CN103601899B - A kind of method preparing graphene oxide enhancing magnetic hydrogel - Google Patents
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- CN103601899B CN103601899B CN201310610991.0A CN201310610991A CN103601899B CN 103601899 B CN103601899 B CN 103601899B CN 201310610991 A CN201310610991 A CN 201310610991A CN 103601899 B CN103601899 B CN 103601899B
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Abstract
The present invention relates to polymeric material field, provide a kind of method preparing graphene oxide enhancing magnetic hydrogel, described graphene oxide strengthens magnetic hydrogel composition and comprises: graphene oxide, Z 250 and polyvinyl alcohol, comprise the following steps: according to the ratio of 1 gram of polyvinyl alcohol than 5 milliliters of ultrapure waters, polyvinyl alcohol and ultrapure water are put into container and slowly stir and heat 10 minutes; Under polyvinyl alcohol under molten state being transferred to the environment of-20 DEG C freezing 21 hours; Polyvinyl alcohol after freezing is thawed 3 hours; After repetition abovementioned steps twice, graphene oxide and Z 250 are added in the polyvinyl alcohol after three times thaw.The graphene oxide that utilizes the present invention to prepare strengthens magnetic hydrogel, and by adding the mechanical property of the favourable enhancing magnetic hydrogel of graphene oxide, favourable to overcome the shock strength that hydrogel material exists low, the shortcoming such as easy fracture under stress.
Description
Technical field
The present invention relates to polymeric material field, provide a kind of method preparing graphene oxide enhancing magnetic hydrogel.
Background technology
Hydrogel is made up of the polymer of three-dimensional net structure and the water molecules medium filled in polymer network chain gap.Hydrogel material is high, soft with its water content, have toughness as rubber and good biocompatibility is widely used in the aspects such as medicine, medical treatment, artificial organs, physiology, environmental protection, due to the application prospect that it is huge, be subject to the favor of people more and more.One scene of flourishing life is presented to the investigation and application exploitation of hydrogel all over the world.In recent years, along with the development of hydrogel, inorganic nano material is added in hydrogel by people, not only can improve the physical strength of hydrogel, can also give gel special new capability simultaneously, as: electroresponse performance, uv absorption property, magnetic susceptibility performance etc. (see " chemical progress ", 2009,21,1008-1014).
Magnetic sensitivity hydrogel (ferrogel or magnetic-field-sensitivehydrogel) refers to class enviromental sensitive hydrogel magnetic field to response characteristic.Generally be made up of polymeric matrix and function ingredients.The function ingredients giving hydrogel magnetic responsiveness characteristic mostly is inorganic particle, and modal have Fe
3o
4, γ-Fe
2o
3deng metal oxide and CoFe
2o
4etc. ferrite material.Wherein, Fe
3o
4owing to having the advantages such as cheap and easy to get, nontoxic, it is magnetic component the most frequently used at present.
Form the kind of polymkeric substance of hydrogel, the kind of magnetic particle, size and the content etc. in system thereof have very large impact to the character of composite aquogel.If magnetic component has superparamagnetism, plural gel also can show superparamagnetism, namely under the action of a magnetic field, has stronger magnetic, and after removing magnetic field, its magnetic disappears very soon, can not be permanently magnetized; If the magnetic particle in gel does not have superparamagnetism, plural gel then has the characteristic of permanent magnet.Because magnetic sensitivity hydrogel can produce response to externally-applied magnetic field; and there is unique snappiness and perviousness; drug controlled release, artificial-muscle, protein separation and enzyme fixing etc. in have broad application prospects; thus in recent years to its research-and-development activity Showed Very Brisk, a current study hotspot is become.But current existing hydrogel material to there is shock strength low, the shortcoming such as easy fracture under stress, so the mechanical property improving molecular gel is particularly important.
The two-dirnentional structure that Graphene is intensive by one deck, the carbon atom arrangement be wrapped in honeycomb crystal lattice becomes, similar with the monoatomic layer of graphite, have another name called " mono-layer graphite sheet ".On microcosmic, difference is single-layer graphene film is not two-dimentional flat structure, but has the single layer structure of " on nanoscale " stable wavy, is the Two Dimensional Free state atomic crystal of the unique existence found at present.Macroscopically, can think that Graphene can be warped into the soccerballene of zero dimension, be rolled into the carbon nanotube of one dimension or be stacked to three-dimensional graphite, be the elementary cell forming sp2 hydridization carbon material.
