CN104479174A - Cellulose-based magnetic aerogel material and preparation method thereof - Google Patents
Cellulose-based magnetic aerogel material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a cellulose-based magnetic aerogel material and a preparation method thereof. The method comprises the following steps: carrying out chemical modification, thereby obtaining high-activity amphoteric cellulose; firmly combining the amphoteric cellulose and a graphene oxide through electrostatic interaction and hydrogen bonding forces and the like to build a framework of the aerogel material. Disperse loading of a magnetic nano ferroferric oxide can be achieved by virtue of the advantages of high surface activity and super-large specific surface area; the structure uniformity and the stability of the magnetic aerogel of the amphoteric cellulose are ensured through the steps of cross-linking, freeze-drying and the like; the characteristics of high specific surface properties, good affinity, biodegradability and the like of the cellulose are kept by the magnetic aerogel; and the magnetic aerogel obtains high surface activity and superparamagnetic property, has the advantages of low cost, high strength, amphoteric characteristic, biocompatibility and the like, has the characteristics of high specific surface area, high loading capacity, high surface activity, intelligent positioning and the like, and has significant adsorption capacity on pollutants such as heavy metal ions and organic molecules.
Description
Technical field
The present invention relates to a kind of magnetic aerogel material and preparation method thereof, be specifically related to a kind of magnetic aerogel material based on amphoteric cellulose and preparation method, belong to advanced function field of compound material.
Background technology
Magnetic porous material can be used for common sewage disposal, target medicine carrier, target function support, target block up the fields such as vascular grafts, target medical adsorption material, microwave absorption (as: radar absorbing material), and Research Significance is large, is subject to extensive concern.The feature that above Application Areas all requires respective material to possess, and density is low, specific surface area large, high adsorption capacity, stowage capacity are strong, good magnetic property be then meet that material easily reclaims, target ability is strong, realize the necessary requirement of microwave absorption, current material is often difficult to meet many-sided performance requirement simultaneously.The porous magnetic material of light weight, except possessing microwave sorbing material to except the high request of absorbing property in high-temperature stability and high band range, it is in fields such as sewage disposal and target medical materials, is also convenient to reclaim and easily realizes target control.Therefore, in order to meet multi-field application demand, to low density, bigger serface, high strength and the development significance of fire resistant magnetic material is great.
Aerogel is the novel porous material of a class, has the character of the multiple uniquenesses such as specific density is low, specific refractory power is low, porosity is high, surface-area is large, adsorptivity is strong, is widely used in multiple research field.In order to realize the low density feature of magneticsubstance, a large amount of investigator is just putting forth effort exploitation magnetic aerogel material, the pure carbon material of the many employings of prior art (as Graphene, carbon nanotube etc.) as the base material of porous material, to meet the multifunctional application demand of material.But raw-material non-renewable, the practical application that high cost, low strength etc. can limit magneticsubstance of carbon back, improves from raw material, developing low-cost, high strength magnetic aerogel material, significant.
Mierocrystalline cellulose is the abundantest renewable resourcess of occurring in nature reserves, and global annual output reaches hundreds billion of ton, is the incomparable renewable great resource such as oil.As a kind of natural macromolecular material possessing biodegradability, Mierocrystalline cellulose is degraded, modification, deep processing, give the focus that its New function and application potential are various countries' research always.Graphene oxide is a kind of monolayer carbon atom two-dimension nano materials that natural graphite obtains after chemical oxidation and stripping, its flakiness ratio is up to 1000, specific surface area is large, physical strength is high, surface and edge stochastic distribution a large amount of oxy radical (in the middle of lamella :-OH, C-O-C, edge :-C=O,-COOH), have amphipathic, present hydrophilic to hydrophobic property distribution from chip edge to central authorities, demonstrate good wettability and surfactivity, and in water, show superior dispersiveness, become after Graphene more to show excellent electroconductibility through chemical reduction, many merits possesses unique advantage when making it prepare for matrix material.
Summary of the invention
Problem to be solved by this invention be overcome existing magnetic aerogel material exist base material non-degradable and high in cost of production is not enough, with degradable Mierocrystalline cellulose for base material, provide a kind of novel magnetic aerogel material and preparation method thereof.
