CN110423299B - Preparation method of polystyrene/graphene composite porous material for oil-water separation - Google Patents
Preparation method of polystyrene/graphene composite porous material for oil-water separation Download PDFInfo
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- CN110423299B CN110423299B CN201910606887.1A CN201910606887A CN110423299B CN 110423299 B CN110423299 B CN 110423299B CN 201910606887 A CN201910606887 A CN 201910606887A CN 110423299 B CN110423299 B CN 110423299B
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- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
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Abstract
The invention relates to a preparation method of a polystyrene/graphene composite porous material for oil-water separation, and belongs to the technical field of composite materials. The preparation method comprises the following steps: s1, uniformly dispersing graphene in a mixed solution of styrene, a cross-linking agent and an emulsifier span80, and heating to a certain temperature; s2, slowly dropwise adding an aqueous solution containing persulfate and sulfate into the mixed solution obtained in the step S1, and keeping a constant stirring speed in the dropwise adding process to obtain a high internal phase emulsion with the graphene particles and the emulsifier span80 being synergistically stable; s3, transferring the high internal phase emulsion obtained in the step S2 after reacting for 0.5-1 hour to a plastic wide-mouth reaction cup, continuing to perform heat preservation reaction for 24-48 hours, and drying after the monomer completely reacts to obtain the polystyrene/graphene composite porous material. The polystyrene/graphene composite porous material prepared by the invention has good mechanical property, uniform pore size, large porosity and high oil absorption rate, and is suitable for being used as an adsorption material for oil-water separation.
Description
Technical Field
The invention relates to the technical field of composite materials, and particularly relates to a polystyrene/graphene composite porous material with an oil-water separation effect and a preparation method thereof.
Background
The polystyrene polymer porous material has the physical properties of low density, large specific surface area, high porosity and the like, so the material has wide application value in the process fields of material transmission, adsorption and separation, surface catalysis, controlled release and the like.
Patent 106008770B relates to a method for preparing an environment-friendly porous polystyrene material, in which biodiesel is used as a pore-forming agent to prepare the environment-friendly porous polystyrene material, the degradation rate of the environment-friendly porous polystyrene material can reach more than 98%, the used pore-forming agent is green, environment-friendly and degradable biodiesel, the sulfur content, sulfide and sulfur dioxide emission are low, no environmental pollution is caused, and meanwhile, aromatic alkane is not contained, and the environmental damage caused by abandonment is small; patent 107082857B reports a preparation method of a PS-B-Tb complex amphiphilic block copolymer, which prepares amphiphilic block copolymer cellular porous membranes with good solubility, good orderliness, fluorescent characteristic, and further modification of polymer ends by using raw materials with different mass ratios.
The pore size of the polystyrene polymer porous material prepared by the method is not easy to control, and the application performance of the polystyrene polymer porous material in the aspects of adsorption and separation is less concerned.
Disclosure of Invention
On the basis, the polystyrene/graphene composite porous material with controllable pore size, uniform distribution and higher mechanical strength is prepared by adopting the water-in-oil type high internal phase emulsion template, has a certain adsorption effect on oily substances such as chloroform, dichloromethane, petroleum ether and the like, and can be used as an oil-water separation adsorption material.
The invention provides a preparation method of a polystyrene/graphene composite porous material for oil-water separation, which comprises the following steps:
s1, uniformly dispersing graphene in a mixed solution of styrene, a cross-linking agent and an emulsifier span80, and heating to a certain temperature;
s2, slowly dropwise adding an aqueous solution containing persulfate and sulfate into the mixed solution obtained in the step S1, and keeping a constant stirring speed in the dropwise adding process to obtain a high internal phase emulsion with the graphene particles and the emulsifier span80 being synergistically stable;
s3, transferring the high internal phase emulsion obtained in the step S2 after reacting for 0.5-1 hour to a plastic wide-mouth reaction cup, continuing to perform heat preservation reaction for 24-48 hours, and drying after the monomer completely reacts to obtain the polystyrene/graphene composite porous material.
Further, in step S1, the graphene is added in an amount of 0.1% to 5% by mass of the styrene monomer, and preferably in an amount of 0.2% to 1% by mass of the styrene monomer.
Further, in step S1, the crosslinking agent is a polyvinyl functional monomer, preferably ethylene glycol dimethacrylate or divinylbenzene.
Further, in step S1, the mass ratio of the styrene to the crosslinking agent is 2:1 to 5: 1.
Further, in step S2, the internal phase of the high internal phase emulsion is controlled to be 74% to 90%, preferably 80% to 85%.
