CN104774285A - Method for preparing through-hole polymer porous aquagel by using graphene oxide (GO) - Google Patents
Method for preparing through-hole polymer porous aquagel by using graphene oxide (GO) Download PDFInfo
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Abstract
The invention belongs to the technical field of materials, and particularly relates to a method for preparing a through-hole polymer porous aquagel by using graphene oxide (GO). The method mainly comprises the following steps: carrying out surface modification on hydrophilic GO by using an oleophylic modifier, wherein the modified GO is used as a stabilizer of a Pickering emulsion; and adding a monomer, a crosslinking agent, an initiator and a pore-forming agent, emulsifying to obtain an oil-in-water high-inner-phase emulsion, and carrying out continuous phase polymerization on the high-inner-phase emulsion to obtain the through-hole-structure polymer porous aquagel. The method has the advantages of simple preparation process and lower cost. The prepared through-hole polymer porous aquagel has the advantages of controllable pore structure, large pore size (5-200 mu m), large interconnection size (2-70 mu m), favorable permeability, favorable swelling capacity and favorable adsorbability.
Description
Technical field
The invention belongs to field of material technology, be specifically related to a kind of method utilizing graphene oxide to prepare through hole polyalcohol stephanoporate hydrogel.
Background technology
Hydrogel is that one has wetting ability but water-fast high molecular polymer, and they can be swelling rapidly and still keep its shape and three-dimensional net structure in water.Because of the water suction of its uniqueness, water conservation and bionical characteristic, hydrogel is widely used in the fields such as drug controlled release, separating substances, organizational project.But conventional hydrogels rate of water absorption is low limits its application, and porous aquagel has higher specific surface area, substantially increases its service efficiency, thus receives increasing concern.
The preparation method of polyalcohol stephanoporate hydrogel mainly comprises phase separation method, foaming and template etc.Wherein High Internal Phase Emulsion template due to preparation porous aquagel aperture controllable and simple operation and other advantages be widely applied.Traditional High Internal Phase Emulsion generally all makees stablizer with tensio-active agent, stabilizing agent dosage is very large, account for 5% ~ 50% of external phase, and the usual price of these tensio-active agents is more expensive and have toxicity, therefore need to remove after polymerisation, this not only makes complex operation also considerably increase the cost preparing polyalcohol stephanoporate hydrogel.In recent years, it is found that solid particulate has almost irreversible absorption behavior at two-phase interface, make it also can be used for stable High Internal Phase Emulsion, this is that the High Internal Phase Emulsion of stablizer is commonly called Pickering High Internal Phase Emulsion with solid particulate.Pickering High Internal Phase Emulsion template has the advantages such as consumption is few, low toxicity, low cost, high stability preparing in polyalcohol stephanoporate hydrogel, in addition, some solid particulates, particularly the introducing of inorganic nanoparticles can also improve the physical strength of polyalcohol stephanoporate hydrogel, and give the physical properties that material is special, as conductance, thermal conductance and magnetic etc.
But, just because of the high sorptive power of solid particulate at droplet interfaces, cause stability of emulsion higher, be difficult in the course of the polymerization process coalescence occur, and solid particulate forms the thicker barrier layer of one deck at droplet interfaces, therefore the volumetric shrinkage in polymerization process and the mechanical effect in last handling process are all difficult to break through this obstruction, so often can only be polymerized the porous material obtaining having unicellular structure, this structure significantly limit the application of porous aquagel in various fields.Therefore the graphene oxide (GO) that the present invention proposes a kind of oleophylic modifier modification is as Pickering emulsion stabilizer, is obtained the method for the polyalcohol stephanoporate hydrogel with through-hole structure by High Internal Phase Emulsion template polymerization.Prepared porous aquagel pore structure is controlled, and greatly, permeability is good, has good swelling behavior and absorption property for aperture and pore interconnection size.
Summary of the invention
The object of the present invention is to provide a kind of method utilizing graphene oxide to prepare through hole polyalcohol stephanoporate hydrogel, by material prepared by the method, pore structure is controlled, aperture and pore interconnection size large, permeability is good, has good swelling behavior and absorption property.