Technical scheme of the present invention is achieved in that a kind of preparation method based on cellulosic magnetic aerogel material, comprises the steps:
1, compound concentration is the aqueous solution of the graphene oxide of 0.01wt% ~ 10wt%; be 1:10 ~ 10:1 by the mass ratio of graphene oxide and amphoteric cellulose; at rotating speed be under the agitation condition of 200r/min ~ 600 r/min by amphoteric cellulose powder dispersion in graphene oxide water solution, obtain the binary complex liquid of amphoteric cellulose/graphene oxide;
2, by Z 250 ultrasonic disperse in ethanol, compound concentration is 0. 1wt% ~ 10wt% Z 250 ethanolic soln, be 1:10 ~ 1:200 by the mass ratio of Z 250 and amphoteric cellulose, Z 250 ethanolic soln is slowly joined in binary composite solution prepared by step 1, stir, obtain the tri compound liquid of amphoteric cellulose/graphene oxide/Z 250;
3, compound concentration is the cross-linking agent aqueous solution of 0.1wt% ~ 2wt%, be 1:50 ~ 1:400 by the mass ratio of linking agent and amphoteric cellulose, under agitation cross-linking agent aqueous solution is added drop-wise in tri compound liquid prepared by step 2, after continuing stirring 1 ~ 60min, obtain the ternary complex of the graphene oxide/Z 250 of thickness, again through lyophilize, obtaining density is 0.1mg/cm
3~ 40mg/cm
3amphoteric cellulose magnetic aerogel material.
In technical solution of the present invention, described amphoteric cellulose powder is both sexes Microcrystalline Cellulose, and median size is 20 ~ 80 μm.
The preparation of both sexes Microcrystalline Cellulose, can take cellulosic fibre as raw material, obtain, comprise step as follows after amphoteric modification process:
1, cellulosic fibre being joined concentration is in the sodium hydroxide solution of 17wt% ~ 18wt%, normal temperature leaves standstill process 40 ~ 50min, through deionized water clean, dry after, being placed in concentration is that the sodium hydroxide solution of 0.1wt% ~ 5wt% boils process 20 ~ 60min, clean through deionized water again, dry, obtain alkali cellulose;
2, joining in ethanol or acetone by alkali cellulose by bath raio 1:10 ~ 1:80, drip sodium hydroxide solution and the 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride of 10wt% ~ 30wt% under agitation condition successively, is react 2 ~ ~ 5h under the condition of 30 ~ 50 DEG C in temperature; The mass volume ratio of alkali cellulose and sodium hydroxide solution is 1:0.5 ~ 1:3, mass ratio 1:1 ~ the 1:3 of alkali cellulose and 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, after reaction terminates, regulate product pH value to neutral with dilute hydrochloric acid, suction filtration is also successively through methyl alcohol, absolute ethanol washing, vacuum-drying, to constant weight, obtains quaternized cellulose;
3, quaternized cellulose is joined in deionized water by bath raio 1:30 ~ 1:100, in protection of inert gas, temperature is stir 10 ~ 30min under the condition of 30 ± 5 DEG C, slowly add ceric ammonium nitrate again, the mass ratio of quaternized cellulose and ceric ammonium nitrate is 1:0.2 ~ 1:3, after stirring reaction 10 ~ 60min, add sulfonated monomers 2-acrylamide-2-methyl propane sulfonic, the mass ratio of quaternized cellulose and 2-acrylamide-2-methyl propane sulfonic is 1:1 ~ 1:5, after stirring reaction 30 ~ 180min, be warming up to 50 ~ 70 DEG C, continue reaction 2 ~ 5h, take out product, naturally cooling, successively through deionized water, acetone, ether filtering and washing, airing 30 ~ 120min under normal temperature, vacuum-drying is to constant weight, obtain amphoteric cellulose, amphoteric cellulose is placed in the dilute acid soln that volumetric concentration is 1% ~ 10%, 20 ~ 30 DEG C of constant temperature soak 1 ~ 6h, obtain both sexes Microcrystalline Cellulose after hydrolysis.
