CN102417606A - Preparation method of chitin aerogel - Google Patents
Preparation method of chitin aerogel Download PDFInfo
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- CN102417606A CN102417606A CN 201110221079 CN201110221079A CN102417606A CN 102417606 A CN102417606 A CN 102417606A CN 201110221079 CN201110221079 CN 201110221079 CN 201110221079 A CN201110221079 A CN 201110221079A CN 102417606 A CN102417606 A CN 102417606A
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Abstract
The invention discloses a preparation method of chitin aerogel, comprising the following steps of: immersing a chitin solution into a coagulant, regenerating, washing to obtain chitin hydrogel; displacing water in the chitin hydrogel with an organic liquid to obtain chitin organogel; drying the chitin hydrogel or organogel to remove the liquid so as to obtain the chitin aerogel; carrying out deacetylation on the chitin hydrogel, washing to obtain chitosan hydrogel; displacing water in the chitosan hydrogel with an organic liquid to obtain chitosan organogel; drying the chitosan hydrogel or organogel to remove the liquid so as to obtain chitosan aerogel; and carrying out heat treatment on the chitin and chitosan aerogel over 150 DEG C so as to obtain carbon aerogel. Through a nitrogen adsorption-desorption test, the specific surface area of the chitin aerogel, chitosan aerogel and carbon aerogel reaches 300m<2>/g or more than 300m<2>/g.
Description
Technical field
The present invention relates to a kind of preparation method of chitin gas gel, belong to field of new.
Technical background
Gas gel is a kind of solid matter form, is one of solid of density minimum in the world.Because density is extremely low, the lightest silica aerogel only has 3 milligrams every cubic centimetre at present, is heavier than air three times, so also be called " cigarette that freezes ".
Gas gel has the nanoporous three-dimensional net structure of high-permeability; Very high porosities, extra-low density, high-specific surface area; Structure and performance obviously are different from pore space structure at the porous material of micron with the millimeter magnitude, have widely at aspects such as separation, absorption, catalysis, photoelectricity, transmitter, biological medicines and use.
Gas gel is as a kind of advanced material of developed recently; Usually make wet gel through sol-gel method or from organic precursor through polyreaction from inorganic pioneer; Utilize technology such as supercritical drying to remove the liquid in the wet gel then, and keep network structure constant basically.
Usually with silicon sol as nanometer glue, doping colloid Pt, Au, carbon black, zeolite, TiO
2, porous chalcogen semiconductor synthetic silica aerogel matrix materials such as (CdS, CdSe, ZnS, PbS); The organic aerogel that is formed by resorcin/formaldehyde, melamine/formaldehyde and phenol/formaldehyde etc. prepares carbon aerogels through high temperature pyrolysis.
Yet the gas gel of having reported at present remains in weak point, as inorganic aerogels to moisture-sensitive, be prone to crisp, need carry out hydrophobically modified and with the crosslinked raising physical strength of polymer; The organic aerogel synthesis condition is comparatively complicated, and does not possess biocompatibility.In recent years, from the natural polymer raw material, also caused extensive concern like Mierocrystalline cellulose and chitin synthetic gas gel.
Chitin is 1, and the 2-acetylaminohydroxyphenylarsonic acid 2-deoxidation-callose of 4-keyed jointing extensively is present in insect, Crustaceans and the fungal cell wall.Can reach hundred million tons of hundreds ofs by biosynthetic chitin on the annual earth, be that occurring in nature is only second to cellulosic second largest type of renewable natural polymer.Chitin can take place deacetylated under alkaline condition, when deacetylation then is called chitosan greater than 50% the time.Their this distinctive molecular structure are given its charming biological activity.Big quantity research shows, the performances such as chitin and chitosan are nontoxic except having, excellent biological compatibility, biodegradability, also has hemostasis, analgesia, promotion wound healing, property such as antibiotic.But, because chitin percent crystallinity is high, contain a large amount of intramolecularly and intermolecular ydrogen bonding, organic solvent water insoluble and commonly used, thus limited the application of chitin.Known chitin solvent; Like the vitriol oil, concentrated hydrochloric acid, trichoroacetic acid(TCA)/methylene dichloride mixed solvent, DMAc/LiCl, lithium thiocyanate saturated aqueous solution etc.; These solvents or have severe corrosive, toxicity big; Seriously polluted, even make degradation of chitin, costing an arm and a leg causes production cost too high.EP051421 is a solvent with the strong acid trichoroacetic acid(TCA), and corrodibility is stronger.The double solvents dissolving chitin that US4029727 forms with amide solvent and LiCl, the solvent expensive, production cost is high.To obtain concentration among the 6%LiCl/DMAc be 1.9% chitin solution as chitin is dissolved in, and treats that its gelation after washing obtains chitin hydrogel, with the methyl alcohol displacement, passes through supercritical CO then
2Drying obtains the chitin gas gel, and specific surface area is at 220～365m
2/ g, density 0.12～0.23g/cm
3, porosity 85～92% [Carbohydrate Polymers, 2009,76,535-540].NMMO and ionic liquid under heating condition, also can dissolve chitin (Green Chemistry, 2006,8,630-633.), but they are responsive to water and oxidation impurities, and exist production cost high, separation, purifying and reclaim problems such as difficulty.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiency of existing chitin solvent; A kind of safety non-toxic, solvent with low cost are provided; Make chitin solution, and the preparation method of chitin formulations prepared from solutions chitin gas gel thus and carbon aerogels further is provided.
