CN104194066B - 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 present invention relates to a kind of silicon oxide chitosan composite aerogel and preparation method thereof, 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 mass fraction 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 side thereof
Method, prepared composite aerogel acid-proof alkaline is good, and specific surface area is high, can grafting different functional groups as required, be used for curing
The fields such as the process of medicine, water, chemical industry.
Background technology
Chitosan derives from natural polymer chitin, nature rich content, and intramolecular contains amino, hydroxyl isoreactivity
Functional group, and there is the excellent properties such as good biocompatibility, microbic resolvability, in medicine, food, chemical industry, cosmetic
The fields such as the process of product, water, METAL EXTRACTION and recovery have important application prospect.
In aqueous, the amino of chitosan molecule is easy to ionizing, and when pH value is less than 5, chitosan can occur
Dissolve, strongly limit the application of chitosan in acid solution.In order to improve the acid-resisting of chitosan, typically by chitosan and friendship
Connection agent crosslinks, but prepared crosslinked chitosan resin specific surface area is little.Chitosan frequently as carrier or adsorbent, than
Surface area is an important parameter index, the less specific surface area strong influence application effect of chitosan.In order to improve
The specific surface area of chitosan, chitosan aeroge is prepared in people's trial.But there is the strongest hydrogen bond between chitosan molecule, cause
There is serious deformation and contraction in gel in dry run, which increases difficulty prepared by chitosan aeroge.Gather for improving shell
The specific surface area of sugar aeroge, typically uses two ways: (1) uses supercritical drying mode, but potential safety hazard is relatively big, one-tenth
This is higher；(2) with inorganic gel as skeletal support, chitosan composite aerogel is prepared.
Chen Dairong etc. (J.Phys.Chem.B 2008,112,7721-7725) disclose the preparation side of a kind of chitosan aeroge
Method.Crosslink reaction with the dilute acid soln of formaldehyde, Biformyl or glutaraldehyde as cross linker and chitosan, form chitosan water-setting
Glue, uses supercritical drying mode to prepare chitosan aeroge, wherein formaldehyde crosslinking chitosan aeroge specific surface area up to
845m2/g.But the method uses supercritical drying mode, potential safety hazard is relatively big, relatively costly, is difficult to the biggest rule
Mould is applied.
Michael R.Ayers (Journal of Non-Crystalline Solids, 2001,285,123-127) discloses a kind of oxidation
The preparation method of silicon-chitosan aeroge.The method, with tetraethyl orthosilicate for silicon source, first prepares silicon oxide-chitosan wet solidifying
Glue, then uses supercritical drying mode to be prepared for the silicon oxide-chitosan composite aerogel of high-specific surface area, and specific surface has
High up to 750m2/g.But chitosan is not reacted by the method with cross-linking agent, limit its answering in sour environment
With.Meanwhile, the method uses supercritical drying mode, and potential safety hazard is relatively big, relatively costly.
Therefore, this field is simple in the urgent need to one, quick way prepares chitosan aeroge.
Summary of the invention
It is contemplated that overcome the defect in terms of existing chitosan aeroge performance and preparation method, the invention provides one
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 shell
Polysaccharide, chitosan crosslinked dose and silicon oxide, wherein, chitosan mass mark is 9%-65%, and siliconoxide mass mark is
30%-90%, the mass fraction of chitosan crosslinked dose is 1%-5%.Should be understood that herein chitosan crosslinked dose includes being present in
In the middle of composite aerogel chitosan crosslinked dose because of with chitosan react formed linking group.
It is preferred that described silicon oxide-chitosan composite aerogel has three-dimensional porous network structure, BET specific surface area is
300-1000m2/ g, tap density is 0.1-1.0g/cm3。
It is preferred that described chitosan crosslinked dose is at least one in formaldehyde, Biformyl, glutaraldehyde, butanedial.