The preparation of both sexes Microcrystalline Cellulose, can take also Microcrystalline Cellulose as raw material, obtain, comprise step as follows after amphoteric modification process:
1, Microcrystalline Cellulose being joined concentration is boil process 20 ~ 60min in the sodium hydroxide solution of 0.1wt% ~ 5wt%, then, oven dry clean through deionized water, obtains alkaline Microcrystalline Cellulose;
2, joining in ethanol or acetone by alkaline Microcrystalline Cellulose by bath raio 1:10 ~ 1:80, drip sodium hydroxide solution and the 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride of 10wt% ~ 30wt% under stirring successively, is react 2 ~ ~ 5h under the condition of 30 ~ 50 DEG C in temperature; The mass volume ratio of alkalescence Microcrystalline Cellulose and sodium hydroxide solution is 1:0.5 ~ 1:3, mass ratio 1:1 ~ the 1:3 of alkalescence Microcrystalline Cellulose and 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, after reaction terminates, regulate product pH value to neutral with dilute hydrochloric acid, suction filtration is also successively through methyl alcohol, absolute ethanol washing, vacuum-drying, to constant weight, obtains quaternized Microcrystalline Cellulose;
3, quaternized Microcrystalline Cellulose is joined in deionized water by bath raio 1:30 ~ 1:100, in protection of inert gas, temperature is stir 10 ~ 30min under the condition of 30 ± 5 DEG C, slowly add ceric ammonium nitrate again, the mass ratio of quaternized Microcrystalline Cellulose and ceric ammonium nitrate is 1:0.2 ~ 1:3, after stirring reaction 10 ~ 60min, sulfonated monomers 2-acrylamide-2-methyl propane sulfonic is added in reaction system, the mass ratio of quaternized Microcrystalline Cellulose and 2-acrylamide-2-methyl propane sulfonic is 1:1 ~ 1:5, after stirring reaction 30 ~ 180min, be warming up to 50 ~ 70 DEG C, continue reaction 2 ~ 5h, take out product, naturally cooling, successively through deionized water, acetone, ether filtering and washing, airing 30 ~ 120min under normal temperature, vacuum-drying is to constant weight, obtain both sexes Microcrystalline Cellulose.
Linking agent of the present invention is the one in mixture containing calcium ion, calcium chloride, divinylsulfone, multiamino compound, genipin, or their arbitrary combination; The described mixture containing calcium ion is the mixture of calcium carbonate and diluted acid, and described diluted acid is the one in dilute hydrochloric acid, dust technology, acetic acid, or multiple; Described multiamino compound is chitosan, silk-protein, quadrol, hydroxyethylethylene diamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines, polymine, N, one in N-methylene-bisacrylamide, Hyperbranched Polymer with Terminal Amido, or their arbitrary combination.
Z 250 of the present invention is dispersed nano Z 250 or polydispersion nano ferriferrous oxide.Described Z 250 is the one in the nanoparticle of Z 250, nanometer rod, nano wire, or multiple.
Technical solution of the present invention also comprises the one that obtains by above-mentioned preparation method based on cellulosic magnetic aerogel material.
Compared with prior art, advantage of the present invention is:
1, the present invention is by chemical modification, obtains and possesses highly active amphoteric cellulose, as carrier, and preparation magnetic aerogel material.Both maintain the features such as cellulosic high-ratio surface characteristic, good affinity, biodegradability, impart again its high surface and superparamagnetic characteristic.
2, with the amphoteric cellulose of high surface for skeleton, amphipathic graphene oxide, as excipient and tackiness agent, easily realizes mortise and builds the framework of aerogel material between the two; The spread loads to nano ferriferrous oxide can be realized by the two surfactivity and extra specific surface area advantage, and by steps such as crosslinked, lyophilizes, structural uniformity and the stability of product amphoteric cellulose magnetic aerogel can be guaranteed.
3, relative to common carbon back magnetic aerogel material, amphoteric cellulose magnetic aerogel of the present invention possesses low density, bigger serface, the strong characteristic such as adsorptive power, superparamagnetic equally, and because be carrier with amphoteric cellulose, this product has also possessed the advantages such as low cost, high strength, amphoteric character, biocompatibility, biodegradable, good affinity, can be used for common sewage disposal, target medicine carrier, target function support, target block up the fields such as vascular grafts, target medical adsorption material, microwave sorbing material.
