CN111925536A - Preparation method of PMMA (polymethyl methacrylate) structure-regulated composite material based on graphene aerogel framework - Google Patents
Preparation method of PMMA (polymethyl methacrylate) structure-regulated composite material based on graphene aerogel framework Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 174
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 162
- 229920003229 poly(methyl methacrylate) Polymers 0.000 title claims abstract description 83
- 239000004926 polymethyl methacrylate Substances 0.000 title claims abstract description 83
- 239000004964 aerogel Substances 0.000 title claims abstract description 76
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 230000001105 regulatory effect Effects 0.000 title description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 title description 3
- 238000011065 in-situ storage Methods 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 239000003999 initiator Substances 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 14
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 14
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 14
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000000017 hydrogel Substances 0.000 claims description 12
- 238000000465 moulding Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000012286 potassium permanganate Substances 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 230000010355 oscillation Effects 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 description 20
- 239000000243 solution Substances 0.000 description 12
- 239000011159 matrix material Substances 0.000 description 11
- 230000009286 beneficial effect Effects 0.000 description 5
- 230000009471 action Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 238000005411 Van der Waals force Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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Abstract
The embodiment of the invention discloses a preparation method of a PMMA structure composite material based on graphene aerogel framework regulation, which comprises the steps of infiltrating a PMMA prepolymer into a graphene aerogel, and then carrying out in-situ polymerization on the PMMA prepolymer to prepare the graphene aerogel/PMMA composite material. According to the invention, the graphene three-dimensional network and the hole structure are pre-constructed through the preparation of the graphene aerogel, then the PMMA prepolymer is infiltrated, and the PMMA/graphene composite material is formed in a mold with a certain shape, so that the PMMA/graphene composite material is prepared, and the composite material has good electric and heat conducting properties and can effectively improve the utilization rate of the graphene performance.
Description
Technical Field
The invention relates to the technical field of composite material preparation, in particular to a preparation method of a composite material with a PMMA structure regulated and controlled based on a graphene aerogel framework.
Background
Graphene is widely applied to polymer reinforcement, electric conduction, heat conduction and other aspects due to excellent performance of graphene. In recent years, companies and research and development institutions around the research of graphene/polymer composite materials are increasing, and particularly, some enterprises urgently need to improve the heat conduction and dissipation performance of polymers by utilizing the excellent heat conduction and dissipation capability of graphene. Common preparation methods of polymer/graphene composite materials include a mechanical blending method, a solution blending method, an emulsion blending method and the like. The graphene/polymer composite material prepared by the mechanical blending method is simple in process and operation and easy for large-scale industrial production, but due to the fact that van der Waals force exists in graphene sheet layers and is easy to agglomerate in a polymer matrix, the utilization rate of graphene in the polymer matrix is reduced, and the performance of the graphene/polymer composite material is further influenced; the solution blending method or the emulsion blending method can effectively improve the dispersibility of the graphene in the polymer matrix, but in the preparation process of the composite material, a large amount of waste liquid (organic solvent or solution carrying polymer monomer and the like) can be generated, which is not beneficial to the large-scale production of the composite material.
The graphene aerogel is a novel carbon matrix phase material, generally has a three-dimensional micro-nano structure, is simple to prepare, has a uniformly dispersed graphene aerogel pore structure, and is beneficial to preparation of a graphene/polymer composite material. The graphene aerogel has the advantages of a series of performances such as excellent electrical conductivity, high superelasticity, large specific surface area, oleophylic fire resistance, ultrahigh porosity and the like, and has the greatest significance of realizing the three-dimensional structure of graphene and endowing the graphene aerogel with a series of excellent performances. The electric and heat conducting performance of the graphene/polymer composite material is based on that graphene forms an effective three-dimensional network in a polymer matrix, which is beneficial to forming an electric conduction path or is beneficial to transmitting heat in the form of phonons or far infrared rays. When the graphene/polymer composite material is actually prepared, the graphene is difficult to form a uniform and complete three-dimensional structure in a polymer matrix, and the performance improvement of the composite material is greatly influenced.