The present invention at first provides the preparation method of chitin solution for solving the problems of the technologies described above:
The solvent system that adopts is in alkali aqueous solution, alkali-aqueous solution of urea, alkali-thiourea solution or alkali-urea-thiourea solution, and solvent system mixes with chitin and is refrigerated to below freezingly, obtains chitin solution above freezing thawing.
As one preferred, chitin solution is dissolved in the NaOH/ aqueous solution of urea by chitin and makes, wherein NaOH concentration is 2～25wt%, is preferably 6～14wt%; Urea concentration is 0.1～20wt%, is preferably 4～12wt%; Surplus is a water.
Preferred as another, chitin solution is dissolved in the LiOH/ aqueous solution of urea by chitin and makes, and wherein LiOH concentration is 3～10wt%, is preferably 4～8wt%; Urea concentration is 0.1～20wt%, is preferably 4～12wt%; Surplus is a water.
Preferred as another, chitin solution is dissolved in the NaOH/ thiourea solution by chitin and makes, and wherein NaOH concentration is 2～25wt%, is preferably 6～14wt%; Thiourea concentration is 0.1～10wt%, is preferably 3～6wt%; Surplus is a water.
Preferred as another, chitin solution is dissolved in the LiOH/ thiourea solution by chitin and makes, and wherein LiOH concentration is 3～10wt%, is preferably 4～8wt%; Thiourea concentration is 0.1～10wt%, is preferably 3～6wt%; Surplus is a water.
As above-mentioned chitin source, can be halobiontic shells such as shrimp, crab, cuttlefish, the epidermis of insects such as cockroach, silkworm chrysalis, and one or more of the chitin in the mushroom cell.Before using through the method purifying of known technology and have no particular limits.Remove calcium salt like s.t., alkaline purification removes Deproteinization, oxide treatment decolouring etc.
The method of the chitin formulations prepared from solutions chitin gas gel that is prepared by front of the present invention is:
Chitin solution is immersed in the peptizer, and regeneration obtains chitin hydrogel after the washing; Water in the chitin hydrogel is replaced into organic liquid obtains the chitin organogel; Chitin hydrogel or organogel drying are removed liquid, obtain the chitin gas gel.
Chitin solution is immersed in the peptizer, and regeneration obtains chitin hydrogel after the washing; Chitin hydrogel is deacetylated, obtain aquagel after the washing; Water in the aquagel is replaced into organic liquid obtains the chitosan organogel; Aquagel or organogel drying are removed liquid, obtain the chitosan gas gel.
Said chitin hydrogel is deacetylated to be that chitin hydrogel is soaked with excess NaOH solution, and remaining NaOH is removed in cooling, promptly gets aquagel.The concentration of said NaOH solution is 20wt%～45wt%, soaks 1～48h down at 40～110 ℃.
In the preparation process of top chitin gas gel and chitosan gas gel,
Said peptizer can be that water cut is lower than 50wt%, preferably is lower than the nonpolar organic liquid of lower boiling of 10wt%.In a preferable preparation technique, liquid water content is lower than 5wt%.The instance of the suitable peptizer of this type comprises alcohol, ketone, ester or its mixture.It is preferred using methyl alcohol, ethanol and acetone to do peptizer.The nonpolar organic liquid of lower boiling has the low character of viscosity, helps solidifying of chitin solution.In addition, in the process that peptizer reclaims, help separating.