4, according to present invention process, by application demand selectivity preparation conduction or nonconducting amphoteric cellulose magnetic aerogel material, the object of required design can be reached.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph (SEM) (amplifying 150 times) of the raw material Microcrystalline Cellulose that the embodiment of the present invention provides;
Fig. 2 is SEM figure (amplifying 150 times) of the both sexes Microcrystalline Cellulose that the embodiment of the present invention provides;
Fig. 3 is that both sexes Microcrystalline Cellulose that the embodiment of the present invention provides contrasts with the infrared spectra (FTIR) of Microcrystalline Cellulose and schemes;
Fig. 4 is that both sexes Microcrystalline Cellulose that the embodiment of the present invention provides contrasts with the photoelectron spectrum (XPS) of Microcrystalline Cellulose and schemes;
Fig. 5 is the X-ray diffractogram (XRD) of the both sexes Microcrystalline Cellulose magnetic aerogel that the embodiment of the present invention provides;
Fig. 6 ~ Figure 11 is the scanning electron microscope (SEM) photograph (SEM) of the both sexes Microcrystalline Cellulose magnetic aerogel that the embodiment of the present invention provides, in the same area amplify successively 50 times, 200 times, 400 times, 800 times, 2K doubly, 8K doubly;
Figure 12,13 is the transmission electron microscope pictures (TEM) of the both sexes Microcrystalline Cellulose magnetic aerogel that the embodiment of the present invention provides;
Figure 14 is both sexes Microcrystalline Cellulose magnetic aerogel (density=9mg/ cm provided by the invention
3) in the mass ratio aerogel material corresponding to (AP-MCC/GO) of amphoteric cellulose and graphene oxide to the relation between the static equilibrium adsorptive capacity of cupric ion.
Embodiment
Below in conjunction with drawings and Examples, technical solution of the present invention is described in detail.
Embodiment 1:
Take Microcrystalline Cellulose 12g, be placed in the sodium hydroxide solution that 150ml concentration is 0.5wt%, boil 40min, deionized water wash 4 times, dry to obtain alkaline Microcrystalline Cellulose.Get 10g alkalescence Microcrystalline Cellulose and be placed in 120ml ethanol, dripping 8ml concentration under stirring is successively 10wt% sodium hydroxide solution, 16g 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, after 45 DEG C of water-bath 3h, regulate product pH value to neutral with dilute hydrochloric acid, suction filtration also uses methyl alcohol, absolute ethanol washing successively, vacuum-drying, to constant weight, obtains quaternized Microcrystalline Cellulose.The quaternized Microcrystalline Cellulose of 8.0g and 150ml deionized water is added in there-necked flask; logical nitrogen protection, stirs 10min in 25 DEG C, adds 9g ceric ammonium nitrate; 2-acrylamide-2-methyl propane sulfonic 15g is added again after reaction 20min; after reaction 60min, system is transferred in 50 DEG C and continues reaction 180min, take out product, naturally cooling; successively through deionized water, acetone, ether filtering and washing; airing 30min under normal temperature, vacuum-drying, to constant weight, obtains both sexes Microcrystalline Cellulose.
Get the graphene oxide water solution 16ml that concentration is 1.86mg/ml, toward wherein adding 116.8mg both sexes Microcrystalline Cellulose, 400r/min stirs 20 min, obtains both sexes Microcrystalline Cellulose/graphene oxide binary complex liquid; Get the Z 250 ethanolic soln 1.2ml of concentration 1wt%, slowly drop under stirring in above-mentioned both sexes Microcrystalline Cellulose/graphene oxide binary complex liquid, mix, obtain the tri compound liquid of amphoteric cellulose/graphene oxide/Z 250; Under high-speed stirring, the calcium chloride water getting 1.0mL concentration 5g/L is dropwise added dropwise in the tri compound liquid of amphoteric cellulose/graphene oxide/Z 250, stir 30min, packing is carried out to the ternary complex of gained amphoteric cellulose/graphene oxide/Z 250, obtains density through lyophilize and be about 9.0mg/cm
3amphoteric cellulose magnetic aerogel.
See accompanying drawing 1, it is the scanning electron microscope (SEM) photograph (SEM) (amplifying 150 times) of the raw material Microcrystalline Cellulose that the present embodiment adopts, and its pattern, size uniform as seen, median size is at 20 μm × 80 μm.
See accompanying drawing 2, be SEM figure (amplifying 150 times) of the both sexes Microcrystalline Cellulose that the present embodiment provides, completing as seen along with amphoteric modification, Microcrystalline Cellulose mean sizes drops to 5 μm × 40 μm, and its scantlings of the structure is subject to certain destruction.