At present, the preparation method of the graphene/PMMA (polymethyl methacrylate) composite material mainly comprises: in-situ synthesis methods, direct blending methods, graphene functionalized in-situ synthesis, and the like, all of which rely on the dispersion of graphene in a PMMA matrix. No matter graphene or graphene oxide, aggregation can occur in a PMMA matrix due to van der Waals force or hydrogen bond action, and a good electric conduction or heat conduction network is difficult to form under the condition of extremely small addition amount, so that the electric conduction and heat conduction performance of the composite material is influenced. A small amount of research focuses on graphene aerogel, PMMA/graphene composite materials are prepared by adopting a PMMA melt or solution infiltration method, although the electric and heat conducting performance of the composite materials is improved, the interface bonding force between the graphene surface of the graphene aerogel hole and the polymer matrix is weak, in addition, the polymer is generally high in molecular weight, cannot fully infiltrate the graphene aerogel, and is easy to fall off under the action of external force, so that the mechanical property and the service life of the composite materials are influenced.
Disclosure of Invention
The embodiment of the invention aims to provide a preparation method of a PMMA (polymethyl methacrylate) structure composite material regulated and controlled based on a graphene aerogel framework, and the method can promote graphene to form a complete three-dimensional network with uniform holes in a PMMA matrix. Specifically, a graphene three-dimensional network and a hole structure are pre-constructed through preparation of graphene aerogel, then the graphene three-dimensional network and the hole structure are soaked through PMMA prepolymer and are formed in a mold with a certain shape, and a PMMA/graphene composite material is prepared.
In order to achieve the above object, an aspect of the embodiments of the present invention provides a method for preparing a PMMA structure composite material based on a graphene aerogel framework, where the method includes the steps of infiltrating a PMMA prepolymer into a graphene aerogel, and then performing in-situ polymerization on the PMMA prepolymer to prepare a graphene aerogel/PMMA composite material. The graphene/polymer composite material prepared by the in-situ bulk method can effectively solve the problems of insufficient polymer infiltration and low acting force of the graphene and polymer interface.
Further, the preparation method comprises the following steps:
(1) preparing graphene oxide;
(2) preparing graphene aerogel;
(3) preparing a PMMA prepolymer; and
(4) and preparing the graphene aerogel/PMMA composite material.
Further, the step (1) comprises the following steps: blending the flake graphite with concentrated sulfuric acid, and stirring in an ice water bath for 1-1.5 h; then adding potassium permanganate, and reacting for 1-1.5 h; then heating to 40-45 ℃ and reacting for 1-1.5 h; and heating to 85-90 ℃, reacting for 1-1.5 h, adding deionized water into the reaction mixture for three times, adding hydrogen peroxide until the reactant turns yellow, cooling the reactant, cleaning with dilute hydrochloric acid, cleaning with deionized water, centrifuging, and drying to obtain the graphene oxide.
Preferably, in the step (1), the concentrated sulfuric acid has a concentration of 98 wt%, the scale graphite is 200-300 meshes, the ratio of the scale graphite to the concentrated sulfuric acid is 1g:20 ml-1 g:30ml, and the ratio of the potassium permanganate to the concentrated sulfuric acid is 1g:4 ml-1 g:6ml, preferably 1g:5 ml; the volume ratio of the total amount of the added deionized water to the concentrated sulfuric acid is 6: 1-7: 1, the concentration of the hydrogen peroxide is 30 wt%, and the concentration of the dilute hydrochloric acid is 2 wt% -3 wt%.
Further, the step (2) comprises the following steps: preparing graphene oxide and deionized water into an aqueous solution, and performing ultrasonic oscillation for 0.1-6 hours to obtain a well-dispersed graphene oxide aqueous solution; adding the graphene oxide aqueous solution into a hydrothermal kettle, and treating for 2-24 hours at 90-200 ℃ to obtain graphene oxide hydrogel; putting the graphene oxide hydrogel into a hydrazine hydrate aqueous solution, soaking for 24-48 h at 90-100 ℃, and freeze-drying; and drying the freeze-dried graphene aerogel at 90-100 ℃ for 8-12 h to obtain the graphene aerogel.
Preferably, the concentration of the graphene oxide aqueous solution in the step (2) is 0.1-50 mg/ml, preferably 15-35 mg/ml; the mass ratio of hydrazine hydrate to graphene oxide in the hydrazine hydrate aqueous solution is 10: 7-10: 10.
Preferably, the concentration of the aqueous hydrazine hydrate solution is from 40 wt% to 80 wt%, preferably from 65 wt% to 72 wt%.
Further, the step (3) comprises the following steps: putting a Methyl Methacrylate (MMA) monomer into a conical flask, adding an initiator dibenzoyl peroxide, wherein the ratio of the initiator to the MMA is 1g:250 ml-1 g:300 ml; and heating the conical flask in a water bath at the temperature of 80-90 ℃ until the viscosity of reactants in the conical flask reaches 600-800 mPa & s, stopping heating, and rapidly cooling the conical flask to room temperature to obtain the PMMA prepolymer.