Also, present invention also offers the preparation method of a kind of above-mentioned silicon oxide-chitosan composite aerogel, described preparation method
Including:
1) silicate solution that pH is 2-3 is mixed homogeneously with the chitosan solution that pH is 1-3 obtain silicic acid-chitosan mixed sols or
Solution；
2) regulating step 1) pH value of silicic acid-chitosan mixed sols of preparing or solution is between 5-7, and to described silicic acid-shell
Polysaccharide mixed sols or solution add chitosan crosslinked dose, reacts 0.5～12 hour at 40～80 DEG C after stirring,
Silicon oxide-chitosan plural gel, wherein, chitosan, mass ratio between chitosan crosslinked dose and silicic acid meet described oxygen
Proportionate relationship between forming in SiClx-chitosan composite aerogel；
3) first by step 2) silicon oxide-chitosan plural gel of preparing is smashed to pieces to particle size less than 1cm, then the oxidation that will smash to pieces
Silicon-chitosan plural gel immerses in polar organic solvent, make polar organic solvent displace silicon oxide-shell by stirring and gather
Water in sugar pluralgel；
4) by step 3) in silicon oxide-chitosan plural gel of being replaced, immerse in non-polar organic solvent, made by stirring
Obtain non-polar organic solvent and 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 process.
It is preferred that step 1) in, the preparation method of silicate solution is: first mixed with water by the waterglass that modulus is 1.0-3.5
Close, obtain water glass solution, then water glass solution is poured in storng-acid cation exchange resin, after stirring 5-30 minute
It is filtrated to get clear liquid and obtains the silicate solution that described pH value is 2-3.
It is preferred that step 1) in, described pH be 1-3 chitosan solution by chitosan powder body be dissolved in 0.01～
Preparing in the diluted acid of 0.1mol/L, the deacetylation of described chitosan powder body is 60%-95%.
It is preferred that step 3) in, polar organic solvent be alcohols solvent, oxolane, DMF, third
At least one in ketone.
It is preferred that step 3) in, repeating to stir 1-24 hour at 25-80 DEG C, the number of times of repetition is 2-5 time, thus
Realize solvent displacement.
It is preferred that step 4) in, non-polar organic solvent surface tension need to be less than 25mN-m, preferably hexamethylene, just oneself
Alkane, normal heptane or a combination thereof.
It is preferred that step 4) in, repeating to stir 1-24 hour at 25-80 DEG C, the number of times of repetition is 2-5 time, thus
Realize solvent displacement.
It is preferred that step 4) in, silicon oxide-chitosan plural gel when immersing non-polar organic solvent for the first time,
In non-polar organic solvent add formula be the silane coupler of RSiX3, R is organic group, it is preferable that vinyl, amino,
Epoxy radicals, sulfydryl, isocyanates, X is facile hydrolysis group, preferably chloro, methoxyl group, ethyoxyl, adding of silane coupler
Enter the 0%-50% that amount is waterglass volume used, according to the actual requirements depending on, the most sometimes without surface chemical modification.
It is preferred that step 5) in, dried is: at 80-120 DEG C, is dried 2-12 hour.
Beneficial effects of the present invention:
It is characteristic of the invention that prepared silicon oxide-chitosan composite aerogel, chitosan mass mark is 9%-65%, and chitosan is handed over
The mass fraction of connection agent is 1%-5%, and siliconoxide mass mark is 30%-90%.The present invention passes through sol-gal process, uses altogether
Polymerization mode prepare silicon oxide-chitosan composite aquogel, be then carried out repeatedly polarity and non-polar solven solvent displacement and
Surface chemical modification, is prepared for high-specific surface area eventually through constant pressure and dry method, silicon oxide-chitosan that acid-proof alkaline is good
Composite aerogel, can be applicable to the fields such as medicine, water process, chemical.The primary raw material that this method is used is industry water
Glass and chitosan, abundance, cheap, and working condition is gentle, short time consumption is short, and step is simple to operation,
Production efficiency is high, is suitable for large-scale industrial production.
Accompanying drawing explanation
Fig. 1 shows that in an embodiment of the invention, the SEM of the silicon oxide-chitosan composite aerogel of preparation shines
Sheet；
Fig. 2 shows the silicon oxide-chitosan aeroge infrared absorption spectroscopy of preparation in an embodiment of the invention；
Fig. 3 shows the amino modified silicon oxide-chitosan aeroge infrared absorption spectroscopy of preparation in an embodiment of the invention；
Fig. 4 shows the silicon oxide-chitosan aeroge infrared absorption spectroscopy of preparation in an embodiment of the invention.
