CN104194066A - Silicon oxide-chitosan composite aerogel and preparation method thereof - Google Patents
Silicon oxide-chitosan composite aerogel and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a silicon oxide-chitosan composite aerogel and a preparation method thereof. The silicon oxide-chitosan composite aerogel comprises chitosan, a chitosan cross-linking agent and silicon oxide, wherein the mass fraction of the chitosan is 9%-65%, the mass fraction of the silicon oxide is 30%-90%, and the mass fraction of the chitosan cross-linking agent is 1%-5%.
Description
Technical field
The invention belongs to composite material field, be specifically related to a kind of silicon oxide-chitosan composite aerogel and preparation method thereof, prepared composite aerogel acid-proof alkaline is good, and specific surface area is high, grafting different functional groups as required, for fields such as medicine, water treatment, chemical industry.
Background technology
Chitosan derives from natural polymer chitin, nature rich content, molecule contains amino, hydroxyl isoreactivity functional group, and there is the excellent properties such as good biocompatibility, microbic resolvability, in fields such as medicine, food, chemical industry, makeup, water treatment, METAL EXTRACTION and recovery, there is important application prospect.
In the aqueous solution, the amino of chitosan molecule is easy to ionization, and when pH value is lower than 5 time, chitosan can dissolve, and has greatly limited the application of chitosan in acidic solution.In order to improve the resistance to acid of chitosan, generally chitosan and linking agent are occurred to be cross-linked, but prepared crosslinked chitosan resin specific surface area is little.Chitosan Chang Zuowei carrier or sorbent material, specific surface area is an important parameter index, less specific surface area has affected the effect of chitosan greatly.In order to improve the specific surface area of chitosan, people attempt preparing chitosan aerogel.But between chitosan molecule, have very strong hydrogen bond, cause gel that serious distortion and contraction occur in drying process, this has increased difficulty prepared by chitosan aerogel.For improving the specific surface area of chitosan aerogel, generally adopt in two ways: (1) adopts supercritical drying mode, but potential safety hazard is large, cost is higher; (2) take inorganic gel as skeleton support, prepare chitosan composite aerogel.
(J.Phys.Chem.B 2008,112,7721-7725) disclose a kind of preparation method of chitosan aerogel for Chen Dairong etc.With the dilute acid soln generation crosslinking reaction of formaldehyde, oxalic dialdehyde or glutaraldehyde as cross linker and chitosan, form aquagel, adopt supercritical drying mode to prepare chitosan aerogel, wherein formaldehyde crosslinking chitosan aerogel specific surface area can reach 845m
2/ g.But the method adopts supercritical drying mode, and potential safety hazard is larger, and cost is higher, is difficult in industrial large-scale application.
Michael R.Ayers (Journal of Non-Crystalline Solids, 2001,285, a kind of preparation method of silicon oxide-chitosan aerogel 123-127) is disclosed.The method be take tetraethoxy as silicon source, first prepares silicon oxide-chitosan wet gel, then adopts supercritical drying mode to prepare silicon oxide-chitosan composite aerogel of high-specific surface area, and specific surface tool reaches as high as 750m
2/ g.But the method does not react chitosan and linking agent, limited its application in sour environment.Meanwhile, the method adopts supercritical drying mode, and potential safety hazard is larger, and cost is higher.
Therefore, this field in the urgent need to a kind of simply, mode is prepared chitosan aerogel efficiently.
Summary of the invention
The present invention is intended to overcome the defect of existing chitosan aerogel performance and preparation method aspect, the invention provides a kind of silicon oxide-chitosan composite aerogel and preparation method thereof.
The invention provides a kind of silicon oxide-chitosan composite aerogel, described silicon oxide-chitosan composite aerogel comprises chitosan, chitosan crosslinked dose and silicon oxide, wherein, chitosan mass mark is 9%-65%, siliconoxide mass mark is 30%-90%, and the massfraction of chitosan crosslinked dose is 1%-5%.Should be understood that herein chitosan crosslinked dose comprises chitosan crosslinked dose of being present in the middle of the composite aerogel linking group because reacting and form with chitosan.
