CN109942732B - Polymethyl methacrylate and graphene oxide composite material and preparation method thereof - Google Patents
Polymethyl methacrylate and graphene oxide composite material and preparation method thereof Download PDFInfo
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- CN109942732B CN109942732B CN201910281194.XA CN201910281194A CN109942732B CN 109942732 B CN109942732 B CN 109942732B CN 201910281194 A CN201910281194 A CN 201910281194A CN 109942732 B CN109942732 B CN 109942732B
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Abstract
The invention relates to the technical field of graphene composite materials, in particular to a polymethyl methacrylate and graphene oxide composite material and a preparation method thereof, wherein (1) graphene oxide is prepared from flake graphite by a hummers method and dried into powder for later use; (2) adding graphene oxide powder into a reaction solvent, adding a surfactant, calcium chloride, sodium carbonate and methyl methacrylate, premixing to form oily liquid drops, and suspending in deionized water; (3) and (3) dropping an initiator for suspension polymerization, and filtering the yellow polymer particles to obtain the polymethyl methacrylate and graphene oxide composite material. The surface of the graphene oxide adopted by the invention has active groups; the suspension polymerization adopts a large amount of deionized water as a reaction solvent, so that the method is environment-friendly, safe and low in cost; the particle size of the macromolecular compound formed by the polymerization reaction can be adjusted through the mixing proportion of the surfactant; the method for compounding the graphene and the high polymer material is more effective.
Description
Technical Field
The invention relates to the technical field of graphene composite materials, in particular to a polymethyl methacrylate and graphene oxide composite material and a preparation method thereof.
Background
The existing technology for combining graphene and macromolecules mainly comprises resin blending and solution polymerization, most of the graphene and macromolecules are combined in a physical mixing state by adopting a resin blending mode, and a solution-liquid polymerization composite macromolecular material is not suitable for being prepared into dry powdery or granular resin and has low purity.
Graphene is a honeycomb-shaped planar thin film formed by carbon atoms in an sp2 hybridization manner, is a quasi-two-dimensional material with the thickness of only one atomic layer, and is also called monoatomic layer graphite. It has a thickness of about 0.335nm, and has various undulations depending on the production method, and generally has a height of about 1nm in the vertical direction and a width of about 10nm to 25nm in the horizontal direction, and is a basic structural unit of all carbon crystals (zero-dimensional fullerene, one-dimensional carbon nanotube, three-dimensional graphite) except diamond.
Due to the conjugated structure of graphene, the compatibility of graphene with water, organic solvents and polymers is poor, and therefore the application difficulty of graphene in the field of high molecules is increased.
The graphene oxide directly participates in the reaction of polymerizing the monomer into a high polymer through the oxygen-containing active functional group on the graphene oxide, so that the graphene oxide is directly bonded to the high polymer material through a chemical bond, and the function of the composite material is better exerted.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a polymethyl methacrylate and graphene oxide composite material and a preparation method thereof, which are used for overcoming the shortcomings of the existing graphene blended high polymer material in the aspect of performance and simultaneously overcoming the problem of combination of graphene and the high polymer material.
The purpose of the invention is realized by the following technical scheme: a preparation method of a polymethyl methacrylate and graphene oxide composite material comprises the following steps:
(1) preparing graphene oxide from flake graphite by a hummers method, and drying the graphene oxide into powder for later use;
(2) adding graphene oxide powder into a reaction solvent, adding a surfactant, calcium chloride, sodium carbonate and methyl methacrylate, premixing to form oily liquid drops, and suspending in deionized water;
(3) and (3) dropping an initiator for suspension polymerization, and filtering the yellow polymer particles to obtain the polymethyl methacrylate and graphene oxide composite material.
Graphene oxide itself contains a large number of oxygen-containing functional groups, such as carboxyl, hydroxyl, ester, carbonyl, aldehyde, and the like, and also contains a large number of unsaturated bonds, and these active functional groups provide conditions for compounding graphene oxide with a high polymer material.
Most of the existing preparation methods of graphene polymer composites require high-temperature conditions or release heat in a large amount under curing conditions, such as melting and mixing of graphene oxide and resin. The oxygen-containing functional group of the graphene oxide is removed at high temperature, so that the graphene oxide is reduced, and the color of the graphene oxide is changed into black, which brings adverse effects to the preparation of the graphene oxide polymer composite material.
The suspension polymerization method has the advantage of high product purity, and the reaction can be carried out at low temperature, which is an important advantage for ensuring that the original performance of the graphene oxide is maintained. Water is used as a solvent, a large amount of heat released by the initiation reaction can be quickly transferred into the reaction solvent, and the controllability of the polymerization reaction is greatly increased. By selecting a proper initiator, the reaction temperature can be controlled between 60 and 80 ℃, and graphene oxide is ensured not to be decomposed due to high temperature.
The suspension polymerization adopts deionized water as a reaction solvent, is environment-friendly and safe, and has low cost. The graphene polymer composite material formed by suspension polymerization can be directly formed into round particles, the particle size of the graphene polymer composite material can be controlled by adjusting the mixing ratio and the reaction conditions of the surfactant, and a double screw or a pulverizer is not needed to mold the product.