Graphene is the material that mankind's known strength is the highest, and because Graphene is made up of monoatomic layer, its specific surface area is extremely large, and calculated value is up to 2600m
2/ g.Researchist uses the metal of atomic size and diamond probe to puncture to Graphene, tests its intensity, allows scientist shock, and the intensity of Graphene is up to 130GPa, also higher 100 times than iron and steel best in the world, also higher 20 times than high-strength carbon fibre.The researchist of Columbia University finds, Graphene sample particulate start cracked before, the peak pressure that their every 100nm distances can be born reaches about 2.9 μ N unexpectedly.According to scientists measuring and calculating, the Graphene fracture that the pressure that this result is equivalent to apply 55N just can make 1m long.Graphene just to be proposed for the first time as far back as 2004 due to its outstanding mechanics, quantum and electrical property and is studied widely in the field such as Materials science, physical chemistry.
Graphene oxide is a kind of Graphene of improved form, its synthetic method craft is ripe, be easy to obtain a large amount of cheap graphene oxide, graphene oxide is light and have higher mechanical property and thermostability, and therefore graphene oxide is a kind of high efficiency packing that can strengthen electricity, mechanics, thermal property.
Summary of the invention
The object of patent of the present invention is to utilize freezing-scorification to prepare graphene oxide (GO), Z 250 (Fe
3o
4), polyvinyl alcohol (PVA) composite aquogel, to solve the low problem of the mechanical strength of polyvinyl alcohol hydrogel in application process, to improving its mechanical property.
For this reason, the invention discloses a kind of method preparing graphene oxide enhancing magnetic hydrogel, described graphene oxide strengthens magnetic hydrogel composition and comprises: graphene oxide, Z 250 and polyvinyl alcohol, said method comprising the steps of:
Step 1, according to the ratio of 1 gram of polyvinyl alcohol than 5 milliliters of ultrapure waters, puts into container and slowly stirs and heat 10 minutes by polyvinyl alcohol and ultrapure water;
Step 2, under polyvinyl alcohol under molten state being transferred to the environment of-20 DEG C freezing 21 hours;
Step 3, thaws the polyvinyl alcohol after freezing 3 hours;
Step 4, after repeating step 1-3 twice, enters step 5;
Step 5, adds to graphene oxide and Z 250 in the polyvinyl alcohol after three times thaw.
The making method of graphene oxide is very ripe, and the present invention has also done improvement to the preparation method of graphene oxide, and described graphene oxide adopts the Hummers legal system improved standby:
Step a1, Graphite Powder 99 being joined volume ratio is in the vitriol oil of 9:1 and the mixing solutions of strong phosphoric acid;
Step a2, stirs and adds potassium permanganate, and the weight ratio of described Graphite Powder 99 and described potassium permanganate is 1:3;
Step a3, reacts 2 hours under temperature is no more than 200 DEG C of conditions;
Step a4, reacts 30 minutes under being transferred to 350 DEG C of conditions;
Step a5, adds deionized water, reaction 40 minutes under more than 980 DEG C of conditions, and in described step a5, in deionized water and described step a1, the volume ratio of mixing solutions is 2:1;
Step a6, when mixture in step a5 is glassy yellow by brown stain, add hydrogen peroxide solution and deionized water and filter, in described step a6, in deionized water and described step a1, the volume ratio of mixing solutions is 6:1, in described hydrogen peroxide solution and step a6, the volume ratio of deionized water is 1:7, and in described hydrogen peroxide solution, the weight percent of hydrogen peroxide is 30%;
Step a7, with the salt acid elution containing 1 mole of often liter of hydrogenchloride;
Step a8, vacuum-drying.
In the process preparing graphene oxide, the graphite oxide adopting the Hummers method improved to obtain is introduced a large amount of hydrophilic functional group, there is good wettability and surfactivity, thus can disperse in diluted alkaline water and pure water and form stable colloidal suspensions, strengthen the consistency of itself and PVA.
