully attach the thermoplastic polymer to a three-dimensional network of the graphene aerogel, and drying to obtain a polymer/graphene aerogel composite material;
(3) supercritical foaming
Carrying out supercritical foaming by adopting a rapid depressurization method or a heating method to obtain a polymer/graphene aerogel composite foam material;
the rapid depressurization method comprises the steps of putting the polymer/graphene aerogel composite material into a reaction kettle, introducing gas, heating and pressurizing to convert the gas into supercritical fluid, keeping the temperature and the pressure, reducing the pressure in the reaction kettle to normal pressure by adopting the rapid depressurization method after the supercritical fluid is saturated in the composite material, and cooling and shaping to obtain the graphene aerogel composite material;
the heating method comprises the steps of placing the polymer/graphene aerogel composite material in a reaction kettle, introducing gas, heating and pressurizing, keeping the temperature and the pressure, releasing pressure after the gas is saturated in the composite material, taking out a foamed green body, placing the foamed green body in an oil bath, keeping the foamed green body for 10-60 s, and cooling and shaping, wherein the temperature of the oil bath is higher than the temperature in the reaction kettle.
In the method, the graphene oxide solution is obtained by dispersing graphite oxide in water and mechanically stirring at a rotating speed of 200-400 r/m or ultrasonically oscillating at a proper power. The graphite oxide is prepared by taking expandable graphite with the lamella size of 100-300 mu m as a raw material, reacting at 900-1000 ℃ for 1-5 min to form the expandable graphite, and then preparing by a modified Hummers method, and comprises the following specific steps:
stirring expanded graphite, sodium nitrate and concentrated sulfuric acid for 5-20 min under an ice bath condition according to the proportion of 1g to 0.5g (30-100) mL, slowly adding potassium permanganate according to the proportion of adding 5-8 g of potassium permanganate to each 1g of expanded graphite, then reacting for 2-5H at 20-40 ℃, adding deionized water according to the proportion of adding 100-300 mL of water to each 1g of expanded graphite for dilution, and then adding H with the excess concentration of 5-30 wt%2O2And stopping the reaction of the solution, repeatedly washing the solution by hydrochloric acid and deionized water in sequence, centrifuging the solution, and freeze-drying the solution for 2 to 4 days after the supernatant obtained by centrifuging the solution is neutral to obtain the graphite oxide. The carbon-oxygen molar ratio of the graphite oxide can be adjusted by adjusting the proportion of the expanded graphite, the sodium nitrate and the concentrated sulfuric acid, the addition amount of the potassium permanganate, the reaction temperature, the reaction time and other conditions.
In the step (1) of the method, when the partially reduced graphene oxide hydrogel or the graphene oxide hydrogel is frozen, the size of ice crystals formed by freezing influences the network structure of the graphene aerogel, the growth speed of the ice crystals can be adjusted by adjusting the freezing temperature and the freezing time, and then the size of the ice crystals is changed, and in the step, the growth speed of the ice crystals is preferably as slow as possible.
In the step (1) of the above method, the reducing agent is ascorbic acid, ethylenediamine, sodium borohydride, hydrazine hydrate, or the like, and the aqueous polymer is polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, hydroxypropyl cellulose, or the like.
In the step (2) of the above method, the thermoplastic polymer is polystyrene, polylactic acid, polypropylene, thermoplastic polyurethane, or the like.
In step (2) of the above method, the content of the polymer in the polymer/graphene aerogel composite material depends on the amount of the polymer attached to the three-dimensional network structure of the graphene aerogel in the step, while the amount of the polymer attached to the graphene aerogel mainly depends on the three-dimensional network structure of the graphene aerogel skeleton, in particular the pore size of the three-dimensional network structure of the graphene, and the degree of vacuum and the standing time in a vacuum environment of the step and the concentration of the thermoplastic polymer solution also affect the amount of the polymer attached to the graphene aerogel. This is also one of the key points of whether the supercritical foaming in step (3) can form effective cells in the polymer attached to the three-dimensional network structure of the graphene aerogel.
