CN110423299A - A kind of water-oil separating polystyrene/graphene composite porous material preparation method - Google Patents
A kind of water-oil separating polystyrene/graphene composite porous material preparation method Download PDFInfo
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- CN110423299A CN110423299A CN201910606887.1A CN201910606887A CN110423299A CN 110423299 A CN110423299 A CN 110423299A CN 201910606887 A CN201910606887 A CN 201910606887A CN 110423299 A CN110423299 A CN 110423299A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
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- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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Abstract
The present invention relates to a kind of water-oil separating polystyrene/graphene composite porous material preparation methods, belong to technical field of composite materials.Preparation method of the present invention is the following steps are included: S1, disperse graphene uniform in the mixed liquor of styrene, crosslinking agent and emulsifier span 80, and be heated to certain temperature；S2, it is slowly added dropwise into the mixed liquor of step S1 into the aqueous solution containing persulfate and sulfate, dropwise addition process keeps constant mixing speed, obtains graphene particle with emulsifier span 80 and cooperates with stable High Internal Phase Emulsion；S3, plastics wide-mouth reaction cup relaying is transferred to after reacting the High Internal Phase Emulsion of step S2 0.5-1 hours continuous insulation reaction 24~48 hours, until monomer reaction is completely dry afterwards to be made polystyrene/graphene composite porous material.Polystyrene/graphene composite porous material produced by the present invention has good mechanical property, and aperture size is uniform in size, and porosity is larger, and oil absorbency is high, is suitable as the adsorbent material of water-oil separating.
Description
Technical field
The present invention relates to a kind of technical field of composite materials, and in particular to a kind of polyphenyl second with oil-water separation
Alkene/graphene composite porous material and preparation method thereof.
Background technique
Polystyrenic polymer's porous material has the physical properties such as low density, large specific surface area, porosity height, therefore
This kind of material has a wide range of applications value in the process areas such as mass transfer, absorption and separation, surface catalysis, control release.
Patent 106008770B is related to a kind of preparation method of environment-friendly type expanded polystyrene material, and this method is using biology
Environment-friendly type expanded polystyrene material is prepared as pore-foaming agent in diesel oil, and degradation rate can reach 98% or more, the cause used
Hole agent is environmentally protective, degradable biological diesel oil, and sulfur content, sulfide and sulfur dioxide (SO2) emissions are low, not will cause ring
Border pollution, while aromatic series alkane is free of, it discards to environmental nuisance very little；Patent 107082857B reports a kind of PS-b-Tb
The preparation method of complex amphipathic nature block polymer, by different quality than raw material be made dissolubility is good, order is good, has
Fluorescent characteristic, polymer ends can further progress modification the features such as the cellular porous film of amphipathic nature block polymer.
Polystyrenic polymer's porous material obtained above, aperture size is not easy to control, and the absorption for material
And the application performance concern of separation aspect is seldom.
Summary of the invention
On this basis, the present invention prepares controllable with pore size and divides using water-in-oil type High Internal Phase Emulsion template
Cloth is uniform, the polystyrene/graphene composite porous material with higher mechanical strength, to chloroform, methylene chloride, petroleum ether
Equal oily matters have certain adsorption effect, can be used as water-oil separating adsorbent material.
In the present invention, a kind of water-oil separating polystyrene/graphene composite porous material preparation method is provided, is wrapped
Include following steps:
S1, it disperses graphene uniform in the mixed liquor of styrene, crosslinking agent and emulsifier span 80, and is heated to
Certain temperature；
S2, it is slowly added dropwise into the mixed liquor of step S1 into the aqueous solution containing persulfate and sulfate, process is added dropwise
Mixing speed is kept constant, graphene particle is obtained with emulsifier span 80 and cooperates with stable High Internal Phase Emulsion；
S3, plastics wide-mouth reaction cup relaying continuation of insurance temperature is transferred to after reacting the High Internal Phase Emulsion of step S2 0.5-1 hours
Reaction 24~48 hours, until monomer reaction is completely dry afterwards to be made polystyrene/graphene composite porous material.
Further, in step sl, the graphene additive amount is the 0.1%-5% of styrene monomer quality, preferably
Additive amount is the 0.2%-1% of styrene monomer quality.
Further, in step sl, the crosslinking agent is more vinyl function monomers, preferably dimethacrylate second
Diol ester or divinylbenzene.
Further, in step sl, the mass ratio of the styrene and crosslinking agent is 2:1-5:1.
Further, in step s 2, interior phase accounting is 74%-90% in the High Internal Phase Emulsion, is preferably controlled in
80%-85%.
In the present invention, it is compound more on the other hand to additionally provide a kind of polystyrene/graphene by above method preparation
Porous materials, material, which is made, has good mechanical property, and aperture size is uniform in size, and porosity is larger, and oil absorbency is high, is suitable for
Water-oil separating.