In order to Simplified flowsheet, save test space, described Z 250 of the present invention can adopt coprecipitation method to prepare:
Step b1, by FeCl
24H
20 and FeCl
36H
20 is that 1:2 carries out proportioning with mol ratio, by material dissolution after proportioning in distilled water, adds PEG solution, and after mixing, solution to be contained in sealed vessel and logical nitrogen protection;
Step b2, gets ammonia container and deposits ammoniacal liquor containing 1.5mol/L ammonium hydroxide, and with nitrogen to ammonia Aeration in the water;
Step b3, under the condition of 300 DEG C, stir the ammoniacal liquor after inflation in step b2, and be slowly added dropwise in the mixing solutions of step b1 by the ammoniacal liquor in step b2, the pH value to mixing solutions reaches 11;
Step b4, when in sealed vessel, the color of solution becomes black by light brown, rapid stirring;
Step b5, under the condition of 600 DEG C, thermostatic crystallization 1 little in sealed vessel solution internal-response complete;
Step b6, separates ferroferric oxide magnetic powder in sealed vessel with magnet;
Step b7, isolated ferroferric oxide magnetic powder is cleaned repeatedly to pH value be 7;
Step b8, adds the hydrochloric acid soln of 0.5 mole often liter, obtains Z 250 transparent colloidal solution after surface treatment;
Step b9, gets part Z 250 transparent colloidal solution and carries out vacuum-drying.
Prepare Z 250 part, adopt coprecipitation process step simply greatly to save experimental period.In thermostatic crystallization process, temperature remained constant and then increase monodispersity ensure even particle size distribution.This kind of method is compared with other prepare Z 250, more easy.In order to the consistency strengthening Z 250 and polyvinyl alcohol is by regulating the consumption of Surfactant PEG, make not only PEG can be coated on Z 250 surface but also be unlikely to too thickness.
The present invention is freezing-and scorification prepared graphene oxide/Z 250 (Fe
3o
4)/polyvinyl alcohol (PVA) composite aquogel, pours into after melts color is homogeneous in mould, avoids and Elongation test result swelling on the later stage to have impact.Therefore the graphite oxide utilizing the present invention to prepare/Z 250 (Fe
3o
4)/polyvinyl alcohol (PVA) composite aquogel, by adding the mechanical property of graphene oxide favourable enhancing magnetic hydrogel, favourable to overcome the shock strength that hydrogel material exists low, the shortcoming such as easy fracture under stress.
Accompanying drawing explanation
The XRD figure of Fig. 1 graphene oxide, graphite oxide and natural graphite powder is composed;
Fig. 2 graphite, graphite oxide, graphene oxide FT-IR comparison diagram;
Fig. 3 graphene oxide TEM schemes;
Fig. 4 graphite, graphite oxide, graphene oxide Raman comparison diagram;
The XRD spectra of Fig. 5 Z 250 particle;
Fig. 6 different content Z 250/graphite oxide is rare/polyvinyl alcohol hydrogel magnetic field threshold value;
Fig. 7 is at Z 250 30% situation Tensile strength and graphene oxide relation with contents figure.
Embodiment
Prepare graphene oxide, Z 250, polyvinyl alcohol composite hydrogel, experimental section is mainly divided into prepares graphene oxide, Z 250, graphene oxide/Z 250/polyvinyl alcohol composite hydrogel three parts, and by XRD(Fig. 1, Fig. 5), FT-IR(Fig. 2), TEM(Fig. 3), Raman(Fig. 4), analyze pattern and the composition of determining prepared material.
Preferably, for the technical scheme solving the problems of the technologies described above patent of the present invention is as follows: adopt the Hummers legal system improved for graphene oxide, be oxidized it with the vitriol oil and strong phosphoric acid nitration mixture; Adopt coprecipitation method to prepare Z 250, then take 40ml ultrapure water, 8gPVA mixing is put into 400ml beaker and is heated in the water-bath of boiling; Heat peripheral PVA and water dissolution after 3 minutes, now cause middle white PVA part with glass stick stirring and mix with water; Continue heating, period slowly stirs; The PVA taken out after 10 minutes under molten state pours in test tube and the refrigerator and cooled transferring to-20 DEG C freezes 21 hours, takes out and thaws 3 hours, be now a freezing melting cycle so repeatedly three all after dates take out; In addition, previously prepared good Z 250 and graphene oxide are added in PVA, prepare the Z 250/graphene oxide/PVA composite aquogel of different content.