Peptizer also can be water or add cationic water, preferably contain for example H of monovalent cation
+, NH
4 +, Li
+, Na
+Or K
+The aqueous solution, such solution is can be for example water-soluble and make with hydrochloric acid, sulfuric acid, nitric acid, acetic acid, ammonium sulfate, ammonium acetate, lithium chloride, sodium sulfate, vitriolate of tartar etc.
The described organic solvent that is used to replace chitin, aquagel is lower boiling, volatile alkanes, halogenated hydrocarbon, alcohols, phenols, ether and acetals, ketone, acid and anhydrides, ester class, itrogenous organic substance, the organic compound of sulfur-bearing, or the mixture of aforementioned all kinds of SOLVENTS.In the organic solvent of enumerating in the above, find in the test, take all factors into consideration, preferably use alkanes, alcohols and ketone compounds, more preferably use methyl alcohol, ethanol or acetone from performance and the cost angle of improving chitin of the present invention, chitosan material.
In the preparation process of top chitin gas gel and chitosan gas gel; Described dry link can be utilized drying means commonly used; For example; Carry out supercritical drying with carbonic acid gas, methyl alcohol, ethanol, acetone as supercutical fluid, perhaps carry out constant pressure and dry and lyophilize and remove liquid medium.
Chitin gas gel or chitosan gas gel under inert atmosphere protection, are obtained carbon aerogels after the thermal treatment more than 150 ℃.
Inert atmosphere does not refer to and reacts with chitin, chitosan, prevents chitin, chitosan material at high temperature incendiary gas or gaseous mixture.Experiment shows that following gas especially is fit to be used as inert atmosphere: nitrogen, carbonic acid gas, helium, neon and argon gas.Also can use the mixture of these gases.An amount of sour gas, but like the carbonization of HCl catalysis chitin, chitosan.
Nitrogen adsorption-the desorption test obtains chitin, chitosan gas gel specific surface area reaches 300m
2/ g reaches 350m preferably
2/ g is higher greater than 400m
2/ g.Nitrogen adsorption-desorption test obtains the carbon aerogels specific surface area and reaches 300m
2/ g reaches 600m preferably
2/ g is higher greater than 1000m
2/ g.
At chitin of the present invention and aquagel, can also carry out surface hydroxyl or amino modification to it, like carboxymethylation, hydroxyethylation, hydroxypropylation, quaternized etc.Can in chitin and aquagel, synthesize and perhaps add inorganics, polymer, filler etc.Inorganics such as silicon-dioxide, red stone, Z 250, clay, titanium oxide etc.Polymer such as Mierocrystalline cellulose, collagen, Lalgine, POLYACTIC ACID, polyacrylate(s), PVA etc.Filler such as carbon black, glycerine, Ucar 35, butyleneglycol or PEG400 etc.Also can add fiber reinforced material such as spun glass, thomel, Mierocrystalline cellulose whisker, chitin whisker etc.Can synthesize or add at least a of these additives or filler.
The present invention provides a kind of inexpensive, pollution-free, easy method to obtain high-quality chitin solution, and utilizes this chitin solution to adopt corresponding method preparation to have chitin, chitosan gas gel and the carbon aerogels thereof of high-specific surface area.The invention has the advantages that: the solvent that is adopted is NaOH, LiOH, urea (and/or thiocarbamide) and water, and production process is nontoxic, pollution-free, helps environment protection and operator ' s health; With respect to organic solvents such as NMMO, ionic liquid and LiCl/DMAc, be to have method more easy to operate, that cost effectively prepares chitin, chitosan gas gel, low price, green non-pollution, simple to operation, practiced thrift the resource and the energy; Chitin/chitosan gas gel product and the carbon aerogels material produced have good performance and function.The not only production technique environmental protection of this novel method, cost are low, and excellent product performance, and it is the important breakthrough to prior art, is suitable for suitability for industrialized production and practical application, has broad application prospects.
Description of drawings
Fig. 1 shows the stereoscan photograph of the embodiment of the invention 8 chitin gas gels;
Fig. 2 shows the stereoscan photograph of the embodiment of the invention 24 chitosan gas gels;
Fig. 3 illustrates the stereoscan photograph of the carbon aerogels after the embodiment 32 chitin gas gel carbonizations.