Further, the step (4) comprises the following steps: cutting the graphene aerogel obtained in the step (2) into a filling shape of a PMMA (polymethyl methacrylate) forming mold, then putting the cut graphene aerogel into the mold with a corresponding shape, and injecting the PMMA prepolymer obtained in the step (3); keeping the temperature at 40-50 ℃, preserving the heat for 5-7 h, then continuously raising the temperature to 90-100 ℃, preserving the heat for 1-2 h, then stopping heating, naturally cooling to 35-40 ℃, and taking down the mold to obtain the graphene aerogel/PMMA composite material.
In some specific embodiments, when the PMMA molding die in step (4) is a rectangular parallelepiped of 20ml, the initiator used in step (3) is dibenzoyl peroxide of 0.06 g; when the PMMA molding mould in the step (4) is a cuboid of 40ml, 0.12g of dibenzoyl peroxide serving as an initiator in the step (3) is used; when the PMMA molding mould in the step (4) is 64ml of cube, the initiator used in the step (3) is 0.20g of dibenzoyl peroxide; when the PMMA molding die in the step (4) is 35ml of a cylinder, the initiator used in the step (3) is 0.11g of dibenzoyl peroxide.
According to the invention, a series of characteristics of excellent electrical conductivity, high superelasticity, large specific surface area, oleophylic fire resistance, ultrahigh porosity and the like of the graphene aerogel are utilized, the graphene aerogel/PMMA composite material is prepared by firstly infiltrating PMMA prepolymer and then carrying out in-situ PMMA polymerization, and the electrical conductivity and the thermal conductivity of the composite material are obviously improved compared with those of the prior art.
The embodiment of the invention has the following advantages:
1. graphene oxide aerogel is prepared by using graphene oxide, and then hydrazine hydrate is used for reduction to prepare the graphene aerogel, so that the defect of graphene sheet layers is reduced, the electric and heat conducting performance of the graphene is improved, the graphene aerogel prepared by reduction of hydrazine hydrate still contains a small amount of oxygen-containing functional groups, and a strong interface acting force is formed between the graphene and PMMA in the processes of infiltration and polymerization of PMMA prepolymer by using hydrogen bonds, molecular winding and other action modes;
2. compared with the direct blending of PMMA and graphene or the blending polymerization of MMA and graphene, the graphene/PMMA composite material is prepared by adopting the graphene aerogel, the graphene is well dispersed in a PMMA matrix, and a complete electric and heat conducting network can be formed, so that the PMMA is beneficial to the application of PMMA in the aspects of electric and heat conducting performance and the like;
3. is convenient for popularization and expanded production.
Detailed Description
The present invention is described in terms of particular embodiments, other advantages and features of the invention will become apparent to those skilled in the art from the following disclosure, and it is to be understood that the described embodiments are merely exemplary of the invention and that it is not intended to limit the invention to the particular embodiments disclosed. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a PMMA structure composite material based on graphene aerogel framework regulation comprises the following steps:
(1) preparing graphene oxide: 1g of flake graphite and 30ml of 98 wt% concentrated sulfuric acid are mixed and stirred in an ice-water bath for 1 hour; then 6g of potassium permanganate is added to react for 1 hour; heating to 40 ℃, reacting for 1 hour, heating to 90 ℃, reacting for 1 hour, adding 200ml of deionized water into the reaction mixture for three times, adding 10ml of hydrogen peroxide with the concentration of 30%, cooling the reactant, cleaning with 3% dilute hydrochloric acid, cleaning with deionized water, centrifuging, and drying to obtain graphene oxide;
(2) preparing the graphene aerogel: preparing 10mg/ml aqueous solution from graphene oxide and deionized water, performing ultrasonic oscillation for 4 hours to obtain well-dispersed graphene oxide aqueous solution, adding the prepared graphene oxide aqueous solution into a hydrothermal kettle, treating at 120 ℃ for 12 hours to prepare graphene oxide hydrogel, putting the prepared graphene oxide hydrogel into a hydrazine hydrate solution with the concentration of 69 wt%, soaking at 95 ℃ for 24 hours, freeze-drying, and drying the freeze-dried graphene aerogel at 100 ℃ for 12 hours to obtain the graphene aerogel;
(3) preparation of PMMA prepolymer: putting 20ml of Methyl Methacrylate (MMA) monomer into a cone, adding 0.06g of initiator dibenzoyl peroxide, heating the conical flask in a water bath at 80 ℃ until the viscosity of the prepolymer in the flask reaches 700mPa & s, immediately stopping heating, and rapidly cooling the conical flask to room temperature to obtain a PMMA prepolymer;
(4) preparing a graphene aerogel/PMMA composite material: cutting the prepared graphene aerogel into 5 multiplied by 4 multiplied by 1cm according to the PMMA molding requirement3Then putting the cut graphene aerogel into the space of 5 multiplied by 4 multiplied by 2cm3And (3) injecting the prepolymer in the step (3) into the mold, keeping the temperature at 45 ℃, keeping the temperature for 5 hours, then continuously raising the temperature to 90 ℃, keeping the temperature for 1-2 hours, then stopping heating, naturally cooling to 35-40 ℃, and taking down the mold to obtain the graphene aerogel/PMMA composite material.