Detailed description of the invention
The present invention is further illustrated, it should be appreciated that accompanying drawing and following embodiment are only below in conjunction with accompanying drawing and following embodiment
For the present invention is described, and the unrestricted present invention.
The present invention relates to a kind of silicon oxide-chitosan composite aerogel and preparation method thereof.Silicon oxide-shell prepared by the present invention
Polysaccharide composite aerogel has three-dimensional porous network structure, and BET specific surface area is 300-1000m2/ g, tap density is 0.1-
1.0g/cm3, its component consists of: chitosan mass mark is 9%-65%, and the mass fraction of chitosan crosslinked dose is 1%-
5%, siliconoxide mass mark is 30%-90%.
The method of the invention comprises the steps: that (1) prepares silicon oxide-chitosan complex sol；(2) prepare silicon oxide-
Chitosan gel rubber；(3) the polar organic solvent displacement of silicon oxide-chitosan gel rubber；(4) the non-pole of silicon oxide-chitosan gel rubber
Property solvent displacement and surface chemical modification；(5) constant pressure and dry and the silicon oxide-chitosan of silicon oxide-chitosan gel rubber is combined airsetting
The acquisition of glue.Composite aerogel acid-proof alkaline prepared by the present invention is good, and specific surface area is high, can the official's energy of grafting difference as required
Group, for fields such as medicine, water process, chemical industry.Composite aerogel preparation method provided by the present invention has low cost, life
The product time short outstanding advantage that waits, applicable large-scale industrial production.
The preparation method of described silicon oxide-chitosan aeroge, specifically includes following steps:
One) preparation of silicon oxide-chitosan complex sol.The industrial waterglass choosing different modulus is silicon source, it is gone with appropriate
Ionized water mixes, and obtains the water glass solution (A) of dilution.Pour the water glass solution (A) of dilution into highly acidic cation to hand over
Change in resin, stir 5min-30min, filter, obtain the clear liquid i.e. pH value silicate solution (B) at 2-3.By chitosan powder
Body is dissolved in diluted acid, prepares chitosan solution (C).Being poured into by silicate solution (B) in chitosan solution (C), stirring is all
Even, it is thus achieved that the mixed sols (D) of chitosan and silicic acid；
Two) preparation of silicon oxide-chitosan gel rubber.Utilize the PH of the mixed sols (D) of base catalyst regulation chitosan and silicic acid
Value, to 5-7, adds chitosan crosslinked dose, and stirs, and reacts 30min-12h, obtain silicon oxide-chitosan at 40-80 DEG C
Pluralgel (E)；
Three) the polar organic solvent displacement of silicon oxide-chitosan gel rubber.By step 2) silicon oxide-chitosan of preparing is compound solidifying
Glue (E) is smashed to pieces to granular size at below 1cm, immerses in polar organic solvent, stirs 1-24h, carry out at 25-80 DEG C
Solvent is replaced.This step repeats 2-5 time, obtains pluralgel (F)；
Four) polar solvent of silicon oxide-chitosan gel rubber is replaced and surface chemical modification.By step 3) in the compound organogel that obtains
(F) immerse in non-polar organic solvent, at 25-80 DEG C, stir 1-24h, carry out solvent displacement.Repeat solvent swap step 2-
5 times, obtain pluralgel (G).To compound organogel (F) is carried out chemical modification, can be nonpolar in first immersion
Add silane coupler during organic solvent, still need to thereafter the solvent displacement of 2-5 time；
Five) constant pressure and dry of silicon oxide-chitosan gel rubber and the acquisition of silicon oxide-chitosan composite aerogel.By step 4) obtain
Pluralgel (G) is put in baking oven, at 80-120 DEG C, is dried 2-12h, i.e. obtains silicon oxide-chitosan and be combined airsetting
Glue.
Step one) used in modulus of water glass be 1.0-3.5.
Step one) used in storng-acid cation exchange resin can be styrene type cation exchange resin and modification thereof
Resin or other cation exchange resin any.
Step one) used in the deacetylation of the chitosan powder body used be 60%-95%.
Step one) used in diluted acid be concentration the hydrochloric acid of 0.01-0.1mol/L, sulphuric acid, nitric acid, acetic acid or other
Any inorganic or organic acid.