The present invention is realized by the following technical programs: first form colloidal sol in a solvent by dispersed for graphene oxide (GO), add oleophylic properties-correcting agent and modification is carried out to GO, the modified GO obtained is scattered in water, add monomer, linking agent, initiator and pore-creating agent wherein again, stable oil-in-water-type High Internal Phase Emulsion is formed after homogeneous or supersound process, temperature reaction, the obtained polyalcohol stephanoporate hydrogel with through-hole structure.
The method utilizing graphene oxide to prepare through hole polyalcohol stephanoporate hydrogel provided by the invention, concrete steps are as follows:
(1) first, GO is in a solvent dispersed, be mixed with the colloidal sol of massfraction 0.05% ~ 1%, GO is of a size of 50 ~ 2000 nm; In GO colloidal sol, add oleophylic properties-correcting agent, oleophylic properties-correcting agent quality accounts for 0.5% ~ 300% of GO quality, at room temperature stirring reaction 0.5 ~ 24 h, then centrifuge washing, and obtains the GO of modification with vacuum drying oven drying under 40 ~ 65 ° of C;
Wherein, oleophylic properties-correcting agent comprises ionogenic surfactant, one in amino modified dose, isocyanate-modified dose, or wherein several; Ionogenic surfactant is the one in the amine salt of carbonatoms 8 ~ 16, quaternary ammonium salt, or wherein several; Amino modified dose is the one in the aliphatic amide of carbonatoms 6 ~ 18, aromatic amine, aliphatic diamine, aromatic diamines, aminosilane, or wherein several; Isocyanate-modified dose is the one in the aliphatics of carbonatoms 6 ~ 18, aromatic isocyanate, or wherein several;
(2) be dispersed in water by the GO of above-mentioned modification, the quality of water is 50-500 times of GO quality; In the above-mentioned water-sol, add monomer, monomer mass is 20 ~ 600 times of GO quality; Add linking agent again, linking agent quality is 1 ~ 75 times of GO quality; Then add initiator, initiator quality is 1 ~ 20 times of GO quality; Add water afterwards, control GO quality accounts for 0.08% ~ 1% of aqueous phase total mass;
Wherein, containing a carbon-carbon double bond and be water-soluble monomer in the molecular structure of monomer, comprise the one in acrylic acid or the like, propene sulfonic acid class, acrylic amide, NVP class, or wherein several; Containing two carbon-carbon double bonds in the molecular structure of linking agent, comprise the one in bisacrylamide class or double methacrylate class; Initiator is the one in Potassium Persulphate, ammonium persulphate, azo-bis-isobutyrate hydrochloride, azo two isobutyl imidazoline hydrochloride or azo dicyano valerate;
(3) last, in above-mentioned aqueous phase, add pore-creating agent, pore-creating agent quality is 2 ~ 8 times of aqueous phase quality; To this mixture with homogeneous or supersound process, the time is 5 ~ 60 min, forms oil-in-water-type High Internal Phase Emulsion; Emulsion is transferred in airtight hydrothermal reaction kettle, at the temperature of 55 ~ 80 ° of C, reacts 12 ~ 48 h; After reaction terminates, remove the pore-creating agent in product and unreacted monomer, use vacuum drying oven dry 24 ~ 48 h at the temperature of 40 ~ 65 ° of C, obtain the polyalcohol stephanoporate hydrogel with through-hole structure;
Wherein, pore-creating agent is the one in the alkane of carbonatoms 6 ~ 20, naphthenic hydrocarbon, or wherein several.
The inventive method technique is simple, and cost is lower, and suitability is wide; Prepared porous aquagel has through-hole structure, pore structure controllable, and aperture is 5 ~ 200 μm, and pore interconnection is of a size of 2 ~ 70 μm, and greatly, permeability is good, has good swelling behavior and absorption property for aperture and pore interconnection size.Regulating and controlling aperture and the pore interconnection size of porous aquagel by changing oleophylic properties-correcting agent and the mass ratio of GO and the mass ratio of GO and aqueous phase, regulating and controlling the permeability of porous aquagel, swelling behavior and absorption property further.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the polyalcohol stephanoporate hydrogel that embodiment 1 is prepared.