In the step (2) of the method, the graphene aerogel is placed in a closed environment, the vacuum is pumped to-0.1 to-0.08 MPa and kept for 1 to 5min in the vacuum environment to fully remove air in the graphene aerogel, then the graphene aerogel is placed in a solution of a thermoplastic polymer and placed in the closed environment, the vacuum is pumped to-0.1 to-0.08 MPa and kept for 0.5 to 3h in the vacuum environment, then the graphene aerogel is kept still at normal pressure for 0.5 to 2h to fully attach the thermoplastic polymer to a three-dimensional network of the graphene aerogel, and finally the polymer/graphene aerogel composite material is obtained after drying.
In the step (2) of the above method, the conductivity of the finally obtained polymer/graphene aerogel composite foam material can be adjusted by changing the concentration of the thermoplastic polymer solution.
In the step (3) of the method, the gas introduced into the reaction kettle is carbon dioxide, nitrogen, air or water vapor; when a rapid depressurization method is adopted, the temperature of the reaction kettle is controlled to be 35-160 ℃, the pressure is 8-25 MPa, and the depressurization rate is 50-80 MPa/s; when the heating method is adopted, the temperature of the reaction kettle is controlled to be 35-50 ℃, the pressure is 8-12 MPa, the pressure relief rate is 4-8 MPa/s, and the temperature of the oil bath is 80-150 ℃.
In the method, the volume fraction of the ethanol in the ethanol-water solution in the step (1) is 10-20%; adding an aqueous polymer solution into the graphene oxide solution in the step (1), uniformly mixing, removing bubbles in the obtained mixed solution by ultrasonic treatment, and standing at room temperature until the graphene oxide is gelatinized.
Compared with the prior art, the invention has the following beneficial technical effects:
1. the polymer/graphene aerogel composite foam material provided by the invention is a novel composite foam material with a structure different from that of the existing polymer/graphene composite foam material, the composite foam material takes graphene aerogel as a framework, a thermoplastic polymer is attached to a three-dimensional network structure of the graphene aerogel, the thermoplastic polymer is provided with closed-cell-structure cells, and the composite foam material is provided with mutually-communicated three-dimensional network structures. The graphene aerogel composite material is formed on the basis of a graphene aerogel network with complete and high connectivity, so that the problems of graphene agglomeration and uneven dispersion are effectively solved, and the graphene aerogel has the characteristics of light weight, good resilience, high mechanical strength, good conductivity and the like, so that the electrical property, the mechanical property and the adsorption property of the polymer/graphene aerogel composite material provided by the invention are superior to those of the existing polymer/graphene composite foam material taking graphene as a filler. Therefore, the composite material prepared by the invention has the characteristics of the graphene aerogel and the porous polymer foam material, and has potential application value in the fields of adsorption materials, electronic devices and the like.
2. The invention also provides a preparation method of the polymer/graphene aerogel composite foam material, which comprises the steps of firstly preparing the graphene aerogel, then preparing the polymer/graphene aerogel composite material on the basis of the graphene aerogel, and then performing supercritical foaming on the basis of the polymer/graphene aerogel composite material to enable the polymer attached to the three-dimensional network structure of the graphene aerogel to form small cells with closed cell structures. The composite foaming material is prepared by taking the graphene aerogel with a stable and highly-connected three-dimensional network structure as a framework, so that the problems of graphene agglomeration and difficulty in forming a highly-connected graphene conductive network existing in the foaming process after blending graphene and a polymer in the prior art are effectively solved, the electrical property, the mechanical property and the adsorption property of the finally prepared polymer/graphene aerogel composite material are superior to those of a polymer foam material prepared by a traditional method, and a new thought different from the prior art is provided for solving the agglomeration problem of graphene in a polymer matrix material.
3. Due to the selection of the graphene oxide lamella size and the matching and control of the process parameters, the method ensures that the pore size of the prepared graphene aerogel three-dimensional network structure is reasonable, which is one of the keys for successfully obtaining the polymer/graphene aerogel composite foam material, and the matching of the subsequent preparation of the polymer/graphene aerogel composite material and the subsequent supercritical foaming process is proper, so that the composite foam material prepared by the method has a good three-dimensional network structure and a good cellular structure, and plays an important role in improving the electrical property, the adsorption property and the mechanical property of the composite foam material.