Step 2) used in base catalyst be ammonia, sodium hydroxide, potassium hydroxide, hexamethylenetetramine, second
Hydramine etc. discharge the material of hydroxide ion in water.
Step 2) used in chitosan crosslinked dose be formaldehyde, Biformyl, glutaraldehyde, butanedial etc. or a combination thereof
Thing.
Step 3) polar organic solvent that used is the polar organic solvent freely mixed with water, can be that alcohols is molten
Agent, oxolane, DMF, acetone etc., be preferably can unitary miscible with water or polyhydric alcohol (as methanol,
Ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol, isobutanol, ethylene glycol).
Step 4) used in non-polar organic solvent surface tension need to be less than 25mN-m, preferably hexamethylene, just oneself
Alkane, normal heptane or a combination thereof.
Step 5) used in the formula of silane coupler be RSiX3, R be organic group, as vinyl, amino,
Epoxy radicals, sulfydryl, isocyanates etc., X is some facile hydrolysis group, such as chloro, methoxyl group, ethyoxyl etc., specifically includes
Trim,ethylchlorosilane, HMDS, 3-aminopropyl triethoxysilane, 3-aminopropyltriethoxy diethoxy silane, 3-
Glycydoxy trimethoxy silane, γ-methacryloxypropyl trimethoxy silane etc. or a combination thereof
Thing, but it is not limited to this.
In order to solve current technical defect, prepare simultaneously high-ratio surface chitosan aeroge, the present invention with oxidation
Silica hydrogel, as support frame, uses combined polymerization gel formats, by solvent replacement process repeatedly and surface chemical modification, adopts
Silicon oxide-chitosan the composite aerogel of high-specific surface area it is prepared for atmosphere pressure desiccation.The present invention passes through sol-gal process, adopts
Preparing silicon oxide-chitosan composite aquogel by the mode of combined polymerization, the solvent being then carried out repeatedly polarity and non-polar solven is put
Change and surface chemical modification, be prepared for high-specific surface area eventually through constant pressure and dry method, silicon oxide-shell that acid-proof alkaline is good
Polysaccharide composite aerogel, can be applicable to the fields such as medicine, water process, chemical.The primary raw material that this method is used is work
Industry waterglass and chitosan, abundance, cheap, and working condition is gentle, short time consumption is short, and step is the most easily grasped
Making, production efficiency is high, is suitable for large-scale industrial production.
List some exemplary embodiments further below so that the present invention is better described.Should be understood that the present invention describes in detail
Above-mentioned embodiment, and following example be merely to illustrate the present invention rather than limit the scope of the present invention, the skill of this area
Some nonessential improvement and adjustment that art personnel make according to the foregoing of the present invention belong to protection scope of the present invention.Separately
Outward, concrete proportioning in following technological parameter, time, temperature etc. are the most only exemplary, and those skilled in the art can be above-mentioned
Suitably value is selected in the range of restriction.
Embodiment 1:
1) choosing the industrial waterglass 10 milliliters that modulus is 3.0, the deionized water with 40 milliliters mixes, and 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, stirs 10min, mistake
Filter obtains the silicate solution (B) that clear liquid i.e. pH value is 2-3.0.5g chitosan powder body is dissolved in the vinegar of 50 milliliters of 0.1mol/L
In acid solution, prepare chitosan solution (C).Pour 50 milliliters of silicate solutions (B) into 50 milliliters of chitosan solutions (C)
In, stir 20min, it is thus achieved that the mixed solution (D) of chitosan and silicate solution；
2) utilizing the pH value of ammonia regulation mixed solution (D) to about 6, adding 100 microlitre mass concentrations is the glutaraldehyde of 25%
And stir 20min, at 60 DEG C, 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,
Stir 2h at 65 DEG C, carry out the solvent displacement of ethanol.Repeat solvent swap step 2 times, obtain pluralgel (F)；
4) by step 3) pluralgel (F) that obtains immerses in the hexamethylene of 100 milliliters, and at 65 DEG C, stir 2h, carry out hexamethylene
The solvent displacement of alkane.Repeat solvent swap step 3 times, obtain pluralgel (G)；
5) by step 4) pluralgel (G) that obtains puts in baking oven, and at 120 DEG C, it is dried 3h, i.e. obtains hydrophilic oxidation
Silicon-chitosan composite aerogel；
Silicon oxide prepared by the present embodiment-chitosan composite aerogel has three-dimensional porous network structure, its SEM photograph such as Fig. 1 institute
Show；Testing through BET isothermal adsorption, specific surface area is 514.4m2/ g, tap density 0.64g/cm3；
Fig. 2 shows the infrared absorption spectroscopy of silicon oxide-chitosan composite aerogel prepared by the present embodiment, 1089,800,468cm-1
The neighbouring vibration absorption peak that absworption peak is silicon oxide skeleton Si-O-Si key, 969cm-1The neighbouring peak occurred is corresponding to silicon oxide bone
The absworption peak of frame Si-OH, 1653cm-1The neighbouring peak occurred absorbs corresponding to glutaraldehyde cross-linking chitosan-C=N-bending vibration
Peak.