Fig. 2 is the stereoscan photograph of the polyalcohol stephanoporate hydrogel that embodiment 2 is prepared.
Embodiment
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention, every following examples are done according to technical spirit of the present invention any simple modification, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.
In following examples, used oleophylic properties-correcting agent has ionogenic surfactant cetyl trimethylammonium bromide (CTAB), amino modified dose of amino dodecane, isocyanate-modified dose of phenylcarbimide.
Raw material in following examples is commercial goods.
embodiment 1
1. be dispersed in water by graphene oxide (GO), be made into the aqueous solution of massfraction 0.5%, the mean sizes of GO lamella is 1000 nm.Add ionogenic surfactant cetyl trimethylammonium bromide (CTAB), its quality accounts for 6% of GO quality.Stirred at ambient temperature reacts 1 h, afterwards centrifuge washing three times, is placed in dry 24 h of vacuum drying oven of 60 ° of C, obtains the GO of modification.
2., by the GO of above-mentioned modification ultrasonic disperse 30 min in water, the quality of water is 500 times of GO quality; In the aqueous dispersions of GO, add Acrylic Acid Monomer, its quality is 360 times of GO quality; Add linking agent N again, N '-methylene-bisacrylamide, its quality is 15 times of GO quality; Add initiator potassium persulfate again, its quality is 12 times of GO quality; Finally add water, control GO quality accounts for 0.08% of aqueous phase total mass.
3. in above-mentioned aqueous phase, add pore-creating agent hexanaphthene, its quality is 2.5 times of aqueous phase quality.Carry out homogenization treatment to above-mentioned mixed solution, homogeneous rotating speed is 10000 r/min, and the time is 10 min, forms oil-in-water-type High Internal Phase Emulsion.Be transferred in hydrothermal reaction kettle by the High Internal Phase Emulsion obtained, sealing is placed in 65 ° of C convection oven, reacts 24 h.
4. the above-mentioned product be obtained by reacting being placed in Soxhlet extractor, take methyl alcohol as solvent, extracting 48 h at the temperature of 75 ° of C, be placed on dry 24 h in 50 ° of C vacuum drying ovens, obtain the polyalcohol stephanoporate hydrogel with through-hole structure.About 100 μm, aperture, pore interconnection size about 50 μm.
embodiment 2
1. experimental installation and operation are with embodiment 1, and the GO aqueous solution in embodiment 1 is changed into the ethanolic soln of GO, GO lamella mean sizes 1000 nm changes 600 nm into; Ionogenic surfactant cetyl trimethylammonium bromide changes amino modified dose of amino dodecane into, and oleophylic properties-correcting agent quality accounts for 6% of GO quality and changes 80% into, and churning time 1 h changes 12 h into.
2. experimental installation and operation are with embodiment 1, are that 500 times of GO quality change 100 times into by the quality of the water in embodiment 1; Monomeric acrylic changes acrylamide into, and its quality is 75 times of GO quality; Linking agent N, N '-methylene-bisacrylamide changes polyethyleneglycol diacrylate into, and its quality is 4 times of GO quality; Initiator potassium persulfate changes ammonium persulphate into, and its quality is 3 times of GO quality; Control GO quality accounts for 0.08% of aqueous phase total mass and changes 0.4% into.
3. experimental installation and operation are with embodiment 1, and change the pore-creating agent hexanaphthene in embodiment 1 into normal heptane, its quality is 3 times of aqueous phase quality; Homogeneous rotating speed 10000 r/min changes 15000 r/min into, and homogenizing time 10 min changes 20 min into; Temperature of reaction 65 ° of C change 75 ° of C into, and the reaction times 24, h changed 12 h into.