4. The method has the characteristics of simple operation, good process controllability, easy popularization and application, and production can be realized by adopting the existing equipment.
Drawings
Fig. 1 is an SEM image of the graphene aerogel, thermoplastic polyurethane/graphene aerogel composite, and thermoplastic polyurethane/graphene aerogel composite foam prepared in example 1.
Detailed Description
The polymer/graphene aerogel composite foam material and the preparation method thereof provided by the present invention are further illustrated by the following examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can make certain insubstantial modifications and adaptations of the present invention based on the above disclosure and still fall within the scope of the present invention.
Example 1
(1) Preparation of graphite oxide
Expandable graphite with a lamella size of about 200 μm is used as a raw material, the expandable graphite is obtained by reacting for 5min at 900 ℃, and graphite oxide is prepared by a modified Hummers method: stirring expanded graphite, sodium nitrate and concentrated sulfuric acid for 10min under an ice bath condition according to the proportion of 1g:0.5g:100mL, slowly adding potassium permanganate according to the proportion of adding 8g of potassium permanganate to each 1g of expanded graphite, reacting for 2.5H at 35 ℃ after the potassium permanganate is added, then adding deionized water according to the proportion of adding 200mL of water to each 1g of expanded graphite for dilution, and adding 120mL of H with the concentration of 5 wt%2O2Stopping the reaction of the solution, repeatedly washing the solution by hydrochloric acid and deionized water in sequence, centrifuging the solution, freezing and drying the solution for 48 hours after the supernatant obtained by centrifuging the solution is neutral to obtain graphite oxide, and measuring the carbon-oxygen molar ratio of the graphite oxide prepared in the step to obtain the result of 1.5: 1.
(2) Preparation of graphene aerogel
Adding graphite oxide into deionized water, and mechanically stirring at a rotating speed of 200r/m for 2 hours to obtain a 10mg/mL graphene oxide solution, wherein the size of a sheet layer of the graphene oxide is 10-25 microns. Adding 10mL of polyvinyl alcohol solution with the concentration of 50mg/mL into 10mL of graphene oxide solution with the concentration of 10mg/mL, mechanically stirring at the rotating speed of 200r/m for 2h, uniformly mixing, then ultrasonically treating at the power of 400W for 20min to remove bubbles, standing at room temperature until the graphene oxide is gelatinized, freezing the obtained graphene oxide hydrogel at-18 ℃ for 12h, then placing the graphene oxide hydrogel in a freeze dryer for freeze drying under the condition that the pressure does not exceed 20Pa for 48h, then transferring the graphene oxide hydrogel to a tubular resistance furnace, raising the temperature to 1000 ℃ at the temperature raising rate of 10 ℃/min, and preserving the temperature for 15min to obtain the graphene aerogel.
(3) Preparation of thermoplastic polyurethane/graphene aerogel composite material
Vacuum drying polyether type thermoplastic polyurethane at 80 ℃ for 12h, then dissolving 10g of dried polyether type thermoplastic polyurethane in 50mL of N-N dimethylformamide to obtain a thermoplastic polyurethane solution, placing the graphene aerogel prepared in the step (2) in a vacuum drying oven, vacuumizing to-0.1 to-0.08 MPa, keeping the vacuum degree for 5min to fully remove air in the graphene aerogel, then immersing the vacuumized graphene aerogel in the thermoplastic polyurethane solution, vacuumizing to-0.1 to-0.08 MPa, keeping the vacuum degree for 1h, standing at normal pressure for 2h to fully enable the thermoplastic polyurethane to enter a three-dimensional network of the graphene aerogel, and then drying at normal pressure to obtain the thermoplastic polyurethane/graphene aerogel composite material.
(4) Supercritical foaming
Placing the thermoplastic polyurethane/graphene aerogel composite material in a high-pressure reaction kettle, introducing carbon dioxide, heating to 105 ℃, pressurizing to 12MPa to convert the carbon dioxide into supercritical fluid, keeping for 2 hours under the conditions of the temperature and the pressure, reducing the pressure in the high-pressure reaction kettle to normal pressure by adopting a rapid depressurization method at a depressurization rate of about 80MPa/s to foam the composite material, and introducing tap water into a cooling water system of the high-pressure reaction kettle to cool and shape a foaming product to obtain the thermoplastic polyurethane/graphene aerogel composite foam material.