1g Graphite Powder 99 is joined in the mixing solutions ice-water bath of the 20.7ml vitriol oil and 2.3ml strong phosphoric acid (9:1), under strong stirring, slowly add the KMnO of 3g
4, react 2 hours under temperature is no more than 200 DEG C of conditions, shift afterwards and react 30min under 350 DEG C of conditions, add 46ml deionized water, under more than 980 DEG C of conditions, react 40min.Mixture is glassy yellow by brown stain, adds 140ml deionized water while hot and 10ml contains 30% weight percent H
2o
2hydrogen peroxide filtered while hot.With the sulfate radical that the salt acid elution of 1mol/L is removed in solution for 1 to 2 times.Washes clean final vacuum is dry.The graphite oxide sealing prepared is preserved.
Carried out powder x-ray diffraction analysis respectively to natural graphite powder, graphite oxide, its analytical results as shown in Figure 1.Graphite curve has the diffraction peak of a higher-strength at ° place, 2 θ=26.5, illustrate natural graphite existence and utilize bragg's formula to calculate be about 0.34nm in the crystal face interlamellar spacing at (002) place.Graphite oxide curve obtains after Strong oxdiative, and the diffraction peak of its (002) interlamellar spacing moves to left to about 9.80, and intensity reduces.This is due to after adding strong oxidizer, the multiple bonding action of oxygen and carbon atom, make graphite flake between layers, and the position such as layer edge introduces C=O, functional group and the other defects such as C-OH ,-COOH, finally make the distance of layer and interlayer increase, the diffraction peak of graphene oxide offsets to low angle.
Fig. 2 is graphite, graphite oxide, graphene oxide FT-IR spectrogram.Be the covalent linkage of sp2 hydridization between carbon atom in graphite-structure layer, interlayer is molecular linkage. as can be seen from the figure, graphite is substantially without infrared absorption peak, and theoretical analysis graphite is without infrared active.At 3458cm-1 place, the stretching vibration peak of water can be thought.Graphite oxide, graphene oxide, in 1720cm-1 place visible absorbance spectrum, demonstrates after peroxidation, introduces carboxyl functional group.
Utilize tem analysis obtain the pattern (Fig. 3) of Graphene sample.Graphene oxide each several part shade differs, and light transmission is not quite similar, and middle portion color comparatively peripheral part is dark, and this illustrates that graphene oxide lamella has the overlap of part, can also see the fold of graphene oxide clearly simultaneously.Thus, we can conclude and have successfully prepared graphene oxide.
1323cm-1 and 1329cm-1 place is the D peak of graphite oxide and graphene oxide as can be seen from Figure 4, is produced by the pattern of sp2 atom breathing vibration in carbocyclic ring.It is all cause .D peak relevant with impurity defect with the size of the crystal grain of graphite by sp2 chemical bond oscillations that the G peak of left and right, 1570cm-1 place produces .G peak with D peak by carbocyclic ring with the stretching motion of all sp2 atom pairss in long-chain.Pure graphite monocrystalline is complete ordering, and Raman spectrum only has a sharp-pointed G peak. when crystalline size reduces, long-range periodic is destroyed, and the degree of disorder increases, and there will be D peak.The appearance at D peak, after proving that graphite is oxidized, defect adds.
Fig. 5 is the diffractogram of Z 250 particle.Diffraction peak in figure appears at 2 θ=30 °, 35 °, 42 °, 58 °, 62.5 ° of places, (220) of the corresponding Emission in Cubic Fe3O4 of difference, (331), (400), (551), (440) crystal face.Consistent with its standard spectrogram, can assert that the nanoparticle of synthesis is Fe
3o
4.
By a certain amount of Fe
3o
4nanoparticle dispersion in aqueous after, with attraction observation, find Fe
3o
4be gathered in magnet side, can be attracted, now, solution becomes clarification.