4. experimental installation and operation are with embodiment 1, are changed into by soxhlet type and are placed in ultrasonic 20 min of alcohol solvent, finally obtain the polyalcohol stephanoporate hydrogel with through-hole structure, about 40 μm, its aperture, pore interconnection size about 20 μm.
embodiment 3
1. experimental installation and operation are with embodiment 1, and the GO aqueous solution in embodiment 1 is changed into the DMF solution of GO, GO lamella mean sizes 1000 nm changes 50 nm into; Ionogenic surfactant cetyl trimethylammonium bromide changes isocyanate-modified dose of phenylcarbimide into, and oleophylic properties-correcting agent quality accounts for 6% of GO quality and changes 200% into, and churning time 1 h changes 24 h into.
2. experimental installation and operation are with embodiment 1, are that 500 times of GO quality change 50 times into by the quality of the water in embodiment 1; Monomeric acrylic changes NVP into, and its quality is 25 times of GO quality; Linking agent N, N '-methylene-bisacrylamide changes polyethylene glycol dimethacrylate into, and its quality is 2 times of GO quality; Initiator potassium persulfate changes azo-bis-isobutyrate hydrochloride into, and its quality is 1 times of GO quality; Control GO quality accounts for 0.08% of aqueous phase total mass and changes 1% into.
3. experimental installation and operation are with embodiment 1, and change the pore-creating agent hexanaphthene in embodiment 1 into normal hexane, its quality is 6 times of aqueous phase quality; Change homogeneous into supersound process, ultrasonic power is 1000 W, and the time is 30 min; Temperature of reaction 65 ° of C change 55 ° of C into, and the reaction times 24, h changed 48 h into.
4. experimental installation and operation are with embodiment 1, product acetone is carried out soxhlet type, finally obtains the polyalcohol stephanoporate hydrogel with through-hole structure, about 10 μm, its aperture, pore interconnection size about 2 μm.
embodiment 4
The transparent performance evaluation of polyalcohol stephanoporate hydrogel
Choose the polyalcohol stephanoporate hydrogel of preparation in embodiment 1,2,3, be cut into the square that the length of side is 1 cm; Measure sample is placed in the nitrogen flow rate under 5000 Pa pressure, and in embodiment 1, sample nitrogen flow rate is 370 mL/min, and in embodiment 2, sample nitrogen flow rate is 410 mL/min, and in embodiment 3, sample nitrogen flow rate is 350 mL/min.
Can find out that polyalcohol stephanoporate hydrogel prepared by the present invention has good permeability by the data of gas flow.
embodiment 5
The swelling behavior evaluation of polyalcohol stephanoporate hydrogel
Choose the polyalcohol stephanoporate hydrogel of preparation in embodiment 1,2,3, the sample taking certain mass is immersed in the aqueous solution of pH=7, measure the hydrogel quality after 2 h, calculate the swelling ratio (quality of absorption water accounts for the per-cent of hydrogel dry) of porous aquagel.In embodiment 1, the swelling ratio of sample is 9000%, and in embodiment 2, the swelling ratio of sample is 12000%, and in embodiment 3, the swelling ratio of sample is 13000%.
Can find out that polyalcohol stephanoporate hydrogel prepared by the present invention has good swelling behavior by the data of swelling ratio.
embodiment 6
The absorption property evaluation of polyalcohol stephanoporate hydrogel
Choose embodiment 1 and dyestuff methylene blue carries out absorption property test, sample is cut into the square that quality is 1.0 g, be dipped in 1.0 L methylene blue solutions (concentration 600 mg/L), at room temperature Keep agitation 24 h, measure the dye strength after absorption 24 h, calculate the loading capacity (the dyestuff quality of the hydrogel absorption of unit mass) of porous aquagel to dyestuff.In embodiment 1, sample is 330 mg/g to the loading capacity of dyestuff methylene blue.