Fig. 1 is SEM images of the graphene aerogel, the thermoplastic polyurethane/graphene aerogel composite material, and the thermoplastic polyurethane/graphene aerogel composite foam material prepared in this embodiment, wherein fig. a 1-a 3 are SEM images of the graphene aerogel under different magnifications, fig. b 1-b 3 are SEM images of the thermoplastic polyurethane/graphene aerogel composite material under different magnifications, and fig. c 1-c 3 are SEM images of the thermoplastic polyurethane/graphene aerogel composite foam material under different magnifications. As can be seen from fig. 1, the graphene aerogel has a uniform connected three-dimensional network structure, after being composited with the thermoplastic polyurethane, the three-dimensional network structure of the graphene aerogel still exists, the thermoplastic polyurethane is attached to the surface of the pore wall of the graphene aerogel, after being foamed by the supercritical carbon dioxide, the three-dimensional network structure of the composite material is not damaged, and the polymer in the composite material forms a microporous structure. Through tests, the pore size of the three-dimensional network structure of the composite foam material is 10-120 microns, the pore size of the closed-cell structure pores on the thermoplastic polyurethane is 5-30 microns, the content of the graphene aerogel in the composite foam material is 5.47 wt%, and the conductivity of the composite foam material is 0.58S/cm.
Example 2
In the implementation, the preparation of the thermoplastic polyurethane/graphene aerogel composite foam material comprises the following steps:
(1) preparation of graphite oxide
Graphite oxide was prepared as in step (1) of example 1 using expandable graphite having a flake size of about 300 μm as a starting material.
(2) Preparation of graphene aerogel
Dispersing graphite oxide into water, and mechanically stirring at a rotating speed of 200r/m for 1h to obtain a 5mg/mL graphene oxide solution, wherein the sheet size of the graphene oxide is 20-30 microns. Adding 100mg of ascorbic acid into 10mL of graphene oxide solution and 5mg/mL of graphene oxide solution, mechanically stirring at a rotating speed of 200r/m for 15min, uniformly mixing, then placing in an oil bath at 90 ℃ under a closed condition, heating and reducing for 3h to obtain partially reduced graphene oxide hydrogel, soaking the obtained hydrogel in deionized water for 7d, replacing new deionized water every 24h, then placing in a freeze dryer for freezing for 24h at the temperature of-10 ℃, placing in a freeze dryer for freeze drying for 36h under the pressure not exceeding 20Pa, and then performing thermal reduction for 3h at the temperature of 200 ℃ to obtain the graphene aerogel.
(3) Preparation of thermoplastic polyurethane/graphene aerogel composite material
Vacuum drying polyether type thermoplastic polyurethane at 80 ℃ for 12h, dissolving 10g of dried polyether type thermoplastic polyurethane in 50mL of tetrahydrofuran to obtain a thermoplastic polyurethane solution, placing the graphene aerogel prepared in the step (2) in a vacuum drying oven, vacuumizing to-0.1-0.08 MPa, keeping the vacuum degree for 2min to fully remove air in the graphene aerogel, immersing the vacuumized graphene aerogel in the thermoplastic polyurethane solution, vacuumizing to-0.1-0.08 MPa, keeping the vacuum degree for 0.5h, standing at normal pressure for 1.5h to fully allow the thermoplastic polyurethane to enter a three-dimensional network of the graphene aerogel, and drying at normal pressure to obtain the thermoplastic polyurethane/graphene aerogel composite material.
(4) Supercritical foaming
Placing the thermoplastic polyurethane/graphene aerogel composite material in a high-pressure reaction kettle, introducing carbon dioxide, heating, pressurizing to 140 ℃ and 10MPa to convert the carbon dioxide into supercritical fluid, keeping for 3 hours under the conditions of the temperature and the pressure, reducing the pressure in the high-pressure reaction kettle to normal pressure by adopting a rapid depressurization method at a depressurization rate of about 60MPa/s to foam the composite material, and introducing tap water into a cooling water system of the high-pressure reaction kettle to cool and shape a foaming product to obtain the thermoplastic polyurethane/graphene aerogel composite foam material. The content of the graphene aerogel in the composite foam material is 2.45 wt%, and the conductivity of the composite foam material is 0.12S/cm.