Preferably, described silicon oxide-chitosan composite aerogel has three-dimensional porous network structure, and BET specific surface area is 300-1000m
2/ g, tap density is 0.1-1.0g/cm
3.
Preferably, described chitosan crosslinked dose be formaldehyde, oxalic dialdehyde, at least one in glutaraldehyde, suceinic aldehyde.
Again, the present invention also provides a kind of preparation method of above-mentioned silicon oxide-chitosan composite aerogel, and described preparation method comprises:
1) chitosan solution that the silicate solution that is 2-3 by pH is 1-3 with pH mixes and obtains silicic acid-chitosan mixed sols or solution;
2) regulating step 1) silicic acid-chitosan mixed sols of preparing or the pH value of solution be between 5-7, and add chitosan crosslinked dose in described silicic acid-chitosan mixed sols or solution, after stirring, at 40～80 ℃, react 0.5～12 hour, obtain silicon oxide-chitosan plural gel, wherein, the mass ratio between chitosan, chitosan crosslinked dose and silicic acid meets the proportionlity between forming in described silicon oxide-chitosan composite aerogel;
3) first by step 2) silicon oxide-chitosan plural gel of preparing smashs to pieces to particle size and is less than 1cm, to in silicon oxide-chitosan plural gel of smashing to pieces, immerse in polar organic solvent again, by stirring, make polar organic solvent displace the water in silicon oxide-chitosan plural gel;
4) by step 3) in silicon oxide-chitosan plural gel of being replaced, immerse in non-polar organic solvent, by stirring, make non-polar organic solvent displace the polar organic solvent in silicon oxide-chitosan plural gel;
5) by step 4) in silicon oxide-chitosan plural gel of being replaced carry out constant pressure and dry processing.
Preferably, step 1) in, the preparation method of silicate solution is: the water glass that is first 1.0-3.5 by modulus mixes with water, obtain water glass solution, then water glass solution is poured in storng-acid cation exchange resin, stirred after 5-30 minute to filter and obtain clear liquid and obtain the silicate solution that described pH value is 2-3.
Preferably, step 1) in, in the diluted acid that the chitosan solution that described pH is 1-3 is dissolved in 0.01～0.1mol/L by chitosan powder, making, the deacetylation of described chitosan powder is 60%-95%.
Preferably, step 3) in, polar organic solvent is at least one in alcoholic solvent, tetrahydrofuran (THF), DMF, acetone.
Preferably, step 3) in, repeating to stir 1-24 hour at 25-80 ℃, the number of times of repetition is 2-5 time, thereby realizes solvent exchange.
Preferably, step 4) in, non-polar organic solvent surface tension need be less than 25mN-m, preferably hexanaphthene, normal hexane, normal heptane or its combination.
Preferably, step 4) in, repeating to stir 1-24 hour at 25-80 ℃, the number of times of repetition is 2-5 time, thereby realizes solvent exchange.
Preferably, step 4) in, silicon oxide-chitosan plural gel is when immersing non-polar organic solvent for the first time, and in non-polar organic solvent, adding general formula is the silane coupling agent of RSiX3, R is organic group, preferably, vinyl, amino, epoxy group(ing), sulfydryl, isocyanic ester, X is facile hydrolysis group, preferred chloro, methoxyl group, oxyethyl group, the add-on of silane coupling agent is the 0%-50% of water glass volume used, determines according to the actual requirements, even sometimes without surface chemical modification.
Preferably, step 5) in, drying treatment is: at 80-120 ℃, and dry 2-12 hour.
Beneficial effect of the present invention:
Feature of the present invention is prepared silicon oxide-chitosan composite aerogel, and chitosan mass mark is 9%-65%, and the massfraction of chitosan crosslinked dose is 1%-5%, and siliconoxide mass mark is 30%-90%.The present invention passes through sol-gel method, adopt the mode of copolymerization to prepare silicon oxide-chitosan composite aquogel, then implement repeatedly solvent exchange and the surface chemical modification of polarity and non-polar solvent, finally by constant pressure and dry method, prepare high-specific surface area, silicon oxide-chitosan composite aerogel that acid-proof alkaline is good, can be applicable to the fields such as medicine, water treatment, chemical.The main raw material that present method is used is service water glass and chitosan, and source is abundant, cheap, and working condition is gentle, the time consuming time is short, and step is simple to operation, and production efficiency is high, is applicable to large-scale industrial production.