Embodiment 2:
1) choosing the industrial waterglass 10 milliliters that modulus is 3.0, the deionized water with 40 milliliters mixes, and 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, stirs 10min, mistake
Filter obtains the silicate solution (B) that clear liquid i.e. pH value is 2-3.1g chitosan powder body is dissolved in the acetic acid of 50 milliliters of 0.1mol/L
In solution, prepare chitosan solution (C).Pour 50 milliliters of silicate solutions (B) into 50 milliliters of chitosan solutions (C)
In, stir 20min, it is thus achieved that the mixed solution (D) of chitosan and silicate solution；
2) utilizing the pH value of hexamethylenetetramine regulation mixed solution (D) to about 6, adding 200 microlitre mass concentrations is 25%
Glutaraldehyde and stir 20min, at 60 DEG C 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,
Stir 2h at 65 DEG C, carry out the solvent displacement of ethanol.Repeat solvent swap step 2 times, obtain pluralgel (F)；
4) by step 3) the compound organogel (F) that obtains immerses in the hexamethylene of 100 milliliters, and at 65 DEG C, stir 2h, carry out
The solvent displacement of hexamethylene.Repeat solvent swap step 3 times, obtain pluralgel (G)；
5) by step 4) pluralgel (G) that obtains puts in baking oven, and at 100 DEG C, it is dried 3h, i.e. obtains silicon oxide-shell
Polysaccharide composite aerogel.Testing through BET isothermal adsorption, specific surface area is 425.7m2/ g, tap density 0.76g/cm3。
Embodiment 3:
1) choosing the industrial waterglass 10 milliliters that modulus is 3.0, the deionized water with 40 milliliters mixes, and 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, stirs 10min, mistake
Filter obtains the silicate solution (B) that clear liquid i.e. pH value is 2-3.1g chitosan powder body is dissolved in the acetic acid of 50 milliliters of 0.1mol-L
In solution, prepare chitosan solution (C), 10ml silicate solution (A) is poured in chitosan solution (B), stirring
20min, it is thus achieved that the mixed solution (D) of chitosan and silicate solution；
2) utilizing the pH value of hexamethylenetetramine regulation mixed solution (D) to about 6, adding 200 microlitre mass concentrations is 25%
Glutaraldehyde and stir 10min, at 60 DEG C 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,
Stir 2h at 65 DEG C, carry out the solvent displacement of ethanol.Repeat solvent swap step 2 times, obtain pluralgel (F)；
4) by step 3) pluralgel (F) that obtains immerses in 100 milliliters of hexamethylene, is subsequently adding 2 milliliters of 3-aminopropyl three second
TMOS (APTES), stirs 4h at 65 DEG C, obtains amino modified pluralgel (G).By amino modified gel
(G) it is again dipped in 100 milliliters of hexamethylene, at 65 DEG C, stirs 2h, carry out solvent displacement, repeat solvent displacement 3
Secondary, it is filtrated to get the amino modified pluralgel (H) after solvent displacement；
5) by step 4) the amino modified pluralgel (H) that obtains puts in baking oven, and at 100 DEG C, it is dried 3h, i.e. obtains ammonia
Base modified silicon oxide-chitosan composite aerogel.Testing through BET isothermal adsorption, specific surface area is 600.3m2/g, jolt ramming
Density is 0.5g/cm3；
Fig. 3 shows amino modified silicon oxide-chitosan aeroge infrared absorption spectroscopy prepared by this enforcement, 1071,784,461cm-1
The neighbouring vibration absorption peak that absworption peak is silicon oxide skeleton Si-O-Si key, compares Fig. 2, and unmodified silicon oxide-chitosan is combined
Aeroge sample, 969cm-1The absworption peak of neighbouring silicon oxide Si-OH substantially dies down, and this shows APTES success modification oxidation
Silicon skeleton, simultaneously 1647cm-1The neighbouring peak occurred is-NH2Superposition peak with-C=N-absworption peak.