Example 3
In this implementation, the preparation of the polystyrene/graphene aerogel composite foam material comprises the following steps:
(1) preparation of graphite oxide
Graphite oxide was prepared by following the procedure of step (1) of example 1.
(2) Preparation of graphene aerogel
Dispersing graphite oxide into water, and ultrasonically stirring at a rotating speed of 200r/m for 0.5h to obtain a 3mg/mL graphene oxide solution, wherein the sheet size of the graphene oxide is 10-25 microns. Adding 120mg of ethylenediamine into 10mL and 3mg/mL of graphene oxide solution, mechanically stirring at a rotating speed of 200r/m for 15min, uniformly mixing, then placing in an oven under a closed condition, heating and reducing at 80 ℃ for 1h to obtain partially reduced graphene oxide hydrogel, soaking the obtained hydrogel in an ethanol-water solution with the ethanol volume percentage of 20% for 2d, replacing new ethanol-water solution every 12h, then freezing at-20 ℃ for 6h, placing in a freeze dryer, freeze-drying under the pressure of no more than 20Pa for 72h, and then thermally reducing at 300 ℃ for 2h to obtain the graphene aerogel.
(3) Preparation of polystyrene/graphene aerogel composite material
Dissolving 10g of polystyrene in 100mL of N-N dimethylformamide to obtain a polystyrene solution, placing the graphene aerogel prepared in the step (2) in a vacuum drying oven, vacuumizing to-0.1 to-0.08 MPa, keeping the vacuum degree for 2min to fully remove air in the graphene aerogel, then immersing the vacuumized graphene aerogel in the polystyrene solution, vacuumizing to-0.1 to-0.08 MPa, keeping the vacuum degree for 1.5h, standing at normal pressure for 2h to fully allow the polystyrene to enter a three-dimensional network of the graphene aerogel, and then drying at normal pressure to obtain the polystyrene/graphene aerogel composite material.
(4) Supercritical foaming
Placing the polystyrene/graphene aerogel composite material in a high-pressure reaction kettle, introducing carbon dioxide, heating, pressurizing to 80 ℃ and 22MPa to convert the carbon dioxide into supercritical fluid, keeping for 3 hours under the conditions of the temperature and the pressure, reducing the pressure in the high-pressure reaction kettle to normal pressure by adopting a rapid depressurization method at a depressurization rate of about 50MPa/s to foam the composite material, introducing tap water into a cooling water system of the high-pressure reaction kettle to cool and shape a foaming product to obtain the polystyrene/graphene aerogel composite foam material, wherein the content of the graphene aerogel in the composite foam material is 4.47 wt%.
Example 4
In the implementation, the polylactic acid/graphene aerogel composite foam material is prepared by the following steps:
(1) preparation of graphite oxide
Graphite oxide was prepared as in step (1) of example 1 using expandable graphite having a flake size of about 100 μm as a starting material.
(2) Preparation of graphene aerogel
Dispersing the graphite oxide prepared in the step (1) into water, and ultrasonically stirring at a rotating speed of 400r/m for 4 hours to obtain a 5mg/mL graphene oxide solution, wherein the sheet size of the graphene oxide is 5-10 microns. Adding 10mL of polyvinyl alcohol solution with the concentration of 5mg/mL into 10mL of graphene oxide solution with the concentration of 5mg/mL of graphene oxide solution, mechanically stirring at the rotation speed of 400r/m for 2h, uniformly mixing, then ultrasonically treating at the power of 400W for 20min to remove bubbles, standing at room temperature until the graphene oxide is gelatinized, freezing the obtained graphene oxide hydrogel at-18 ℃ for 12h, then placing the graphene oxide hydrogel in a freeze dryer, freeze-drying for 48h under the condition that the pressure does not exceed 20Pa, then transferring the graphene oxide hydrogel to a tubular resistance furnace, raising the temperature to 1000 ℃ at the temperature raising rate of 10 ℃/min, and preserving the temperature for 25min to obtain the graphene aerogel.