Accompanying drawing explanation
Fig. 1 shows the SEM photo of silicon oxide-chitosan composite aerogel of preparing in an embodiment of the invention;
Fig. 2 shows silicon oxide-chitosan aerogel infrared absorption spectrum of preparing in an embodiment of the invention;
Fig. 3 shows amino modified silicon oxide-chitosan aerogel infrared absorption spectrum of preparing in an embodiment of the invention;
Fig. 4 shows silicon oxide-chitosan aerogel infrared absorption spectrum of preparing in an embodiment of the invention.
Embodiment
Below in conjunction with accompanying drawing and following embodiment, further illustrate the present invention, should be understood that accompanying drawing and following embodiment are only for the present invention is described, and unrestricted the present invention.
The present invention relates to a kind of silicon oxide-chitosan composite aerogel and preparation method thereof.Prepared silicon oxide-chitosan the composite aerogel of the present invention has three-dimensional porous network structure, and BET specific surface area is 300-1000m
2/ g, tap density is 0.1-1.0g/cm
3, its component consists of: chitosan mass mark is 9%-65%, and the massfraction of chitosan crosslinked dose is 1%-5%, and siliconoxide mass mark is 30%-90%.
The method of the invention comprises the steps: that (1) prepare silicon oxide-chitosan complex sol; (2) prepare silicon oxide-chitosan gel rubber; (3) polar organic solvent of silicon oxide-chitosan gel rubber displacement; (4) displacement of the non-polar solvent of silicon oxide-chitosan gel rubber and surface chemical modification; (5) acquisition of the constant pressure and dry of silicon oxide-chitosan gel rubber and silicon oxide-chitosan composite aerogel.Composite aerogel acid-proof alkaline prepared by the present invention is good, and specific surface area is high, and grafting different functional groups as required, for fields such as medicine, water treatment, chemical industry.Composite aerogel preparation method provided by the present invention has the outstanding advantages such as cost is low, the production time is short, is applicable to large-scale industrial production.
The preparation method of described silicon oxide-chitosan aerogel, specifically comprises the steps:
One) preparation of silicon oxide-chitosan complex sol.The service water glass of choosing different moduluses is silicon source, and it is mixed with appropriate deionized water, obtains the water glass solution (A) of dilution.The water glass solution (A) of dilution is poured in storng-acid cation exchange resin, stirred 5min-30min, filter, obtaining clear liquid is that pH value is at the silicate solution (B) of 2-3.Chitosan powder is dissolved in diluted acid, makes chitosan solution (C).Silicate solution (B) is poured in chitosan solution (C), stirred, obtain the mixed sols (D) of chitosan and silicic acid;
Two) preparation of silicon oxide-chitosan gel rubber.Utilize basic catalyst to regulate the pH value of mixed sols (D) of chitosan and silicic acid to 5-7, add chitosan crosslinked dose, and stir, at 40-80 ℃, react 30min-12h, obtain silicon oxide-chitosan plural gel (E);
Three) polar organic solvent of silicon oxide-chitosan gel rubber displacement.By step 2) silicon oxide-chitosan plural gel (E) of preparing smashs to pieces to granular size below 1cm, immerses in polar organic solvent, at 25-80 ℃, stirs 1-24h, carries out solvent exchange.This step repeats 2-5 time, obtains plural gel (F);
Four) displacement of the polar solvent of silicon oxide-chitosan gel rubber and surface chemical modification.By step 3) in the compound organogel (F) that obtains immerse in non-polar organic solvent, at 25-80 ℃, stir 1-24h, carry out solvent exchange.Repeat solvent swap step 2-5 time, obtain plural gel (G).If will carry out chemical modification to compound organogel (F), can when first immersion non-polar organic solvent, add silane coupling agent, still need thereafter the solvent exchange of 2-5 time;
Five) acquisition of the constant pressure and dry of silicon oxide-chitosan gel rubber and silicon oxide-chitosan composite aerogel.By step 4) plural gel (G) that obtains puts into baking oven, and at 80-120 ℃, dry 2-12h, obtains silicon oxide-chitosan composite aerogel.