See accompanying drawing 3, be that both sexes Microcrystalline Cellulose that the present embodiment provides contrasts with the infrared spectra (FTIR) of Microcrystalline Cellulose and schemes, 1238.4 cm
-1(δ
c-O) place belongs to Microcrystalline Cellulose (MCC, curve is C a)
6primary hydroxyl stretching vibration peak on position, disappears in both sexes Microcrystalline Cellulose after modification (, curve b), shows that 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride has been received on Microcrystalline Cellulose by etherification reaction; In addition, 1647.0 cm in curve b
-1with 1552.6 cm
-1the absorption peak at place belongs to amide Ⅰ (ν respectively
c=O) flexural vibration peak and acid amides II be with (δ
n-H) stretching vibration peak, 1747.1 cm
-1then belong to fiber prime ring C
3aldehyde radical (ν on position
c=O) stretching vibration peak, the appearance of these characteristic peaks shows: Mierocrystalline cellulose open loop under the effect of initiator ceric ammonium nitrate, in C
2, C
3position generates aldehyde radical, and anionic monomer 2-acrylamide-2-methyl propane sulfonic has been grafted on Mierocrystalline cellulose by free radicals copolymerization reaction simultaneously, thus occurs amide Ⅰ (ν
c=O) and acid amides II be with (δ
n-H) characteristic peak, the amphoteric modification of preliminary proof Microcrystalline Cellulose is successful.
See accompanying drawing 4, be that both sexes Microcrystalline Cellulose that the present embodiment provides contrasts with the photoelectron spectrum (XPS) of Microcrystalline Cellulose and schemes, be used for confirming further the amphoteric modification result of Microcrystalline Cellulose.Curve a is Microcrystalline Cellulose (MCC), curve b is both sexes Microcrystalline Cellulose (AP-MCC), compares curve a, and 168,285,400 in curve b, and 530 eV places have occurred belonging to S2p respectively
3/2, C1s, N1s, O1s characteristic strip absorption peak.Wherein N1s and S2p
3/2come from cationic monomer 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and anionic monomer 2-acrylamide-2-methyl propane sulfonic respectively, further both confirmations have been grafted on Microcrystalline Cellulose by Chemical bond, and modified product is both sexes Microcrystalline Cellulose really.
See accompanying drawing 5, it is the X-ray diffractogram (XRD) of the amphoteric cellulose magnetic aerogel that the present embodiment provides.First, occurred respectively belonging to Mierocrystalline cellulose pars amorpha (I in diffraction angle 18 ° and 22.5 ° of places
am) and crystallizing field (I
002) diffractive features peak, and relative intensity is higher, illustrates that in product, content of cellulose is more; In addition, clearly can see the crystallographic plane diffraction peak belonging to C in graphene oxide (001) diffraction angle about 10 °, show that product includes graphene oxide; Moreover, contrast with Z 250 XRD standard card (JCPDS No.26-1136), this product in (111), (220), all there is corresponding XRD crystallographic plane diffraction peak in (311), (222), (400), (422), (511) and (440) place, completely corresponding with the standard spectrogram of Z 250 XRD, in its intensity lower explanation product, Z 250 content is lower.Namely XRD result shows that this example products obtained therefrom is made up of Mierocrystalline cellulose, graphene oxide and Z 250.
See accompanying drawing 6 ~ Figure 11, be the scanning electron microscope (SEM) photograph (SEM) of the amphoteric cellulose magnetic aerogel that the present embodiment provides respectively, in the same area amplify successively 50 times, 200 times, 400 times, 800 times, 2K doubly, 8K doubly.Clearly, the composition-formed that Fig. 6 ~ Fig. 8 shows both sexes Microcrystalline Cellulose aerogel is: both sexes Microcrystalline Cellulose makes skeleton, the agent structure of aerogel is formed with state of disarray, graphene oxide is by forms such as coated, curling and extensions, bridge and bonding effect is played each other at both sexes Microcrystalline Cellulose, both sexes Microcrystalline Cellulose framework is connected, forms through three-dimensional porous structure.Fig. 9 ~ Figure 11 is clear display then, the both sexes Microcrystalline Cellulose of composition aerogel and surface of graphene oxide are all by ferroferric oxide nano granules uniform fold, grain diameter is at 100 ~ 500nm, and Large stone shows that it may be the aggregate of ferriferrous oxide nano-particle.
See accompanying drawing 12,13, be the transmission electron microscope picture (TEM) of the amphoteric cellulose magnetic aerogel that the present embodiment provides respectively.Because both sexes Microcrystalline Cellulose size is comparatively large, shown in figure, be only the pattern of graphene oxide-loaded Z 250.Figure 12 shows Z 250 and is really uniformly distributed in surface of graphene oxide with the morphology of the aggregate, size is about 100nm ~ 1 μm, it is formed by the ferriferrous oxide nano-particle reunion of particle diameter at 5 ~ 10nm that Figure 13 shows single Z 250 aggregate further, and small particle size determines that corresponding ferriferrous oxide nano-particle or aggregate can possess superparamagnetism.