(3) Preparation of polylactic acid/graphene aerogel composite material
Dissolving 10g of polylactic acid in 50mL of trichloromethane to obtain a polylactic acid solution, placing the graphene aerogel prepared in the step (2) in a vacuum drying oven, vacuumizing to-0.1 to-0.08 MPa, keeping the vacuum degree for 1min to fully remove air in the graphene aerogel, then immersing the vacuumized graphene aerogel in the polylactic acid solution, vacuumizing to-0.1 to-0.08 MPa, keeping the vacuum degree for 3h, standing at normal pressure for 0.5h to fully introduce the polylactic acid into a three-dimensional network of the graphene aerogel, and then drying at normal pressure to obtain the polylactic acid/graphene aerogel composite material.
(4) Supercritical foaming
Placing the polylactic acid/graphene aerogel composite material in a high-pressure reaction kettle, introducing nitrogen, heating, pressurizing to 130 ℃ and 14MPa to convert the nitrogen into supercritical fluid, keeping for 4 hours under the conditions of the temperature and the pressure, reducing the pressure in the high-pressure reaction kettle to normal pressure by adopting a rapid depressurization method at a depressurization rate of about 80MPa/s to foam the composite material, introducing tap water into a cooling water system of the high-pressure reaction kettle to cool and shape a foaming product to obtain the polylactic acid/graphene aerogel composite foam material, wherein the content of the graphene aerogel in the composite foam material is 2.23 wt%.
Example 5
In this implementation, the preparation of the polypropylene/graphene aerogel composite foam material comprises the following steps:
(1) preparation of graphite oxide
Graphite oxide was prepared by following the procedure of step (1) of example 1.
(2) Preparation of graphene aerogel
Dispersing the graphite oxide prepared in the step (1) into water, and ultrasonically stirring at a rotating speed of 200r/m for 4 hours to obtain a 10mg/mL graphene oxide solution, wherein the sheet size of the graphene oxide is 10-25 microns. Adding 10mL and 1mg/mL hydroxypropyl cellulose solution into 10mL and 10mg/mL graphene oxide solution, mechanically stirring at a rotation speed of 200r/m for 2h, uniformly mixing, then ultrasonically treating at a power of 400W for 20min to remove bubbles, standing at room temperature until the graphene oxide is gelatinized, freezing the obtained graphene oxide hydrogel at-18 ℃ for 12h, then placing the graphene oxide hydrogel in a freeze dryer, freeze-drying for 48h under the condition that the pressure does not exceed 20Pa, then transferring the graphene oxide hydrogel into a tubular resistance furnace, raising the temperature to 400 ℃ at a temperature raising rate of 10 ℃/min, and preserving the temperature for 2h to obtain the graphene aerogel.
(3) Preparation of polypropylene/graphene aerogel composite material
Dissolving 10g of polypropylene in 20mL of toluene to obtain a polypropylene solution, placing the graphene aerogel prepared in the step (2) in a vacuum drying oven, vacuumizing to-0.1 to-0.08 MPa, keeping the vacuum degree for 4min to sufficiently remove air in the graphene aerogel, then immersing the vacuumized graphene aerogel in the polypropylene solution, vacuumizing to-0.1 to-0.08 MPa, keeping the vacuum degree for 2h, standing at normal pressure for 2h to ensure that the polypropylene sufficiently enters a three-dimensional network of the graphene aerogel, and then drying at normal pressure to obtain the polypropylene/graphene aerogel composite material.
(4) Supercritical foaming
Placing the polypropylene/graphene aerogel composite material in a high-pressure reaction kettle, introducing carbon dioxide, heating, pressurizing to 35 ℃ and 12MPa to convert the carbon dioxide into supercritical fluid, keeping for 12 hours under the conditions of the temperature and the pressure, enabling the supercritical fluid to reach a saturated state in the composite material, reducing the pressure in the high-pressure reaction kettle to normal pressure at a decompression rate of about 4MPa/s to obtain a foaming blank body, taking out the foaming blank body, placing in an oil bath at 140 ℃ for 50s, taking out, cooling and shaping to obtain the polypropylene/graphene aerogel composite foam material.