Step 1) modulus of water glass using in is 1.0-3.5.
Step 1) storng-acid cation exchange resin using in can be styrene type cation exchange resin and modified resin or any other Zeo-karb.
The deacetylation of the chitosan powder using using step 1) is 60%-95%.
Step 1) diluted acid using in is hydrochloric acid, sulfuric acid, nitric acid, acetic acid or other any inorganic or organic acid of concentration at 0.01-0.1mol/L.
Step 2) basic catalyst using in discharges the material of hydroxide ion for ammoniacal liquor, sodium hydroxide, potassium hydroxide, vulkacit H, thanomin etc. in water.
Step 2) in, use chitosan crosslinked dose for formaldehyde, oxalic dialdehyde, glutaraldehyde, suceinic aldehyde etc. or its composition.
Step 3) polar organic solvent of the polar organic solvent using for freely mixing with water, it can be alcoholic solvent, tetrahydrofuran (THF), N, dinethylformamide, acetone etc., be preferably monobasic or the polyvalent alcohol (as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, ethylene glycol) that can dissolve each other with water.
Step 4) the non-polar organic solvent surface tension of using in need be less than 25mN-m, preferably hexanaphthene, normal hexane, normal heptane or its combination.
The general formula of the silane coupling agent using step 5) is RSiX3, R is organic group, as vinyl, amino, epoxy group(ing), sulfydryl, isocyanic ester etc., X is some facile hydrolysis group, as chloro, methoxyl group, oxyethyl group etc., specifically comprise trimethylchlorosilane, hexamethyldisilazane, 3-aminopropyl triethoxysilane, 3-aminopropyl methyldiethoxysilane, 3-glycidyl ether oxygen base propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane etc. or its composition, but be not limited to this.
In order to solve current technical defect, prepare simultaneously high-ratio surface chitosan aerogel, the present invention is usingd silica gel as support frame, adopt copolymerization gel mode, by solvent exchange process and surface chemical modification repeatedly, adopt atmosphere pressure desiccation to prepare silicon oxide-chitosan composite aerogel of high-specific surface area.The present invention passes through sol-gel method, adopt the mode of copolymerization to prepare silicon oxide-chitosan composite aquogel, then implement repeatedly solvent exchange and the surface chemical modification of polarity and non-polar solvent, finally by constant pressure and dry method, prepare high-specific surface area, silicon oxide-chitosan composite aerogel that acid-proof alkaline is good, can be applicable to the fields such as medicine, water treatment, chemical.The main raw material that present method is used is service water glass and chitosan, and source is abundant, cheap, and working condition is gentle, the time consuming time is short, and step is simple to operation, and production efficiency is high, is applicable to large-scale industrial production.
Below further list some exemplary embodiments so that the present invention to be described better.Should understand; the above-mentioned embodiment that the present invention describes in detail; and following examples are only not used in and limit the scope of the invention for the present invention is described, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjust and all belong to protection scope of the present invention.In addition, the concrete proportioning in following processing parameter, time, temperature etc. are only also exemplary, and those skilled in the art can select suitable value in the scope of above-mentioned restriction.