Choose embodiment 2 and dyestuff Sunset yellow carries out absorption property test, sample is cut into the square that quality is 1.0 g, be dipped in 1.0 L Sunset yellow solution (concentration 600 mg/L), at room temperature Keep agitation 24 h, measure the dye strength after absorption 24 h, calculate the loading capacity (the dyestuff quality of the hydrogel absorption of unit mass) of porous aquagel to dyestuff.In embodiment 2, sample is 210 mg/g to the loading capacity of dyestuff Sunset yellow.
Can find out that polyalcohol stephanoporate hydrogel prepared by the present invention has good absorption property by the data of loading capacity.
Claims (5)
1. utilize graphene oxide to prepare a method for through hole polyalcohol stephanoporate hydrogel, it is characterized in that concrete steps are as follows:
(1) first, GO is in a solvent dispersed, be mixed with the colloidal sol of massfraction 0.05% ~ 1%, GO is of a size of 50 ~ 2000 nm; In GO colloidal sol, add oleophylic properties-correcting agent, oleophylic properties-correcting agent quality accounts for 0.5% ~ 300% of GO quality, at room temperature stirring reaction 0.5 ~ 24 h, then centrifuge washing, and obtains the GO of modification with vacuum drying oven drying under 40 ~ 65 ° of C;
(2) be dispersed in water by the GO of above-mentioned modification, the quality of water is 50-500 times of GO quality; In the above-mentioned water-sol, add monomer, monomer mass is 20 ~ 600 times of GO quality; Add linking agent again, linking agent quality is 1 ~ 75 times of GO quality; Then add initiator, initiator quality is 1 ~ 20 times of GO quality; Add water afterwards, control GO quality accounts for 0.08% ~ 1% of aqueous phase total mass;
(3) last, in above-mentioned aqueous phase, add pore-creating agent, pore-creating agent quality is 2 ~ 8 times of aqueous phase quality; To this mixture with homogeneous or supersound process, the time is 5 ~ 60 min, forms oil-in-water-type High Internal Phase Emulsion; Emulsion is transferred in airtight hydrothermal reaction kettle, at the temperature of 55 ~ 80 ° of C, reacts 12 ~ 48 h; After reaction terminates, remove the pore-creating agent in product and unreacted monomer, use vacuum drying oven dry 24 ~ 48 h at the temperature of 40 ~ 65 ° of C, obtain the polyalcohol stephanoporate hydrogel with through-hole structure;
Wherein, pore-creating agent is the one in the alkane of carbonatoms 6 ~ 20, naphthenic hydrocarbon, or wherein several;
GO is graphene oxide.
2. preparation method according to claim 1, is characterized in that, described oleophylic properties-correcting agent comprises ionogenic surfactant, one in amino modified dose, isocyanate-modified dose, or wherein several; Ionogenic surfactant is the one in the amine salt of carbonatoms 8 ~ 16, quaternary ammonium salt, or wherein several; Amino modified dose is the one in the aliphatic amide of carbonatoms 6 ~ 18, aromatic amine, aliphatic diamine, aromatic diamines, aminosilane, or wherein several; Isocyanate-modified dose is the one in the aliphatics of carbonatoms 6 ~ 18, aromatic isocyanate, or wherein several.
3. preparation method according to claim 1 and 2, it is characterized in that, containing a carbon-carbon double bond and be water-soluble monomer in the molecular structure of described monomer, comprise the one in acrylic acid or the like, propene sulfonic acid class, acrylic amide, NVP class, or wherein several; Containing two carbon-carbon double bonds in the molecular structure of linking agent, comprise the one in bisacrylamide class or double methacrylate class; Initiator is the one in Potassium Persulphate, ammonium persulphate, azo-bis-isobutyrate hydrochloride, azo two isobutyl imidazoline hydrochloride or azo dicyano valerate.
4. preparation method according to claim 3, is characterized in that, described in step (1), GO is of a size of 50 ~ 2000 nm.
5. preparation method according to claim 4, is characterized in that the polyalcohol stephanoporate hydrogel prepared has through-hole structure, and the aperture of porous aquagel is 5 ~ 200 μm, and pore interconnection is of a size of 2 ~ 70 μm, porosity 75% ~ 90%.
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Application publication date: 20150715 |