Compared with prior art, technical solution of the present invention has the advantage that as follows: the present invention uses water-in-oil type
High Internal Phase Emulsion template prepare and size distribution controllable with aperture uniformly, the polystyrene/graphene of larger porosity
Composite porous material.For the preparation method using water phase as dispersed phase, minimizing technology is simple；Continuous phase-polymerization, which is formed, has grading-hole knot
The porous material of structure.Porous material produced by the present invention has preferable mechanical performance, to chloroform, methylene chloride, petroleum ether etc.
Oily matter has certain adsorption effect, can be used as water-oil separating material.
Detailed description of the invention
Attached drawing is only used for showing the purpose of specific embodiment, and is not to be construed as limiting the invention.
Fig. 1 a is the scanning electron microscope (SEM) photograph of polystyrene/graphene composite porous material made from the embodiment of the present invention 1；
Fig. 1 b is the scanning electron microscope (SEM) photograph of polystyrene/graphene composite porous material made from the embodiment of the present invention 3；
Fig. 2 is absorption of the polystyrene/graphene composite porous material to various organic matters made from the embodiment of the present invention 1
Moving curve figure；
Fig. 3 is the compression performance test chart of polystyrene/graphene composite porous material made from the embodiment of the present invention；
Fig. 4 is the thermogravimetric curve figure of polystyrene/graphene composite porous material made from the embodiment of the present invention.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with attached drawing to embodiment party of the present invention
Formula is further described.
Embodiment 1
(1) 4g styrene (St), 1.2g ethylene glycol dimethacrylate (EGDMA), 1g department are added in 250ml four-hole bottle
Disk 80 (Span80) and 0.004g graphene, agitating and heating are warming up to 60 DEG C；
(2) 0.25g potassium peroxydisulfate (KPS) is weighed, 0.1g potassium sulfate is dissolved in 45ml deionized water；
(3) after in four-hole bottle temperature stablize after, will in (2) with solution with constant pressure funnel instillation four-hole boiling flask in,
Time for adding is 0.5h or so；
(4) it is added dropwise and continues to stir 3min, obtain the thick shape lotion of milky to get High Internal Phase Emulsion (HIPE)；
(5) High Internal Phase Emulsion is transferred in plastics column tube, is placed in drying after 60 DEG C of baking ovens react 48 hours, obtains
Polystyrene-graphene composite porous material.
Polystyrene made from embodiment 1-graphene composite porous material scanning electron microscope (SEM) photograph is as shown in Figure 1a.
Embodiment 2
(1) 4g styrene, 1.2g EGDMA, 1g Span80 and 0.008g graphene, stirring are added in 250ml four-hole bottle
It is heated to 60 DEG C；
(2) 0.25g KPS is weighed, 0.1g potassium sulfate is dissolved in 45ml deionized water；
(3) after in four-hole bottle temperature stablize after, will in (2) with solution with constant pressure funnel instillation four-hole boiling flask in,
Time for adding is 0.5h or so；
(4) it is added dropwise and continues to stir 3min, obtain the thick shape lotion of milky to get High Internal Phase Emulsion (HIPE)；
(5) High Internal Phase Emulsion is transferred in plastics column tube, is placed in drying after 60 DEG C of baking ovens react 48 hours, obtains
Polystyrene-graphene composite porous material.
The absorption moving curve such as Fig. 2 of polystyrene made from embodiment 2-graphene composite porous material to various organic matters
It is shown.
Embodiment 3
(1) 4g styrene, 1.2g EGDMA, 1g Span80 and 0.012g graphene, stirring are added in 250ml four-hole bottle
It is heated to 60 DEG C；
(2) 0.25g KPS is weighed, 0.1g potassium sulfate is dissolved in 45ml deionized water；
(3) after in four-hole bottle temperature stablize after, will in (2) with solution with constant pressure funnel instillation four-hole boiling flask in,
Time for adding is 0.5h or so；
(4) it is added dropwise and continues to stir 3min, obtain the thick shape lotion of milky to get High Internal Phase Emulsion (HIPE)；
(5) High Internal Phase Emulsion is transferred in plastics column tube, is placed in drying after 60 DEG C of baking ovens react 48 hours, obtains
Polystyrene-graphene composite porous material.
Polystyrene made from embodiment 3-graphene composite porous material scanning electron microscope (SEM) photograph is as shown in Figure 1 b.