Embodiment 1:
1) choosing modulus is 10 milliliters, 3.0 service water glass, mixes with the deionized water of 40 milliliters, stirs, and obtains dilution water glass solution (A).The strong-acid ion exchange resin of volume ratio 1:1 is mixed with dilution water glass, stir 10min, filtering and obtaining clear liquid is that pH value is the silicate solution (B) of 2-3.0.5g chitosan powder is dissolved in the acetum of 50 milliliters of 0.1mol/L, makes chitosan solution (C).50 milliliters of silicate solutions (B) are poured in 50 milliliters of chitosan solutions (C), stirred 20min, obtain the mixing solutions (D) of chitosan and silicate solution;
2) utilize ammoniacal liquor to regulate pH value to 6 left and right of mixing solutions (D), add the glutaraldehyde that 100 microlitre mass concentrations are 25% and stir 20min, at 60 ℃, react 1h, obtain silicon oxide-chitosan composite aquogel (E);
3) by step 2) in silicon oxide-chitosan composite aquogel (E) of obtaining smash to pieces and immerse in the ethanol of 100 milliliters, at 65 ℃, stir 2h, carry out the solvent exchange of ethanol.Repeat solvent swap step 2 times, obtain plural gel (F);
4) by step 3) plural gel (F) that obtains immerses in the hexanaphthene of 100 milliliters, at 65 ℃, stirs 2h, carries out the solvent exchange of hexanaphthene.Repeat solvent swap step 3 times, obtain plural gel (G);
5) by step 4) plural gel (G) that obtains puts into baking oven, and at 120 ℃, dry 3h, obtains hydrophilic silicon oxide-chitosan composite aerogel;
Silicon oxide-chitosan composite aerogel prepared by the present embodiment has three-dimensional porous network structure, and its SEM photo as shown in Figure 1; Through the test of BET isothermal adsorption, specific surface area is 514.4m
2/ g, tap density 0.64g/cm
3;
Fig. 2 shows the infrared absorption spectrum of silicon oxide-chitosan composite aerogel prepared by the present embodiment, and 1089,800,468cm
-1near absorption peak is the vibration absorption peak of silicon oxide skeleton Si-O-Si key, 969cm
-1near the peak occurring is corresponding to the absorption peak of silicon oxide skeleton Si-OH, 1653cm
-1near the peak occurring is corresponding to glutaraldehyde cross-linking chitosan-C=N-flexural vibration absorption peak.
Embodiment 2:
1) choosing modulus is 10 milliliters, 3.0 service water glass, mixes with the deionized water of 40 milliliters, stirs, and obtains dilution water glass solution (A).The strong-acid ion exchange resin of volume ratio 1:1 is mixed with dilution water glass, stir 10min, filtering and obtaining clear liquid is that pH value is the silicate solution (B) of 2-3.1g chitosan powder is dissolved in the acetum of 50 milliliters of 0.1mol/L, makes chitosan solution (C).50 milliliters of silicate solutions (B) are poured in 50 milliliters of chitosan solutions (C), stirred 20min, obtain the mixing solutions (D) of chitosan and silicate solution;
2) utilize vulkacit H to regulate pH value to 6 left and right of mixing solutions (D), add the glutaraldehyde that 200 microlitre mass concentrations are 25% and stir 20min, at 60 ℃, react 1h, obtain silicon oxide-chitosan composite aquogel (E);
3) by step 2) in silicon oxide-chitosan composite aquogel (E) of obtaining smash to pieces and immerse in the ethanol of 100 milliliters, at 65 ℃, stir 2h, carry out the solvent exchange of ethanol.Repeat solvent swap step 2 times, obtain plural gel (F);
4) by step 3) the compound organogel (F) that obtains immerses in the hexanaphthene of 100 milliliters, at 65 ℃, stirs 2h, carries out the solvent exchange of hexanaphthene.Repeat solvent swap step 3 times, obtain plural gel (G);
5) by step 4) plural gel (G) that obtains puts into baking oven, and at 100 ℃, dry 3h, obtains silicon oxide-chitosan composite aerogel.Through the test of BET isothermal adsorption, specific surface area is 425.7m
2/ g, tap density 0.76g/cm
3.