Preferably, in the step (1), the particle size of the flake graphite is 2000-12000 meshes.
Preferably, in the step (2), the premixing conditions are as follows: premixing for 0.4-0.6h under the conditions of mechanical stirring at 200 and 400 rpm.
Preferably, in the step (2), the reaction solvent is a mixed solution of deionized water and an organic solvent in a mass ratio of 4-16: 1.
Preferably, the organic solvent is at least one of absolute ethyl alcohol and isopropyl alcohol.
Preferably, in the step (2), the surfactant is a mixture of at least two of a PVA solution with a mass fraction of 0.5-1.5%, a CMC solution with a mass fraction of 0.5-1.5%, and an OP solution with a mass fraction of 0.5-1.5%.
Preferably, in the step (2), the molar ratio of calcium chloride to sodium carbonate is 0.8-1.2: 1.
preferably, in the step (2), the initiator is at least one of AIBN, BPO and APS.
Preferably, in the step (3), the suspension polymerization reaction conditions are as follows: the mechanical stirring is carried out for 200r/min, the reaction temperature is 75-85 ℃, and the reaction time is 1.5-2.5 h.
The other purpose of the invention is realized by the following technical scheme: a polymethyl methacrylate and graphene oxide composite material, which is prepared according to the preparation method of the above claims.
The invention has the beneficial effects that: the surface of the graphene oxide adopted by the invention has active groups; the suspension polymerization adopts a large amount of deionized water as a reaction solvent, so that the method is environment-friendly, safe and low in cost; the particle size of the macromolecular compound formed by the polymerization reaction can be adjusted through the mixing proportion of the surfactant; the method for compounding the graphene and the high polymer material is more effective.
Drawings
Fig. 1 is a process flow diagram of the graphene oxide composite material prepared by the present invention.
Fig. 2 is an infrared spectrum of the graphene oxide composite material prepared by the present invention.
Fig. 3 is a scanning electron microscope image of the graphene oxide composite material prepared by the present invention.
Detailed Description
For the understanding of those skilled in the art, the present invention will be further described with reference to the following examples and accompanying drawings 1-1, and the content of the embodiments is not intended to limit the present invention.
Example 1
A preparation method of a polymethyl methacrylate and graphene oxide composite material comprises the following steps:
(1) preparing graphene oxide from flake graphite by a hummers method, and drying the graphene oxide into powder for later use;
(2) adding graphene oxide powder into a reaction solvent, adding a surfactant, calcium chloride, sodium carbonate and methyl methacrylate, premixing to form oily liquid drops, and suspending in deionized water;
(3) and (3) dropping an initiator for suspension polymerization, and filtering the yellow polymer particles to obtain the polymethyl methacrylate and graphene oxide composite material.
In the step (1), the particle size of the crystalline flake graphite is 2000 meshes.
In the step (2), the premixing conditions are as follows: premixing for 0.5h under the condition of mechanical stirring at 300 rpm.
In the step (2), the reaction solvent is a mixed solution of deionized water and an organic solvent in a mass ratio of 16: 1.
The organic solvent is absolute ethyl alcohol.
In the step (2), the surfactant is a mixed solution composed of a PVA solution with a mass fraction of 1%, a CMC solution with a mass fraction of 1% and an OP solution with a mass fraction of 1% in a mass ratio of 1:1: 0.1.
In the step (2), the molar ratio of calcium chloride to sodium carbonate is 1: 1.
in the step (2), the initiator is BPO.
In the step (3), the suspension polymerization reaction conditions are as follows: mechanically stirring for 300r/min, wherein the reaction temperature is 80 ℃ and the reaction time is 2 h.
A polymethyl methacrylate and graphene oxide composite material, which is prepared according to the preparation method of the above claims.
Example 2
This embodiment is different from embodiment 1 described above in that:
in the step (1), the particle size of the crystalline flake graphite is 8000 meshes.
In the step (2), the premixing conditions are as follows: premixing for 0.5h under the condition of mechanical stirring at 300 rpm.
In the step (2), the reaction solvent is a mixed solution of deionized water and an organic solvent in a mass ratio of 4: 1.
The organic solvent is isopropanol.
In the step (2), the surfactant is a mixed solution of a PVA solution with the mass fraction of 1% and a CMC solution with the mass fraction of 1% in a mass ratio of 1: 1.
In the step (2), the molar ratio of calcium chloride to sodium carbonate is 1: 1.
in the step (2), the initiator is a mixture of AIBN and BPO in a weight ratio of 1: 1.
In the step (3), the suspension polymerization reaction conditions are as follows: mechanically stirring for 300r/min, wherein the reaction temperature is 80 ℃ and the reaction time is 2 h.
Example 3
This embodiment is different from embodiment 1 described above in that:
in the step (1), the particle size of the crystalline flake graphite is 4000 meshes.