Example 2
Preparation and performance of a PMMA structure composite material based on graphene aerogel skeleton regulation and control are as follows:
(1) preparing graphene oxide: 1g of flake graphite and 30ml of 98 wt% concentrated sulfuric acid are mixed and stirred in an ice-water bath for 1 hour; then 6g of potassium permanganate is added to react for 1 hour; heating to 40 ℃, reacting for 1h, finally heating to 90 ℃, reacting for 1h, adding 200ml of deionized water into the reaction mixture for three times, then adding 10ml of hydrogen peroxide with the concentration of 30%, after the reactant is cooled, firstly cleaning with 3% dilute hydrochloric acid, then cleaning with deionized water, centrifuging, and drying to obtain graphene oxide;
(2) preparing the graphene aerogel: preparing a 20mg/ml aqueous solution from graphene oxide and deionized water, performing ultrasonic oscillation for 4 hours to obtain a well-dispersed graphene oxide aqueous solution, adding the prepared graphene oxide aqueous solution into a hydrothermal kettle, treating at 120 ℃ for 12 hours to prepare a graphene oxide hydrogel, putting the prepared graphene oxide hydrogel into a hydrazine hydrate solution with the concentration of 72 wt%, soaking at 95 ℃ for 24 hours, freeze-drying, and drying the freeze-dried graphene aerogel at 100 ℃ for 12 hours to obtain the graphene aerogel;
(3) preparation of PMMA prepolymer: putting 40ml of Methyl Methacrylate (MMA) monomer into a cone, adding 0.12g of initiator dibenzoyl peroxide, heating the conical flask in a water bath at 80 ℃ until the viscosity of the prepolymer in the flask reaches 650mPa & s, immediately stopping heating, and rapidly cooling the conical flask to room temperature to obtain a PMMA prepolymer;
(4) preparing a graphene aerogel/PMMA composite material: cutting the prepared graphene aerogel into 5 multiplied by 4 multiplied by 2cm according to the PMMA molding requirement3Then putting the cut graphene aerogel into the space of 5 multiplied by 4cm3And (3) injecting the prepolymer obtained in the step (3) into the mold, keeping the temperature at 45 ℃, keeping the temperature for 5 hours, then continuously raising the temperature to 90 ℃, keeping the temperature for 1-2 hours, then stopping heating, naturally cooling to 35-40 ℃, and taking down the mold to obtain the graphene aerogel/PMMA composite material.