Example 6
In this implementation, the preparation of the polystyrene/graphene aerogel composite foam material comprises the following steps:
(1) preparation of graphite oxide
Graphite oxide was prepared by following the procedure of step (1) of example 1.
(2) Preparation of graphene aerogel
Dispersing graphite oxide into water, and ultrasonically stirring at a rotating speed of 200r/m for 0.5h to obtain a 4mg/mL graphene oxide solution, wherein the sheet size of the graphene oxide is 10-25 microns. Adding 360mg of sodium borohydride into 10mL and 4mg/mL of graphene oxide solution, mechanically stirring at a rotating speed of 200r/m for 15min, uniformly mixing, then reducing in a water bath at 35 ℃ for 24h under a closed condition to obtain partially reduced graphene oxide hydrogel, soaking the obtained hydrogel in an ethanol-water solution with the ethanol volume percentage of 100% for 4d, replacing new ethanol-water solution every 24h, then freezing at-18 ℃ for 12h, freeze-drying in a freeze-drying machine under the pressure not exceeding 20Pa for 48h, and then thermally reducing at 250 ℃ for 2h to obtain the graphene aerogel.
(3) Preparation of polystyrene/graphene aerogel composite material
Dissolving 5g of polystyrene in 100mL of N-N dimethylformamide to obtain a polystyrene solution, placing the graphene aerogel prepared in the step (2) in a vacuum drying oven, vacuumizing to-0.1 to-0.08 MPa, keeping the vacuum degree for 5min to fully remove air in the graphene aerogel, then immersing the vacuumized graphene aerogel in the polystyrene solution, vacuumizing to-0.1 to-0.08 MPa, keeping the vacuum degree for 3h, standing at normal pressure for 1h to fully allow the polystyrene to enter a three-dimensional network of the graphene aerogel, and then drying at normal pressure to obtain the polystyrene/graphene aerogel composite material.
(4) Supercritical foaming
Placing the polystyrene/graphene aerogel composite material in a high-pressure reaction kettle, introducing carbon dioxide, heating, pressurizing to 50 ℃ and 8MPa to convert the carbon dioxide into supercritical fluid, keeping for 4 hours under the conditions of the temperature and the pressure, enabling the supercritical fluid to reach a saturated state in the composite material, reducing the pressure in the high-pressure reaction kettle to normal pressure at a decompression rate of about 8MPa/s to obtain a foaming blank body, taking out the foaming blank body, placing in an oil bath at 80 ℃ for 10s, taking out, cooling and shaping to obtain the polystyrene/graphene aerogel composite foam material.
Claims (7)
1. The polymer/graphene aerogel composite foam material is characterized by comprising graphene aerogel and a thermoplastic polymer, wherein the graphene aerogel is used as a framework, the thermoplastic polymer is attached to a three-dimensional network structure of the graphene aerogel, cells with a closed cell structure are arranged on the thermoplastic polymer, the composite foam material has a mutually communicated three-dimensional network structure, the content of the graphene aerogel in the composite foam material is 2-6 wt%, and the preparation method of the composite foam material comprises the following steps:
(1) preparation of graphene aerogel
Adding a reducing agent into the graphene oxide solution, uniformly mixing, and then adding the reducing agent into the graphene oxide solution at 35-90 DEG CoC, reducing for 1-24 hours to obtain partially reduced graphene oxide hydrogel, soaking the obtained hydrogel in water or an ethanol-water solution for 2-7 days, and keeping the temperature at-20 to-10oC, freezing for 6-24 h, then placing in a freeze dryer for freeze drying for 36-72 h, and then freezing for 200-300 hoC, carrying out thermal reduction for 2-3 h to obtain graphene aerogel; the mass ratio of the graphene oxide to the reducing agent is 1 (1-10);
or
Adding a solution of an aqueous polymer into a graphene oxide solution, uniformly mixing, standing at room temperature until the graphene oxide is gelatinized, and allowing the obtained graphene oxide hydrogel to be in the range of-20 to-10oC, freezing for 6-24 h, then placing in a freeze dryer for freeze drying for 36-72 h, and then freezing for 400-1000 hoC, carrying out thermal reduction for 0.2-2 h to obtain graphene aerogel; the mass ratio of the graphene oxide to the water-based polymer is 1 (0.1-10);