By FeC1
24H2O and FeCl
36H
2o is that mol (A): mol (B)=1:2 carries out proportioning with mol ratio; above-mentioned raw materials is dissolved in the distilled water of 50mL, then solution is transferred to there-necked flask, add in the 150mlPEG aqueous solution; with plastics stopper good seal there-necked flask, logical nitrogen protection simultaneously; Get another beaker to measure certain ammoniacal liquor and mix with water and be made into 1.5mol/L, in solution, inflate for some time with nitrogen in advance.300.At C temperature, while solution stirring in beaker, in there-necked flask, slowly drip the NH of 1.5mol/L
3/ H
2o solution is about 11 to pH value, and in flask, the color of solution becomes black by light brown, rapid stirring, 600.At C temperature, thermostatic crystallization lh is complete to solution internal-response.After reaction terminates, make Fe with magnet
3o
4magnetic powder is separated, and repeatedly cleaning 3-5 all over being 7 to solution pH value, adding the hydrochloric acid soln of a small amount of 0.5mmol/L, after this surface treatment, obtaining Fe
3o
4transparent colloidal solution is got a part and is put into vacuum-drying indoor seasoning 48h, obtains dry nano particle.
After adding different content Z 250 more as seen from Figure 6, content more critical magnetic fields threshold value of Z 250 is less.With Fe
3o
4the increase of content, magnetic hydrogel threshold value progressively reduces, and what the magneticstrength threshold value of magnetic hydrogel reflected is to make magnetic hydrogel that the minimum applied field strengths of moment needed for huge skew occurs.After minimum externally-applied magnetic field this explanation less occurred needed for huge skew itself is magnetized, magnetic is stronger.Along with the amount of Z 250 increases, the magnetic of PVA/ graphene oxide hydrogel is stronger.
Fig. 7 is that each group of PVA/GO composite aquogel Elongation test curve of the Z 250 of 30 weight percents is respectively for graphene oxide content is after treatment to the interact relation figure of composite aquogel tensile property.By in figure, we can see that the stretch-proof performance of Graphene content increase hydrogel has had obvious enhancing along with in composite aquogel.This experiment gained will improve the tensile strength of composite aquogel 6.33% at hydrogel and quality than the graphene oxide GO often increasing by 0.125 weight percent when being 1:10.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (2)
1. prepare the method that graphene oxide strengthens magnetic hydrogel, described graphene oxide strengthens magnetic hydrogel composition and comprises: graphene oxide, Z 250 and polyvinyl alcohol, is characterized in that said method comprising the steps of:
Step 1, according to the ratio of 1 gram of polyvinyl alcohol than 5 milliliters of ultrapure waters, puts into container and slowly stirs and heat 10 minutes by polyvinyl alcohol and ultrapure water;
Step 2, under polyvinyl alcohol under molten state being transferred to the environment of-20 DEG C freezing 21 hours;
Step 3, thaws the polyvinyl alcohol after freezing 3 hours;
Step 4, after repeating step 1-3 twice, enters step 5;
Step 5, adds in the polyvinyl alcohol after three times thaw by graphene oxide and Z 250;
Described graphene oxide adopts the Hummers legal system improved standby:
Step a1, Graphite Powder 99 being joined volume ratio is in the vitriol oil of 9:1 and the mixing solutions of strong phosphoric acid;
Step a2, stirs and adds potassium permanganate, and the weight ratio of described Graphite Powder 99 and described potassium permanganate is 1:3;
Step a3, reacts 2 hours under temperature is no more than 200 DEG C of conditions;
Step a4, reacts 30 minutes under being transferred to 350 DEG C of conditions;
Step a5, adds deionized water, reaction 40 minutes under more than 980 DEG C of conditions, and in described step a5, in deionized water and described step a1, the volume ratio of mixing solutions is 2:1;
Step a6, when mixture in step a5 is glassy yellow by brown stain, add hydrogen peroxide solution and deionized water and filter, in described step a6, in deionized water and described step a1, the volume ratio of mixing solutions is 6:1, in described hydrogen peroxide solution and step a6, the volume ratio of deionized water is 1:7, and in described hydrogen peroxide solution, the weight percent of hydrogen peroxide is 30%;
Step a7, with the salt acid elution containing 1 mole of often liter of hydrogenchloride;
Step a8, vacuum-drying.