Example 3
Preparation and performance of a PMMA structure composite material based on graphene aerogel skeleton regulation and control are as follows:
(1) preparing graphene oxide: 1g of flake graphite and 30ml of 98 wt% concentrated sulfuric acid are mixed and stirred in an ice-water bath for 1 hour; then 6g of potassium permanganate is added to react for 1 hour; heating to 40 ℃, reacting for 1h, finally heating to 90 ℃, reacting for 1h, adding 200ml of deionized water into the reaction mixture for three times, then adding 10ml of hydrogen peroxide with the concentration of 30%, after the reactant is cooled, firstly cleaning with 3% dilute hydrochloric acid, then cleaning with deionized water, centrifuging, and drying to obtain graphene oxide;
(2) preparing the graphene aerogel: preparing graphene oxide and deionized water into a water solution of 5mg/ml, performing ultrasonic oscillation for 4 hours to obtain a well-dispersed graphene oxide water solution, adding the prepared graphene oxide water solution into a hydrothermal kettle, treating at 120 ℃ for 12 hours to prepare a graphene oxide hydrogel, putting the prepared graphene oxide hydrogel into a hydrazine hydrate solution with the concentration of 65 wt%, soaking at 95 ℃ for 24 hours, performing freeze drying, and drying the freeze-dried graphene aerogel at 100 ℃ for 12 hours to obtain the graphene aerogel;
(3) preparation of PMMA prepolymer: putting 64ml of Methyl Methacrylate (MMA) monomer into a cone, adding 0.20g of initiator dibenzoyl peroxide, heating the conical flask in a water bath at 80 ℃ until the viscosity of the prepolymer in the flask reaches 750mPa & s, immediately stopping heating, and rapidly cooling the conical flask to room temperature to obtain a PMMA prepolymer;
(4) preparing a graphene aerogel/PMMA composite material: cutting the prepared graphene aerogel into 4 multiplied by 4cm according to the PMMA molding requirement3Then putting the cut graphene aerogel into the space of 4 multiplied by 6cm3And (3) injecting the prepolymer in the step (3), keeping the temperature at 45 ℃, preserving the heat for 5 hours, then continuously raising the temperature to 90 ℃, preserving the heat for 1-2 hours, then stopping heating, naturally cooling to 35-40 ℃, and taking down the mold to obtain the graphene aerogel/PMMA composite material.
Example 4
Preparation and performance of a PMMA structure composite material based on graphene aerogel skeleton regulation and control are as follows:
(1) preparing graphene oxide: 1g of flake graphite and 30ml of 98 wt% concentrated sulfuric acid are mixed and stirred in an ice-water bath for 1 hour; then 6g of potassium permanganate is added to react for 1 hour; heating to 40 ℃, reacting for 1h, finally heating to 90 ℃, reacting for 1h, adding 200ml of deionized water into the reaction mixture for three times, then adding 10ml of hydrogen peroxide with the concentration of 30%, after the reactant is cooled, firstly cleaning with 3% dilute hydrochloric acid, then cleaning with deionized water, centrifuging, and drying to obtain graphene oxide;
(2) preparing the graphene aerogel: preparing graphene oxide and deionized water into a 30mg/ml aqueous solution, performing ultrasonic oscillation for 4 hours to obtain a well-dispersed graphene oxide aqueous solution, adding the prepared graphene oxide aqueous solution into a hydrothermal kettle, treating at 120 ℃ for 12 hours to prepare a graphene oxide hydrogel, putting the prepared graphene oxide hydrogel into a hydrazine hydrate solution with the concentration of 69 wt%, soaking at 95 ℃ for 24 hours, freeze-drying, and drying the freeze-dried graphene aerogel at 100 ℃ for 12 hours to obtain the graphene aerogel;
(3) preparation of PMMA prepolymer: putting 35ml of Methyl Methacrylate (MMA) monomer into a cone, adding 0.11g of initiator dibenzoyl peroxide, heating the conical flask in a water bath at 80 ℃ until the viscosity of the prepolymer in the flask reaches 720mPa & s, immediately stopping heating, and rapidly cooling the conical flask to room temperature to obtain a PMMA prepolymer;
(4) preparing a graphene aerogel/PMMA composite material: cutting the prepared graphene aerogel into cylinders with the radius of 2cm and the height of 6cm according to PMMA (polymethyl methacrylate) molding requirements, then putting the cut graphene aerogel into a mold with the radius of 2cm and the height of 8cm, injecting the prepolymer in the step (3), keeping the temperature at 45 ℃, keeping the temperature for 5 hours, then continuously raising the temperature to 90 ℃, keeping the temperature for 1-2 hours, then stopping heating, naturally cooling to 35-40 ℃, taking down the mold, and thus obtaining the graphene aerogel/PMMA composite material.
According to the embodiment of the invention, a series of characteristics of excellent electrical conductivity, high superelasticity, large specific surface area, oleophylic fire resistance, ultrahigh porosity and the like of the graphene aerogel are utilized, the graphene aerogel/PMMA composite material is prepared by firstly infiltrating the PMMA prepolymer and then carrying out in-situ PMMA polymerization, and the electrical and thermal conductivity and other properties of the composite material are obviously improved compared with those of the prior art.
Although the invention has been described in detail above with reference to a general description and specific examples, it will be apparent to one skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. The preparation method of the PMMA structure composite material based on graphene aerogel skeleton regulation is characterized by comprising the steps of infiltrating a PMMA prepolymer into graphene aerogel, and then carrying out in-situ polymerization on the PMMA prepolymer to prepare the graphene aerogel/PMMA composite material.