Embodiment 3:
1) choosing modulus is 10 milliliters, 3.0 service water glass, mixes with the deionized water of 40 milliliters, stirs, and obtains dilution water glass solution (A).The strong-acid ion exchange resin of volume ratio 1:1 is mixed with dilution water glass, stir 10min, filtering and obtaining clear liquid is that pH value is the silicate solution (B) of 2-3.1g chitosan powder is dissolved in the acetum of 50 milliliters of 0.1mol-L, make chitosan solution (C), 10ml silicate solution (A) is poured in chitosan solution (B), stirred 20min, obtain the mixing solutions (D) of chitosan and silicate solution;
2) utilize vulkacit H to regulate pH value to 6 left and right of mixing solutions (D), add the glutaraldehyde that 200 microlitre mass concentrations are 25% and stir 10min, at 60 ℃, react 2h, obtain silicon oxide-chitosan composite aquogel (E);
3) by step 2) in silicon oxide-chitosan composite aquogel (E) of obtaining smash to pieces and immerse in the ethanol of 100 milliliters, at 65 ℃, stir 2h, carry out the solvent exchange of ethanol.Repeat solvent swap step 2 times, obtain plural gel (F);
4) by step 3) plural gel (F) that obtains immerses in 100 milliliters of hexanaphthenes, then adds 2 milliliters of 3-aminopropyl triethoxysilanes (APTES), at 65 ℃, stirs 4h, obtains amino modified plural gel (G).Amino modified gel (G) is immersed in 100 milliliters of hexanaphthenes again, at 65 ℃, stir 2h, carry out solvent exchange, repeat solvent exchange 3 times, filter and obtain the amino modified plural gel (H) after solvent exchange;
5) by step 4) the amino modified plural gel (H) that obtains puts into baking oven, and at 100 ℃, dry 3h, obtains amino modified silicon oxide-chitosan composite aerogel.Through the test of BET isothermal adsorption, specific surface area is 600.3m2/g, and tap density is 0.5g/cm3;
Fig. 3 shows amino modified silicon oxide-chitosan aerogel infrared absorption spectrum of this enforcement preparation, and 1071,784,461cm
-1near absorption peak is the vibration absorption peak of silicon oxide skeleton Si-O-Si key, compares Fig. 2, unmodified silicon oxide-chitosan composite aerogel sample, 969cm
-1near the absorption peak of silicon oxide Si-OH obviously die down, this has shown APTES success modification silicon oxide skeleton, simultaneously 1647cm
-1near the peak occurring is-NH
2stack peak with-C=N-absorption peak.
Embodiment 4:
1) choosing modulus is 10 milliliters, 3.0 service water glass, mixes with the deionized water of 40 milliliters, stirs, and obtains dilution water glass solution (A).The strong-acid ion exchange resin of volume ratio 1:1 is mixed with dilution water glass, stir 10min, filtering and obtaining clear liquid is that pH value is the silicate solution (B) of 2-3.1g chitosan powder is dissolved in the acetum of 50 milliliters of 0.1mol/L, makes chitosan solution (C).50 milliliters of silicate solutions (B) are poured in 50 milliliters of chitosan solutions (C), stirred 20min, obtain the mixing solutions (D) of chitosan and silicate solution;
2) utilize vulkacit H to regulate pH value to 6 left and right of mixing solutions (D), add the formaldehyde solution that 1.5 milliliters of massfractions are 40% and stir 20min, at 60 ℃, react 1h, obtain silicon oxide-chitosan composite aquogel (E);
3) by step 2) in silicon oxide-chitosan composite aquogel (E) of obtaining smash to pieces and immerse in the ethanol of 100 milliliters, at 65 ℃, stir 2h, carry out the solvent exchange of ethanol.Repeat solvent swap step 2 times, obtain plural gel (F);
4) by step 3) the compound organogel (F) that obtains immerses in the hexanaphthene of 100 milliliters, at 65 ℃, stirs 2h, carries out the solvent exchange of hexanaphthene.Repeat solvent swap step 3 times, obtain plural gel (G);
5) by step 4) plural gel (G) that obtains puts into baking oven, and at 100 ℃, dry 3h, obtains silicon oxide-chitosan composite aerogel.Through the test of BET isothermal adsorption, specific surface area is 843.2m
2/ g, tap density 0.2g/cm
3;
Fig. 4 shows silicon oxide-chitosan aerogel infrared absorption spectrum of this enforcement preparation, and 1087,799,466cm
-1near absorption peak is the vibration absorption peak of silicon oxide skeleton Si-O-Si key, 970cm
-1near the peak occurring is corresponding to the absorption peak of silicon oxide skeleton Si-OH, 1639cm
-1near the peak occurring is corresponding to formaldehyde crosslinking chitosan-C=N-flexural vibration absorption peak.
Claims (12)
1. silicon oxide-chitosan composite aerogel, it is characterized in that, described silicon oxide-chitosan composite aerogel comprises chitosan, chitosan crosslinked dose and silicon oxide, wherein, chitosan mass mark is 9%-65%, siliconoxide mass mark is 30%-90%, and chitosan crosslinked dose of massfraction is 1%-5%.