Embodiment 4
(1) 4g styrene, 1.2g EGDMA, 1g Span80 and 0.016g graphene, stirring are added in 250ml four-hole bottle
It is heated to 60 DEG C；
(2) 0.25g KPS is weighed, 0.1g potassium sulfate is dissolved in 45ml deionized water；
(3) after in four-hole bottle temperature stablize after, will in (2) with solution with constant pressure funnel instillation four-hole boiling flask in,
Time for adding is 0.5h or so；
(4) it is added dropwise and continues to stir 3min, obtain the thick shape lotion of milky to get High Internal Phase Emulsion (HIPE)；
(5) High Internal Phase Emulsion is transferred in plastics column tube, is placed in drying after 60 DEG C of baking ovens react 48 hours, obtains
Polystyrene-graphene composite porous material.
Property representation is carried out to polystyrene made from the embodiment of the present invention-graphene composite porous material:
As illustrated in figs. 1A and ib, Electronic Speculum is scanned to porous material made from the embodiment of the present invention 1 and embodiment 3 to survey
Examination, as can be seen from the figure porous material obtained has size running through in 10 μm -20 μm of macroporous structure and 1 μm -5 μm
Hole, pore-size distribution is more uniform, and porosity is high.
As shown in Fig. 2, doing absorption property test to porous material made from the embodiment of the present invention 2, the results showed that this is porous
Material all has adsorption effect to organic matters such as chloroform, methylene chloride, n-hexane, toluene and petroleum ethers；The porous material is to oil
Property material has certain adsorptivity, stronger to substance adsorption capacity similar in solubility parameters.
As shown in figure 3, pressing porous material made from the embodiment of the present invention 1, embodiment 2, embodiment 3, embodiment 4
Contracting performance test, the results showed that the raising for facilitating porous material mechanical performance of the invention is added in suitable graphene.
Fig. 4 a, 4b, 4c and 4d show the embodiment of the present invention 1, embodiment 2, embodiment 3, porous material made from embodiment 4
The thermogravimetric curve figure of material.
In the absence of conflict, the feature in embodiment and embodiment herein-above set forth can be combined with each other.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (7)
1. a kind of water-oil separating polystyrene/graphene composite porous material preparation method, which is characterized in that including following step
It is rapid:
S1, it disperses graphene uniform in the mixed liquor of styrene, crosslinking agent and emulsifier span80, and is heated to certain temperature
Degree；
S2, it is slowly added dropwise into the mixed liquor of step S1 into the aqueous solution containing persulfate and sulfate, process is added dropwise and keeps
Constant agitation speed obtains graphene particle with emulsifier span80 and cooperates with stable High Internal Phase Emulsion；
S3, the continuous insulation reaction of plastics wide-mouth reaction cup relaying is transferred to after reacting the High Internal Phase Emulsion of step S2 0.5-1 hours
24~48 hours, until monomer reaction is completely dry afterwards to be made polystyrene/graphene composite porous material.
2. a kind of water-oil separating according to claim 1 polystyrene/graphene composite porous material preparation method,
It is characterized in that, in step sl, the graphene additive amount is the 0.1%-5% of styrene monomer quality.
3. a kind of water-oil separating according to claim 1 polystyrene/graphene composite porous material preparation method,
It is characterized in that, in step sl, the crosslinking agent is more vinyl function monomers.
4. a kind of water-oil separating according to claim 3 polystyrene/graphene composite porous material preparation method,
It is characterized in that, in step sl, the crosslinking agent is any one in ethylene glycol dimethacrylate or divinylbenzene.
5. a kind of water-oil separating according to claim 1 polystyrene/graphene composite porous material preparation method,
It is characterized in that, in step sl, the mass ratio of the styrene and crosslinking agent is 2:1-5:1.
6. a kind of water-oil separating according to claim 1 polystyrene/graphene composite porous material preparation method,
It is characterized in that, in step s 2, interior phase accounting is 74%-90% in the High Internal Phase Emulsion.
7. a kind of polystyrene/graphene composite porous material prepared such as any one of claim 1-6 the method, is suitable for using
Make the adsorbent material of water-oil separating.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110975330A (en) * | 2019-12-17 | 2020-04-10 | 华东理工大学 | Synthesis method of novel rapid oil-water separation material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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- 2019-07-06 CN CN201910606887.1A patent/CN110423299B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 (3)
| Title |
|---|
| LING L. CHING WONG等: "Macroporous polym er nanocomp osites synthesis ed from high internal phase emulsion templates stabilised by reduced graphene oxide", 《POLYMER》 * |
| 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》 * |
| 范欣等: "高内相乳液模板法制备聚合物多孔材料研究进展", 《高分子材料科学与工程》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110975330A (en) * | 2019-12-17 | 2020-04-10 | 华东理工大学 | Synthesis method of novel rapid oil-water separation material |
| CN110975330B (en) * | 2019-12-17 | 2021-10-12 | 华东理工大学 | Synthesis method of rapid oil-water separation material |
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