Embodiment 4:
1) choosing the industrial waterglass 10 milliliters that modulus is 3.0, the deionized water with 40 milliliters mixes, and 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, stirs 10min, mistake
Filter obtains the silicate solution (B) that clear liquid i.e. pH value is 2-3.1g chitosan powder body is dissolved in the acetic acid of 50 milliliters of 0.1mol/L
In solution, prepare chitosan solution (C).Pour 50 milliliters of silicate solutions (B) into 50 milliliters of chitosan solutions (C)
In, stir 20min, it is thus achieved that the mixed solution (D) of chitosan and silicate solution；
2) utilizing the pH value of hexamethylenetetramine regulation mixed solution (D) to about 6, adding 1.5 milliliters of mass fractions is 40%
Formalin and stir 20min, at 60 DEG C 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,
Stir 2h at 65 DEG C, carry out the solvent displacement of ethanol.Repeat solvent swap step 2 times, obtain pluralgel (F)；
4) by step 3) the compound organogel (F) that obtains immerses in the hexamethylene of 100 milliliters, and at 65 DEG C, stir 2h, carry out
The solvent displacement of hexamethylene.Repeat solvent swap step 3 times, obtain pluralgel (G)；
5) by step 4) pluralgel (G) that obtains puts in baking oven, and at 100 DEG C, it is dried 3h, i.e. obtains silicon oxide-shell
Polysaccharide composite aerogel.Testing through BET isothermal adsorption, specific surface area is 843.2m2/ g, tap density 0.2g/cm3；
Fig. 4 shows silicon oxide-chitosan aeroge infrared absorption spectroscopy prepared by this enforcement, 1087,799,466cm-1Near
Absworption peak is the vibration absorption peak of silicon oxide skeleton Si-O-Si key, 970cm-1The neighbouring peak occurred is corresponding to silicon oxide skeleton Si-
The absworption peak of OH, 1639cm-1The neighbouring peak occurred is corresponding to formaldehyde crosslinking chitosan-C=N-bending vibration absworption peak.
Claims (10)
1. the preparation method of 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 mass fraction is 1%-5%, and described preparation method includes:
1) silicate solution that pH is 2-3 is mixed homogeneously with the chitosan solution that pH is 1-3 obtain silicic acid-chitosan mixed sols or solution, wherein, the preparation method of silicate solution is: first mixed with water by the waterglass that modulus is 1.0-3.5, obtain water glass solution, then water glass solution is poured in storng-acid cation exchange resin, it is filtrated to get clear liquid after stirring 5-30 minute, i.e. obtains the silicate solution that described pH value is 2-3；
2) regulating step 1) pH value of silicic acid-chitosan mixed sols of preparing or solution is between 5-7, and add chitosan crosslinked dose in described silicic acid-chitosan mixed sols or solution, react 0.5～12 hour at 40～80 DEG C after stirring, obtain silicon oxide-chitosan plural gel, wherein, chitosan, mass ratio between chitosan crosslinked dose and silicic acid meet the proportionate relationship in described silicon oxide-chitosan composite aerogel between composition；
3) first by step 2) silicon oxide-chitosan plural gel of preparing smashs to pieces to particle size less than 1cm, again silicon oxide-the chitosan plural gel smashed to pieces is immersed in polar organic solvent, make polar organic solvent displace the water in silicon oxide-chitosan plural gel by stirring；
4) silicon oxide-chitosan plural gel being replaced in step 3), immerse in non-polar organic solvent, non-polar organic solvent is made to displace the polar organic solvent in silicon oxide-chitosan plural gel by stirring, wherein, non-polar organic solvent surface tension need to be less than 25mN/m, and described non-polar organic solvent is hexamethylene, normal hexane, normal heptane or a combination thereof；
5) silicon oxide-chitosan plural gel being replaced in step 4) is carried out constant pressure and dry process.