See accompanying drawing 14, be 9mg/ cm in amphoteric cellulose magnetic aerogel density provided by the invention
3time, along with the proportioning of amphoteric cellulose and graphene oxide changes, corresponding aerogel is to the static saturated adsorption capacity changing conditions of cupric ion.Adsorption conditions is: pH value 5.5, adsorption temp 30 DEG C, adsorption time 12h.Under result shows most of proportioning, aerogel adsorptive capacity is all higher than 100mg/g, is far superior to the Studies On Preparation And Properties of Cellulose-based Adsorbents material of existing report.And when the mass ratio of amphoteric cellulose and graphene oxide is 3:7, the adsorptive capacity of respective magnetic aerogel is maximum, up to 135.2mg/g, when the two proportioning is below or above this ratio, corresponding adsorptive capacity all has and reduces in various degree, prove that the proportioning of amphoteric cellulose and graphene oxide directly affects the microtexture of aerogel, and then affect its adsorptive power.Physical structure and chemical feature determine amphoteric cellulose magnetic aerogel material of the present invention and possess wide spectrum absorption, stowage capacity, and application potential is large.
Embodiment 2:
Take Microcrystalline Cellulose 8g, be placed in the sodium hydroxide solution that 120ml concentration is 0.2wt%, boil 60min, deionized water wash 4 times, dry to obtain alkaline Microcrystalline Cellulose.Get 6g alkalescence Microcrystalline Cellulose and be placed in 10ml acetone, dripping 5ml concentration under stirring is successively 12wt% sodium hydroxide solution, 12g 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, after 45 DEG C of water-bath 3h, regulate product pH value to neutral with dilute hydrochloric acid, suction filtration also uses methyl alcohol, absolute ethanol washing successively, vacuum-drying, to constant weight, obtains quaternized Microcrystalline Cellulose.The quaternized Microcrystalline Cellulose of 6g and 150ml deionized water is added in there-necked flask; logical nitrogen protection, stirs 10min in 25 DEG C, adds 8g ceric ammonium nitrate; 2-acrylamide-2-methyl propane sulfonic 12g is added again after reaction 20min; after reaction 60min, system is transferred in 50 DEG C and continues reaction 180min, take out product, naturally cooling; successively through deionized water, acetone, ether filtering and washing; airing 20min under normal temperature, vacuum-drying, to constant weight, obtains both sexes Microcrystalline Cellulose.
Get the graphene oxide water solution 60ml that concentration is 1.6mg/ml, toward wherein adding 96mg both sexes Microcrystalline Cellulose, 300r/min stirs 20 min, obtains both sexes Microcrystalline Cellulose/graphene oxide binary complex liquid; Get the Z 250 ethanolic soln 0.6ml of concentration 4wt%, slowly drop under stirring in above-mentioned both sexes Microcrystalline Cellulose/graphene oxide binary complex liquid, mix, obtain the tri compound liquid of amphoteric cellulose/graphene oxide/Z 250; Under high-speed stirring, the aq. polyethyleneimine getting 1.2mL concentration 5g/L is dropwise added dropwise in the tri compound liquid of amphoteric cellulose/graphene oxide/Z 250, stir 30min, packing is carried out to the ternary complex of gained amphoteric cellulose/graphene oxide/Z 250, obtains density through lyophilize and be about 2.0mg/cm
3amphoteric cellulose magnetic aerogel.
Embodiment 3:
Take cotton fibre 10g, be placed in the sodium hydroxide solution that 1000ml concentration is 18wt%, room temperature leaves standstill 45min, taking-up is clean with deionized water wash, dry after, be placed in the sodium hydroxide solution that 1000ml concentration is 0.4wt%, boil 60min, deionized water repetitive scrubbing, dry to obtain alkali cellulose.Get 5g alkali cellulose and be placed in 10ml ethanol, dripping 4.5ml concentration under stirring is successively 18wt% sodium hydroxide solution, 10g 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, after 45 DEG C of water-bath 3h, regulate product pH value to neutral with dilute hydrochloric acid, suction filtration also uses methyl alcohol, absolute ethanol washing successively, vacuum-drying, to constant weight, obtains quaternized cellulose.4g quaternized cellulose and 120ml deionized water is added in there-necked flask; logical nitrogen protection, stirs 10min in 25 DEG C, adds 6g ceric ammonium nitrate; 2-acrylamide-2-methyl propane sulfonic 10g is added again after reaction 20min; after reaction 60min, system is transferred in 50 DEG C and continues reaction 180min, take out product, naturally cooling; successively through deionized water, acetone, ether filtering and washing; airing 20min under normal temperature, vacuum-drying, to constant weight, obtains amphoteric cellulose.Amphoteric cellulose is placed in the hydrochloric acid soln that volumetric concentration is 5%, stirring at room temperature hydrolysis 2h, obtains both sexes Microcrystalline Cellulose.