in the graphene oxide solution, the concentration of graphene oxide is 3-10 mg/mL, the carbon-oxygen ratio of the graphene oxide is (1.4-3): 1, and the size of the graphene oxide is 5-30 μm;
(2) preparation of Polymer/graphene aerogel composite
Vacuumizing the graphene aerogel to fully remove air in the graphene aerogel, then placing the vacuumized graphene aerogel into a thermoplastic polymer solution with the concentration of 0.05-0.5 g/mL, standing in vacuum to fully attach the thermoplastic polymer to a three-dimensional network of the graphene aerogel, and drying to obtain a polymer/graphene aerogel composite material;
(3) supercritical foaming
Carrying out supercritical foaming by adopting a rapid depressurization method or a heating method to obtain a polymer/graphene aerogel composite foam material;
the rapid depressurization method comprises the steps of putting the polymer/graphene aerogel composite material into a reaction kettle, introducing gas, heating and pressurizing to convert the gas into supercritical fluid, keeping the temperature and the pressure, reducing the pressure in the reaction kettle to normal pressure by adopting the rapid depressurization method after the supercritical fluid is saturated in the composite material, and cooling and shaping to obtain the graphene aerogel composite material;
the heating method comprises the steps of placing the polymer/graphene aerogel composite material in a reaction kettle, introducing gas, heating and pressurizing, keeping the temperature and the pressure, releasing pressure after the gas is saturated in the composite material, taking out a foamed green body, placing the foamed green body in an oil bath, keeping the foamed green body for 10-60 s, and cooling and shaping, wherein the temperature of the oil bath is higher than the temperature in the reaction kettle.
2. The polymer/graphene aerogel composite foam material according to claim 1, wherein the three-dimensional network structure of the composite foam material has a pore size of 10 to 120 μm, and the closed cell structure of the thermoplastic polymer has a cell pore size of 5 to 30 μm.
3. The polymer/graphene aerogel composite foam material according to claim 1 or 2, characterized in that the thermoplastic polymer is polystyrene, polylactic acid, polypropylene or thermoplastic polyurethane.
4. The polymer/graphene aerogel composite foam material according to claim 1, wherein the reducing agent in step (1) is ascorbic acid, ethylenediamine, sodium borohydride or hydrazine hydrate.
5. The polymer/graphene aerogel composite foam material according to claim 1, wherein the aqueous polymer in step (1) is polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide or hydroxypropyl cellulose.
6. The polymer/graphene aerogel composite foam material of claim 1, wherein in the step (2), the graphene aerogel is placed in a closed environment, the vacuum environment is vacuumized to-0.1 to-0.08 MPa and kept for 1 to 5min under the vacuum environment to sufficiently remove air therein, then the graphene aerogel is placed in a solution of a thermoplastic polymer, the closed environment is placed, the vacuum environment is vacuumized to-0.1 to-0.08 MPa and kept for 0.5 to 3h under the vacuum environment, then the mixture is kept for 0.5 to 2h under normal pressure to sufficiently attach the thermoplastic polymer to a three-dimensional network of the graphene aerogel, and finally the polymer/graphene aerogel composite material is obtained after drying.
7. The polymer/graphene gas of claim 1The gel composite foam material is characterized in that in the step (3), the gas introduced into the reaction kettle is carbon dioxide, nitrogen, air or water vapor; the temperature of the reaction kettle is controlled to be 35-160 ℃ when a rapid depressurization method is adoptedoC, the pressure is 8-25 MPa, and the pressure reduction rate is 50-80 MPa/s; controlling the temperature of the reaction kettle to be 35-50 ℃ when a temperature rising method is adoptedoC, the pressure is 8-12 MPa, the pressure relief rate is 4-8 MPa/s, and the oil bath temperature is 80-150oC。
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