Preparation method the most according to claim 1, it is characterised in that described silicon oxide-chitosan composite aerogel has three-dimensional porous network structure, BET specific surface area is 300-1000m2/ g, tap density is 0.1-1.0 g/cm3。
Preparation method the most according to claim 1, it is characterised in that described chitosan crosslinked dose is at least one in formaldehyde, Biformyl, glutaraldehyde, butanedial.
Preparation method the most according to claim 1, it is characterised in that in step 1), described pH is that the chitosan solution of 1-3 is dissolved in the diluted acid of 0.01～0.1mol/L prepared by chitosan powder body, and the deacetylation of described chitosan powder body is 60%-95%.
Preparation method the most according to claim 1, it is characterised in that in step 3), polar organic solvent is at least one in alcohols solvent, oxolane, DMF, acetone.
Preparation method the most according to claim 1, it is characterised in that in step 3), repeats to stir 1-24 hour at 25-80 DEG C, and the number of times of repetition is 2-5 time, thus realizes solvent displacement.
Preparation method the most according to claim 1, it is characterised in that in step 4), repeats to stir 1-24 hour at 25-80 DEG C, and the number of times of repetition is 2-5 time, thus realizes solvent displacement.
Preparation method the most according to claim 1, it is characterised in that in step 4), silicon oxide-chitosan plural gel is when immersing non-polar organic solvent for the first time, and adding formula in non-polar organic solvent is RSiX3Silane coupler, R is organic group, and X is facile hydrolysis group, the volume ratio 50% of the addition of silane coupler and waterglass used.
Preparation method the most according to claim 8, it is characterised in that R is vinyl, amino, epoxy radicals, sulfydryl, isocyanates, X is chloro, methoxyl group, ethyoxyl.
Preparation method the most according to claim 1, it is characterised in that in step 5), dried is: at 80-120 DEG C, is dried 2-12 hour.
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| SI3397651T1 (en) | 2015-12-29 | 2020-11-30 | Galderma S.A. | Carbohydrate crosslinker |
| CN107715852B (en) * | 2017-11-02 | 2020-05-22 | 湘潭大学 | Vanillin modified chitosan-SiO2Composite aerogel material and preparation method and application thereof |
| CN108421534B (en) * | 2018-02-08 | 2020-10-20 | 中山大学 | Chitosan gel material, preparation method thereof, wastewater treatment method and application |
| CN109225150A (en) * | 2018-10-10 | 2019-01-18 | 烟台工程职业技术学院 | A kind of preparation method of the dioxide composite silica aerogel of adsorbable formaldehyde |
| CN109718726B (en) * | 2018-12-29 | 2021-08-03 | 江苏脒诺甫纳米材料有限公司 | Production process of amphiphilic silica-chitosan composite aerogel |
| EP4069753A1 (en) | 2019-12-02 | 2022-10-12 | Galderma Holding SA | High molecular weight esthetic compositions |
| CN111285345B (en) * | 2020-02-25 | 2021-07-27 | 中国科学院化学研究所 | Method for preparing carbon aerogel from hydrogel precursor material through hydrothermal process |
| CN112244925B (en) * | 2020-10-26 | 2022-04-22 | 河北爱能生物科技股份有限公司 | Composite chitosan uterine cavity hemostatic balloon and preparation method thereof |
| CN113546585B (en) * | 2021-08-05 | 2022-09-09 | 内蒙古科技大学 | Hydrophobic agarose-SiO 2 Composite aerogel microspheres and preparation method thereof |
| CN113979773A (en) * | 2021-12-03 | 2022-01-28 | 南京工业大学 | Method for preparing polymer-converted ceramic aerogel |
| CN114588936B (en) * | 2022-03-14 | 2023-06-16 | 南京大学 | Zirconium-based Fenton-like catalyst and preparation method and application thereof |
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| CN102557052A (en) * | 2012-03-05 | 2012-07-11 | 中国科学院上海硅酸盐研究所 | Method for rapidly preparing low-density silicon oxide aerogel |
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