2. the method for claim 1, is characterized in that, described Z 250 adopts coprecipitation method preparation:
Step b1, by FeCl
24H
20 and FeCl
36H
20 is that 1:2 carries out proportioning with mol ratio, by material dissolution after proportioning in distilled water, adds PEG solution, and after mixing, solution to be contained in sealed vessel and logical nitrogen protection;
Step b2, gets ammonia container and deposits ammoniacal liquor containing 1.5mol/L ammonium hydroxide, and with nitrogen to ammonia Aeration in the water;
Step b3, under the condition of 300 DEG C, stir the ammoniacal liquor after inflation in step b2, and be slowly added dropwise in the mixing solutions of step b1 by the ammoniacal liquor in step b2, the pH value to mixing solutions reaches 11;
Step b4, when in sealed vessel, the color of solution becomes black by light brown, rapid stirring;
Step b5, under the condition of 600 DEG C, thermostatic crystallization 1 little in sealed vessel solution internal-response complete;
Step b6, separates ferroferric oxide magnetic powder in sealed vessel with magnet;
Step b7, isolated ferroferric oxide magnetic powder is cleaned repeatedly to pH value be 7;
Step b8, adds the hydrochloric acid soln of 0.5 mole often liter, obtains Z 250 transparent colloidal solution after surface treatment;
Step b9, gets part Z 250 transparent colloidal solution and carries out vacuum-drying.
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| CN104226281B (en) * | 2014-10-13 | 2016-06-15 | 江南大学 | A kind of composite aquogel of Adsorption of Heavy Metal Ions and preparation method thereof |
| CN104744713B (en) * | 2015-03-06 | 2018-03-23 | 陕西正丰航天科技有限公司 | Polyvinyl alcohol graphite oxide Fe3O4The preparation method of laminated film |
| CN107964396A (en) * | 2017-11-30 | 2018-04-27 | 陕西理工大学 | A kind of graphene photothermal conversion materiat preparation method |
| CN108439478B (en) * | 2018-04-16 | 2020-05-19 | 中国科学院生态环境研究中心 | Three-dimensional nano iron oxide, gel in-situ preparation method and application thereof |
| CN108530653A (en) * | 2018-04-18 | 2018-09-14 | 福州大学 | A kind of preparation method of polyvinyl alcohol magnetic hydrogel |
| CN109880122A (en) * | 2019-01-15 | 2019-06-14 | 温州医科大学附属第二医院、温州医科大学附属育英儿童医院 | A kind of supersonically preparation method of magnetic response graphene oxide hydrogel |
| CN109837080B (en) * | 2019-04-12 | 2019-08-02 | 中国石油大学(华东) | A kind of viscosity reduction system and preparation method thereof for microwave heavy crude producing |
| CN111359591A (en) * | 2020-03-26 | 2020-07-03 | 山东建筑大学 | Superparamagnetic graphene oxide/sodium alginate composite gel material and preparation method thereof |
| CN114197201B (en) * | 2022-01-11 | 2023-03-21 | 四川大学 | Magnetic graphene oxide modified carbon fiber and preparation method and application thereof |
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| US4988761A (en) * | 1988-09-22 | 1991-01-29 | Dow Corning K.K. | Process for producing a low water content PVA hydrogel |
| CN101941842A (en) * | 2010-10-11 | 2011-01-12 | 东华大学 | Method for preparing graphene loaded ferroferric oxide magnetic nanometer particle composite material |
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| US4988761A (en) * | 1988-09-22 | 1991-01-29 | Dow Corning K.K. | Process for producing a low water content PVA hydrogel |
| CN101941842A (en) * | 2010-10-11 | 2011-01-12 | 东华大学 | Method for preparing graphene loaded ferroferric oxide magnetic nanometer particle composite material |
| CN101993056A (en) * | 2010-12-01 | 2011-03-30 | 天津大学 | Graphene-based porous macroscopic carbon material and preparation method thereof |
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