In the step (2), the premixing conditions are as follows: premixing for 0.6h under the condition of mechanical stirring at 200 rpm.
In the step (2), the reaction solvent is a mixed solution of deionized water and an organic solvent in a mass ratio of 8: 1.
The organic solvent is isopropanol.
In the step (2), the surfactant is a mixed solution of a PVA solution with the mass fraction of 0.5% and an OP solution with the mass fraction of 0.5% in a mass ratio of 1: 0.1.
In the step (2), the molar ratio of calcium chloride to sodium carbonate is 0.8: 1.
in the step (2), the initiator is AIBN.
In the step (3), the suspension polymerization reaction conditions are as follows: mechanically stirring for 200r/min at 75 deg.C for 2.5 h.
Example 4
This embodiment is different from embodiment 1 described above in that:
in the step (1), the particle size of the flake graphite is 12000 meshes.
In the step (2), the premixing conditions are as follows: premixing for 0.4h under the condition of mechanical stirring at 400 rpm.
In the step (2), the reaction solvent is a mixed solution of deionized water and an organic solvent in a mass ratio of 12: 1.
The organic solvent is absolute ethyl alcohol.
In the step (2), the surfactant is a mixed solution of a CMC solution with the mass fraction of 1.5% and an OP solution with the mass fraction of 1.5% in a mass ratio of 1: 0.1.
In the step (2), the molar ratio of calcium chloride to sodium carbonate is 1.2: 1.
in the step (2), the initiator is APS.
In the step (3), the suspension polymerization reaction conditions are as follows: mechanically stirring for 400r/min at 85 deg.C for 1.5 h.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (2)
1. A preparation method of a polymethyl methacrylate and graphene oxide composite material is characterized by comprising the following steps: the method comprises the following steps: preparing graphene oxide from flake graphite by a hummers method, and drying the graphene oxide into powder for later use; (2) adding graphene oxide powder into a reaction solvent, adding a surfactant, calcium chloride, sodium carbonate and methyl methacrylate, premixing to form oily liquid drops, and suspending in deionized water; (3) dropping an initiator for suspension polymerization, and filtering the yellow polymer particles to obtain a polymethyl methacrylate and graphene oxide composite material;
in the step (1), the particle size of the crystalline flake graphite is 2000-12000 meshes;
in the step (2), the premixing conditions are as follows: premixing for 0.4-0.6h under the conditions of mechanical stirring at 200-;
in the step (2), the reaction solvent is a mixed solution of deionized water and an organic solvent in a mass ratio of 4-16: 1;
the organic solvent is at least one of absolute ethyl alcohol and isopropanol;
in the step (2), the surfactant is formed by mixing at least two of PVA solution with the mass fraction of 0.5-1.5%, CMC solution with the mass fraction of 0.5-1.5% and OP solution with the mass fraction of 0.5-1.5%;
in the step (2), the molar ratio of calcium chloride to sodium carbonate is 0.8-1.2: 1;
in the step (2), the initiator is at least one of AIBN, BPO and APS;
in the step (3), the suspension polymerization reaction conditions are as follows: the mechanical stirring is carried out for 200r/min, the reaction temperature is 75-85 ℃, and the reaction time is 1.5-2.5 h.
2. A polymethyl methacrylate and graphene oxide composite material is characterized in that: the composite material is prepared according to the preparation method of claim 1.
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| US20110133134A1 (en) * | 2009-06-09 | 2011-06-09 | Vorbeck Materials Corp. | Crosslinkable and Crosslinked Compositions of Olefin Polymers and Graphene Sheets |
| US9540498B1 (en) * | 2010-04-03 | 2017-01-10 | Dan Scheffer | Method of coating a substrate with a graphene containing composition |
| CN102786614B (en) * | 2012-09-03 | 2014-05-07 | 四川省金路树脂有限公司 | Method for preparing graphene-polrvinyl chloride nanocomposite through in-situ emulsion polymerization |
| CN102786615B (en) * | 2012-09-03 | 2014-05-07 | 四川省金路树脂有限公司 | Method for preparing grapheme-polyvinyl chloride nano composite resin through in situ suspension polymerization |
| CN104311713A (en) * | 2014-09-23 | 2015-01-28 | 广州大学 | Graphene/epoxy acrylic acid composite resin and graphene/epoxy acrylic acid composite resin IMD ink preparation method |
| CN106928413A (en) * | 2017-03-26 | 2017-07-07 | 天津工业大学 | A kind of method of styrene maleic anhydride copolymer graft modification Graphene |
| US10214620B2 (en) * | 2017-04-28 | 2019-02-26 | The Boeing Company | Nano-reinforcement filler material for epoxy resin systems and methods of making the same |
| CN107141680B (en) * | 2017-06-12 | 2019-07-09 | 常州大学 | A kind of preparation method of modified graphene oxide/PMMA composite material |
| CN108440717B (en) * | 2018-03-15 | 2020-04-03 | 厦门大学 | Graphene oxide coated poly glycidyl methacrylate microsphere composite anticorrosive coating additive and preparation method thereof |
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