2. The method of claim 1, comprising the steps of:
(1) preparing graphene oxide;
(2) preparing graphene aerogel;
(3) preparing a PMMA prepolymer; and
(4) and preparing the graphene aerogel/PMMA composite material.
3. The method according to claim 2, wherein the step (1) comprises: blending the flake graphite with concentrated sulfuric acid, and stirring in an ice water bath for 1-1.5 h; then adding potassium permanganate, and reacting for 1-1.5 h; then heating to 40-45 ℃ and reacting for 1-1.5 h; and heating to 85-90 ℃, reacting for 1-1.5 h, adding deionized water into the reaction mixture for three times, adding hydrogen peroxide until the reactant turns yellow, cooling the reactant, cleaning with dilute hydrochloric acid, cleaning with deionized water, centrifuging, and drying to obtain the graphene oxide.
4. The preparation method according to claim 3, wherein in the step (1), the concentrated sulfuric acid has a concentration of 98 wt%, the scale graphite has a mesh size of 200-300, the ratio of the scale graphite to the concentrated sulfuric acid is 1g:20 ml-1 g:30ml, the ratio of potassium permanganate to the concentrated sulfuric acid is 1g:4 ml-1 g:6ml, the volume ratio of the total amount of deionized water to the concentrated sulfuric acid is 6: 1-7: 1, the concentration of hydrogen peroxide is 30 wt%, and the concentration of dilute hydrochloric acid is 2 wt% -3 wt%.
5. The method according to claim 3, wherein the step (2) comprises: preparing graphene oxide and deionized water into an aqueous solution, and performing ultrasonic oscillation for 0.1-6 hours to obtain a well-dispersed graphene oxide aqueous solution; adding the graphene oxide aqueous solution into a hydrothermal kettle, and treating for 2-24 hours at 90-200 ℃ to obtain graphene oxide hydrogel; putting the graphene oxide hydrogel into a hydrazine hydrate aqueous solution, soaking for 24-48 h at 90-100 ℃, and freeze-drying; and drying the freeze-dried graphene aerogel at 90-100 ℃ for 8-12 h to obtain the graphene aerogel.
6. The preparation method according to claim 5, wherein the concentration of the graphene oxide aqueous solution in the step (2) is 0.1-50 mg/ml; the mass ratio of hydrazine hydrate to graphene oxide in the hydrazine hydrate aqueous solution is 10: 7-10: 10.
7. A preparation method according to claim 6, characterized in that the concentration of the hydrazine hydrate aqueous solution is 40-80 wt%.
8. The method according to claim 5, wherein the step (3) comprises: putting a Methyl Methacrylate (MMA) monomer into a conical flask, adding an initiator dibenzoyl peroxide, wherein the ratio of the initiator to the MMA is 1g:250 ml-1 g:300 ml; and heating the conical flask in a water bath at the temperature of 80-90 ℃ until the viscosity of reactants in the conical flask reaches 600-800 mPa & s, stopping heating, and rapidly cooling the conical flask to room temperature to obtain the PMMA prepolymer.
9. The method according to claim 8, wherein the step (4) comprises: cutting the graphene aerogel obtained in the step (2) into a filling shape of a PMMA (polymethyl methacrylate) forming mold, then putting the cut graphene aerogel into the mold with a corresponding shape, and injecting the PMMA prepolymer obtained in the step (3); keeping the temperature at 40-50 ℃, preserving the heat for 5-7 h, then continuously raising the temperature to 90-100 ℃, preserving the heat for 1-2 h, then stopping heating, naturally cooling to 35-40 ℃, and taking down the mold to obtain the graphene aerogel/PMMA composite material.
10. The production method according to claim 9, wherein when the PMMA molding die in step (4) is a rectangular parallelepiped of 20ml, the initiator used in step (3) is dibenzoyl peroxide of 0.06 g; when the PMMA molding mould in the step (4) is a cuboid of 40ml, 0.12g of dibenzoyl peroxide serving as an initiator in the step (3) is used; when the PMMA molding mould in the step (4) is 64ml of cube, the initiator used in the step (3) is 0.20g of dibenzoyl peroxide; when the PMMA molding die in the step (4) is 35ml of a cylinder, the initiator used in the step (3) is 0.11g of dibenzoyl peroxide.
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| CN115849350A (en) * | 2022-12-28 | 2023-03-28 | 东莞市鸿亿导热材料有限公司 | Graphene aerogel and preparation method thereof |
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