Get the graphene oxide water solution 7.8ml that concentration is 3.72mg/ml, toward wherein adding 29.2mg both sexes Microcrystalline Cellulose, 400r/min stirs 20 min, obtains both sexes Microcrystalline Cellulose/graphene oxide binary complex liquid; Get the Z 250 ethanolic soln 1ml of concentration 0.5wt%, slowly drop under stirring in above-mentioned both sexes Microcrystalline Cellulose/graphene oxide binary complex liquid, mix, obtain the tri compound liquid of amphoteric cellulose/graphene oxide/Z 250; Under high-speed stirring, the Hyperbranched Polymer with Terminal Amido aqueous solution getting 2mL concentration 6g/L is dropwise added dropwise in the tri compound liquid of amphoteric cellulose/graphene oxide/Z 250, stir 30min, packing is carried out to the ternary complex of gained amphoteric cellulose/graphene oxide/Z 250, obtains density through lyophilize and be about 15.1mg/cm
3amphoteric cellulose magnetic aerogel.
Claims (8)
1., based on a preparation method for cellulosic magnetic aerogel material, it is characterized in that comprising the steps:
(1) compound concentration is the aqueous solution of the graphene oxide of 0.01wt% ~ 10wt%; be 1:10 ~ 10:1 by the mass ratio of graphene oxide and amphoteric cellulose; at rotating speed be under the agitation condition of 200r/min ~ 600 r/min by amphoteric cellulose powder dispersion in graphene oxide water solution, obtain the binary complex liquid of amphoteric cellulose/graphene oxide;
(2) by Z 250 ultrasonic disperse in ethanol, compound concentration is 0. 1wt% ~ 10wt% Z 250 ethanolic soln, be 1:10 ~ 1:200 by the mass ratio of Z 250 and amphoteric cellulose, Z 250 ethanolic soln is slowly joined in binary composite solution prepared by step (1), stir, obtain the tri compound liquid of amphoteric cellulose/graphene oxide/Z 250;
(3) compound concentration is the cross-linking agent aqueous solution of 0.1wt% ~ 2wt%, be 1:50 ~ 1:400 by the mass ratio of linking agent and amphoteric cellulose, under agitation cross-linking agent aqueous solution is added drop-wise in tri compound liquid prepared by step (2), after continuing stirring 1 ~ 60min, obtain the ternary complex of the graphene oxide/Z 250 of thickness, again through lyophilize, obtaining density is 0.1mg/cm
3~ 40mg/cm
3amphoteric cellulose magnetic aerogel material.
2. the preparation method based on cellulosic magnetic aerogel material according to claim 1, it is characterized in that: described amphoteric cellulose powder is both sexes Microcrystalline Cellulose, median size is 20 ~ 80 μm.
3. the preparation method based on cellulosic magnetic aerogel material according to claim 2, is characterized in that: described both sexes Microcrystalline Cellulose, take cellulosic fibre as raw material, obtain, comprise step as follows after amphoteric modification process:
(1) cellulosic fibre being joined concentration is in the sodium hydroxide solution of 17wt% ~ 18wt%, normal temperature leaves standstill process 40 ~ 50min, through deionized water clean, dry after, being placed in concentration is that the sodium hydroxide solution of 0.1wt% ~ 5wt% boils process 20 ~ 60min, clean through deionized water again, dry, obtain alkali cellulose;
(2) alkali cellulose is joined in ethanol or acetone by bath raio 1:10 ~ 1:80, dripping sodium hydroxide solution and the 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride of 10wt% ~ 30wt% under agitation condition successively, is react 2 ~ ~ 5h under the condition of 30 ~ 50 DEG C in temperature; The mass volume ratio of alkali cellulose and sodium hydroxide solution is 1:0.5 ~ 1:3, mass ratio 1:1 ~ the 1:3 of alkali cellulose and 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, after reaction terminates, regulate product pH value to neutral with dilute hydrochloric acid, suction filtration is also successively through methyl alcohol, absolute ethanol washing, vacuum-drying, to constant weight, obtains quaternized cellulose;
(3) quaternized cellulose is joined in deionized water by bath raio 1:30 ~ 1:100, in protection of inert gas, temperature is stir 10 ~ 30min under the condition of 30 ± 5 DEG C, slowly add ceric ammonium nitrate again, the mass ratio of quaternized cellulose and ceric ammonium nitrate is 1:0.2 ~ 1:3, after stirring reaction 10 ~ 60min, add sulfonated monomers 2-acrylamide-2-methyl propane sulfonic, the mass ratio of quaternized cellulose and 2-acrylamide-2-methyl propane sulfonic is 1:1 ~ 1:5, after stirring reaction 30 ~ 180min, be warming up to 50 ~ 70 DEG C, continue reaction 2 ~ 5h, take out product, naturally cooling, successively through deionized water, acetone, ether filtering and washing, airing 30 ~ 120min under normal temperature, vacuum-drying is to constant weight, obtain amphoteric cellulose, amphoteric cellulose is placed in the dilute acid soln that volumetric concentration is 1% ~ 10%, 20 ~ 30 DEG C of constant temperature soak 1 ~ 6h, obtain both sexes Microcrystalline Cellulose after hydrolysis.