2. silicon oxide-chitosan composite aerogel according to claim 1, is characterized in that, described silicon oxide-chitosan composite aerogel has three-dimensional porous network structure, and BET specific surface area is 300-1000m
2/ g, tap density is 0.1-1.0 g/cm
3.
3. silicon oxide-chitosan composite aerogel according to claim 1 and 2, is characterized in that, described chitosan crosslinked dose be formaldehyde, oxalic dialdehyde, at least one in glutaraldehyde, suceinic aldehyde.
4. a preparation method for arbitrary described silicon oxide-chitosan composite aerogel in claim 1-3, is characterized in that, described preparation method comprises:
1) chitosan solution that the silicate solution that is 2-3 by pH is 1-3 with pH mixes and obtains silicic acid-chitosan mixed sols or solution;
2) regulating step 1) silicic acid-chitosan mixed sols of preparing or the pH value of solution be between 5-7, and add chitosan crosslinked dose in described silicic acid-chitosan mixed sols or solution, after stirring, at 40～80 ℃, react 0.5～12 hour, obtain silicon oxide-chitosan plural gel, wherein, the mass ratio between chitosan, chitosan crosslinked dose and silicic acid meets the proportionlity between forming in described silicon oxide-chitosan composite aerogel;
3) first by step 2) silicon oxide-chitosan plural gel of preparing smashs to pieces to particle size and is less than 1cm, again the silicon oxide of smashing to pieces-chitosan plural gel is immersed in polar organic solvent, by stirring, make polar organic solvent displace the water in silicon oxide-chitosan plural gel;
4) by the silicon oxide-chitosan plural gel being replaced in step 3), immerse in non-polar organic solvent, by stirring, make non-polar organic solvent displace the polar organic solvent in silicon oxide-chitosan plural gel;
5) silicon oxide-chitosan plural gel being replaced in step 4) is carried out to constant pressure and dry processing.
5. according to the preparation method described in right 4, it is characterized in that, in step 1), the preparation method of silicate solution is: the water glass that is first 1.0-3.5 by modulus mixes with water, obtain water glass solution, then water glass solution is poured in storng-acid cation exchange resin, stirred after 5-30 minute to filter and obtain clear liquid and obtain the silicate solution that described pH value is 2-3.
6. according to the preparation method described in right 4 or 5, it is characterized in that, in step 1), the chitosan solution that described pH is 1-3 has chitosan powder to be dissolved in the diluted acid of 0.01～0.1mol/L to make, and the deacetylation of described chitosan powder is 60%-95%.
7. according to arbitrary described preparation method in right 4-6, it is characterized in that, in step 3), polar organic solvent is at least one in alcoholic solvent, tetrahydrofuran (THF), DMF, acetone.
8. according to arbitrary described preparation method in right 4-7, it is characterized in that, in step 3), repeat to stir 1-24 hour at 25-80 ℃, the number of times of repetition is 2-5 time, thereby realizes solvent exchange.
9. according to arbitrary described preparation method in right 4-8, it is characterized in that, in step 4), non-polar organic solvent surface tension need be less than 25mN-m, preferably hexanaphthene, normal hexane, normal heptane or its combination.
10. according to arbitrary described preparation method in right 4-9, it is characterized in that, in step 4), repeat to stir 1-24 hour at 25-80 ℃, the number of times of repetition is 2-5 time, thereby realizes solvent exchange.
11. according to arbitrary described preparation method in right 4-10, it is characterized in that, in step 4), silicon oxide-chitosan plural gel is when immersing non-polar organic solvent for the first time, and in non-polar organic solvent, adding general formula is RSiX
3silane coupling agent, R is organic group, preferably, vinyl, amino, epoxy group(ing), sulfydryl, isocyanic ester, X is facile hydrolysis group, preferably chloro, methoxyl group, oxyethyl group, Ti Ji Bi≤50% of the add-on of silane coupling agent and water glass used.
12. according to arbitrary described preparation method in right 4-11, it is characterized in that, in step 5), drying treatment is: at 80-120 ℃, and dry 2-12 hour.
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