In the invention, on the other hand, the polystyrene/graphene composite porous material prepared by the method is provided, and the prepared material has the advantages of good mechanical property, uniform pore size, large porosity and high oil absorption rate, and is suitable for oil-water separation.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects: the invention adopts a water-in-oil type high internal phase emulsion template method to prepare the polystyrene/graphene composite porous material with controllable aperture, uniform size distribution and larger porosity. The preparation method takes the water phase as a dispersion phase, and the removal method is simple; the continuous phase polymerizes to form a porous material having a hierarchical pore structure. The porous material prepared by the method has good mechanical properties, has a certain adsorption effect on oily substances such as chloroform, dichloromethane, petroleum ether and the like, and can be used as an oil-water separation material.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention.
FIG. 1a is a scanning electron microscope image of a polystyrene/graphene composite porous material prepared in example 1 of the present invention;
FIG. 1b is a scanning electron microscope image of a polystyrene/graphene composite porous material prepared in example 3 of the present invention;
fig. 2 is a graph showing the adsorption kinetics of the polystyrene/graphene composite porous material prepared in example 2 of the present invention to various organic substances;
FIG. 3 is a graph illustrating the compression performance of a polystyrene/graphene composite porous material prepared according to an embodiment of the present invention;
fig. 4a, 4b, 4c, and 4d are graphs of the thermal weight loss of the polystyrene/graphene composite porous material prepared in the embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be further described with reference to the accompanying drawings.
Example 1
(1) Adding 4g of styrene (St), 1.2g of Ethylene Glycol Dimethacrylate (EGDMA), 1g of Span80 (Span80) and 0.004g of graphene into a 250ml four-mouth bottle, stirring and heating to 60 ℃;
(2) weighing 0.25g of potassium persulfate (KPS) and 0.1g of potassium sulfate, and dissolving in 45ml of deionized water;
(3) after the temperature in the four-mouth flask is stable, dripping the solution prepared in the step (2) into the four-mouth flask by using a constant-pressure dropping funnel, wherein the dripping time is about 0.5 h;
(4) stirring for 3min to obtain milky thick emulsion (HIPE);
(5) and transferring the high internal phase emulsion into a plastic cylindrical tube, placing the plastic cylindrical tube into a 60 ℃ oven for reaction for 48 hours, and drying to obtain the polystyrene-graphene composite porous material.
A scanning electron microscope image of the polystyrene-graphene composite porous material prepared in example 1 is shown in fig. 1 a.
Example 2
(1) Adding 4g of styrene, 1.2g of EGDMA, 1g of Span80 and 0.008g of graphene into a 250ml four-mouth bottle, stirring and heating to 60 ℃;
(2) weighing 0.25g of KPS and 0.1g of potassium sulfate, and dissolving in 45ml of deionized water;
(3) after the temperature in the four-mouth flask is stable, dripping the solution prepared in the step (2) into the four-mouth flask by using a constant-pressure dropping funnel, wherein the dripping time is about 0.5 h;
(4) stirring for 3min to obtain milk white thick emulsion (HIPE);
(5) and transferring the high internal phase emulsion into a plastic cylindrical tube, placing the plastic cylindrical tube into a 60 ℃ oven for reaction for 48 hours, and drying to obtain the polystyrene-graphene composite porous material.
The adsorption kinetic curve of the polystyrene-graphene composite porous material prepared in example 2 on various organic substances is shown in fig. 2.
Example 3
(1) Adding 4g of styrene, 1.2g of EGDMA, 1g of Span80 and 0.012g of graphene into a 250ml four-mouth bottle, stirring and heating to 60 ℃;
(2) weighing 0.25g of KPS and 0.1g of potassium sulfate, and dissolving in 45ml of deionized water;
(3) after the temperature in the four-mouth flask is stable, dripping the solution prepared in the step (2) into the four-mouth flask by using a constant-pressure dropping funnel, wherein the dripping time is about 0.5 h;
(4) stirring for 3min to obtain milky thick emulsion (HIPE);
(5) and transferring the high internal phase emulsion into a plastic cylindrical tube, placing the plastic cylindrical tube into a 60 ℃ oven for reaction for 48 hours, and drying to obtain the polystyrene-graphene composite porous material.
A scanning electron microscope image of the polystyrene-graphene composite porous material prepared in example 3 is shown in fig. 1 b.
Example 4
(1) Adding 4g of styrene, 1.2g of EGDMA, 1g of Span80 and 0.016g of graphene into a 250ml four-mouth bottle, stirring and heating to 60 ℃;
(2) weighing 0.25g of KPS and 0.1g of potassium sulfate, and dissolving in 45ml of deionized water;
(3) after the temperature in the four-mouth flask is stable, dripping the solution prepared in the step (2) into the four-mouth flask by using a constant-pressure dropping funnel, wherein the dripping time is about 0.5 h;
(4) stirring for 3min to obtain milk white thick emulsion (HIPE);
(5) and transferring the high internal phase emulsion into a plastic cylindrical tube, placing the plastic cylindrical tube into a 60 ℃ oven for reaction for 48 hours, and drying to obtain the polystyrene-graphene composite porous material.