4. the preparation method based on cellulosic magnetic aerogel material according to claim 2, is characterized in that: described both sexes Microcrystalline Cellulose, take Microcrystalline Cellulose as raw material, obtain, comprise step as follows after amphoteric modification process:
(1) Microcrystalline Cellulose being joined concentration is boil process 20 ~ 60min in the sodium hydroxide solution of 0.1wt% ~ 5wt%, then, oven dry clean through deionized water, obtains alkaline Microcrystalline Cellulose;
(2) alkaline Microcrystalline Cellulose is joined in ethanol or acetone by bath raio 1:10 ~ 1:80, dripping sodium hydroxide solution and the 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride of 10wt% ~ 30wt% under stirring successively, is react 2 ~ ~ 5h under the condition of 30 ~ 50 DEG C in temperature; The mass volume ratio of alkalescence Microcrystalline Cellulose and sodium hydroxide solution is 1:0.5 ~ 1:3, mass ratio 1:1 ~ the 1:3 of alkalescence Microcrystalline Cellulose and 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, after reaction terminates, regulate product pH value to neutral with dilute hydrochloric acid, suction filtration is also successively through methyl alcohol, absolute ethanol washing, vacuum-drying, to constant weight, obtains quaternized Microcrystalline Cellulose;
(3) quaternized Microcrystalline Cellulose is joined in deionized water by bath raio 1:30 ~ 1:100, in protection of inert gas, temperature is stir 10 ~ 30min under the condition of 30 ± 5 DEG C, slowly add ceric ammonium nitrate again, the mass ratio of quaternized Microcrystalline Cellulose and ceric ammonium nitrate is 1:0.2 ~ 1:3, after stirring reaction 10 ~ 60min, sulfonated monomers 2-acrylamide-2-methyl propane sulfonic is added in reaction system, the mass ratio of quaternized Microcrystalline Cellulose and 2-acrylamide-2-methyl propane sulfonic is 1:1 ~ 1:5, after stirring reaction 30 ~ 180min, be warming up to 50 ~ 70 DEG C, continue reaction 2 ~ 5h, take out product, naturally cooling, successively through deionized water, acetone, ether filtering and washing, airing 30 ~ 120min under normal temperature, vacuum-drying is to constant weight, obtain both sexes Microcrystalline Cellulose.
5. the preparation method based on cellulosic magnetic aerogel material according to claim 1, it is characterized in that: described linking agent is the one in mixture containing calcium ion, calcium chloride, divinylsulfone, multiamino compound, genipin, or their arbitrary combination; The described mixture containing calcium ion is the mixture of calcium carbonate and diluted acid, and described diluted acid is the one in dilute hydrochloric acid, dust technology, acetic acid, or multiple; Described multiamino compound is chitosan, silk-protein, quadrol, hydroxyethylethylene diamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines, polymine, N, one in N-methylene-bisacrylamide, Hyperbranched Polymer with Terminal Amido, or their arbitrary combination.
6. the preparation method based on cellulosic magnetic aerogel material according to claim 1, is characterized in that: described Z 250 is dispersed nano Z 250 or polydispersion nano ferriferrous oxide.
7. the preparation method based on cellulosic magnetic aerogel material according to claim 6, is characterized in that: described Z 250 is the one in the nanoparticle of Z 250, nanometer rod, nano wire, or multiple.
8. the one prepared by preparation method according to claim 1 is based on cellulosic magnetic aerogel material.
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