The polystyrene-graphene composite porous material prepared by the embodiment of the invention is characterized by comprising the following steps:
as shown in FIGS. 1a and 1b, when the porous materials obtained in examples 1 and 3 of the present invention were tested by scanning electron microscopy, it can be seen that the porous materials obtained have a macroporous structure with a size of 10 μm to 20 μm and a through hole with a size of 1 μm to 5 μm, and have uniform pore size distribution and high porosity.
As shown in fig. 2, the porous material prepared in example 2 of the present invention was subjected to an adsorption performance test, and the result shows that the porous material has an adsorption effect on organic substances such as chloroform, dichloromethane, n-hexane, toluene, petroleum ether, etc.; the porous material has certain adsorbability to oily materials and stronger adsorbability to substances with similar solubility parameters.
As shown in fig. 3, the compression performance test of the porous materials prepared in examples 1, 2, 3 and 4 of the present invention shows that the addition of a proper amount of graphene contributes to the improvement of the mechanical properties of the porous material of the present invention.
FIGS. 4a, 4b, 4c and 4d are graphs showing the thermogravimetry of the porous materials obtained in examples 1, 2, 3 and 4 of the present invention.
The features of the embodiments and embodiments described herein above may be combined with each other without conflict.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (3)
1. A preparation method of a polystyrene/graphene composite porous material for oil-water separation is characterized by comprising the following steps:
s1, uniformly dispersing graphene in a mixed solution of styrene, ethylene glycol dimethacrylate and an emulsifier span80, and heating to a certain temperature; the addition amount of the graphene is 0.1-0.4% of the mass of the styrene monomer; the mass ratio of the styrene to the ethylene glycol dimethacrylate is 10: 3; the mass ratio of the styrene to the emulsifier span80 is 4: 1;
s2, slowly dropwise adding an aqueous solution containing persulfate and sulfate into the mixed solution obtained in the step S1, and keeping a constant stirring speed in the dropwise adding process to obtain a high internal phase emulsion with the graphene particles and the emulsifier span80 being synergistically stable; the mass-volume ratio of the persulfate to the sulfate to the water is 5g:2g:900mL, and the mass ratio of the persulfate to the styrene monomer is 1: 16;
s3, transferring the high internal phase emulsion obtained in the step S2 after reacting for 0.5-1 hour to a plastic wide-mouth reaction cup, continuing to perform heat preservation reaction for 24-48 hours, and drying after the monomer completely reacts to obtain the polystyrene/graphene composite porous material.
2. The method for preparing a polystyrene/graphene composite porous material for oil-water separation according to claim 1, wherein in step S2, the internal phase of the high internal phase emulsion accounts for 74% to 90%.
3. A polystyrene/graphene composite porous material prepared by the method according to any one of claims 1 to 2, which is suitable for being used as an adsorption material for oil-water separation.
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Citations (3)
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| CN103408786A (en) * | 2013-07-26 | 2013-11-27 | 复旦大学 | Preparation method of porous graphene-polymer composite material |
| CN104774285A (en) * | 2015-04-03 | 2015-07-15 | 复旦大学 | Method for preparing through-hole polymer porous aquagel by using graphene oxide (GO) |
| CN105884952A (en) * | 2015-01-07 | 2016-08-24 | 中国科学院大学 | Synthesis and application of high-porosity and ultra-large porous polystyrene material |
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Patent Citations (3)
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| CN103408786A (en) * | 2013-07-26 | 2013-11-27 | 复旦大学 | Preparation method of porous graphene-polymer composite material |
| CN105884952A (en) * | 2015-01-07 | 2016-08-24 | 中国科学院大学 | Synthesis and application of high-porosity and ultra-large porous polystyrene material |
| CN104774285A (en) * | 2015-04-03 | 2015-07-15 | 复旦大学 | Method for preparing through-hole polymer porous aquagel by using graphene oxide (GO) |
Non-Patent Citations (4)
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| Macroporous polym er nanocomp osites synthesis ed from high internal phase emulsion templates stabilised by reduced graphene oxide;Ling L. Ching Wong等;《Polymer》;20131005;第55卷;第395-402页 * |
| 滕菲月.高内相乳液模板法制备石墨烯/聚合物复合多孔材料.《中国优秀硕士学位论文全文数据库 工程科技I辑》.2016,(第02期),第B020-234页. * |
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