Embodiment
Below in conjunction with concrete embodiment technical scheme of the present invention is described further:
Embodiment 1
With the rare HCl soaking at room temperature of 5wt% 12h, filtering the washing back, to use oven dry behind the 4wt%NaOH aqueous solution soaking 12h to obtain the acetyl degree be 92% chitin powder with commercially available chitin.The mixed solvent precooling of 11g NaOH, 4g urea and 85g water to-12 ℃, is added after 6g chitin powder stirs, keep 12h at-20 ℃.At room temperature thaw, promptly obtain transparent chitin solution.On sheet glass, take casting method to obtain the thick chitin solution of 1mm, immerse 5wt%H
2SO
4Place in the aqueous solution and made its gelation in 10 minutes, replace with absolute ethyl alcohol again after the washing, through supercritical CO
2Dry (40 ℃ of temperature, pressure 100kg/cm
2) make the chitin gas gel.It is 376m that nitrogen adsorption-desorption test obtains chitin gas gel specific surface area
2/ g, porosity 89%, density are 0.24g/cm
3
Embodiment 2
Chitin hydrogel among the embodiment 1 with after the trimethyl carbinol displacement, is made the chitin gas gel through lyophilize, and other steps are identical.It is 336m that nitrogen adsorption-desorption test obtains chitin gas gel specific surface area
2/ g, porosity 87%, density are 0.22g/cm
3
(comparative example 1)
Chitin solution among the embodiment 1 is obtained the chitin cross-linked hydrogel with the linking agent epoxy chloropropane through chemical reaction, be similar to jelly.Hydrogel intensity is merely tens of kPa.After absolute ethyl alcohol and trimethyl carbinol displacement, volumetric shrinkage reaches more than 90%, can't obtain gas gel.
(comparative example 2)
Chitin solution among the embodiment 1 is obtained the chitin cross-linked hydrogel with the linking agent epoxy chloropropane through chemical reaction, be similar to jelly.Hydrogel intensity is merely tens of kPa.Hydrogel place under the liquid nitrogen temperature freezing after, place the dry 12h of freeze drier, obtain the macroporous chitin foam.It is 146m that nitrogen adsorption-desorption test obtains macroporous chitin foam specific surface area
2/ g.
Embodiment 3
With the rare HCl soaking at room temperature of 5wt% 12h, filtering the washing back, to use oven dry behind the 4wt%NaOH aqueous solution soaking 12h to obtain the acetyl degree be 92% chitin powder with commercially available chitin.The mixed solvent precooling of 2g NaOH, 20g urea and 78g water to-12 ℃, is added after 0.5g chitin powder stirs, keep 12h at-20 ℃.At room temperature thaw, promptly obtain transparent chitin solution.On sheet glass, take casting method to obtain the thick chitin solution of 1mm, made its gelation in 10 minutes, replace with anhydrous methanol again after the washing, through supercritical CO with placing in the chitin solution immersion 5wt%HCl aqueous solution
2Dry (40 ℃ of temperature, pressure 100kg/cm
2) make the chitin gas gel.It is 375m that nitrogen adsorption-desorption test obtains chitin gas gel specific surface area
2/ g, porosity 97%, density are 0.04g/cm
3
Embodiment 4
The mixed solvent precooling of 25g NaOH, 0.1g urea and 79.9g water to-12 ℃, is added after the commercially available chitin powder of 1g stirs, keep 12h at-20 ℃.At room temperature thaw, promptly obtain transparent chitin solution.On sheet glass, take casting method to obtain the thick chitin solution of 1mm, chitin solution is immersed 10wt%NH
4Place in the Cl aqueous solution and made its gelation in 10 minutes, replace with acetone again after the washing, through supercritical CO
2Dry (40 ℃ of temperature, pressure 100kg/cm
2) make the chitin gas gel.It is 406m that nitrogen adsorption-desorption test obtains chitin gas gel specific surface area
2/ g, porosity 96%, density are 0.06g/cm
3
Embodiment 5
With the rare HCl soaking at room temperature of 5wt% 12h, filtering the washing back, to use oven dry behind the 4wt%NaOH aqueous solution soaking 12h to obtain the acetyl degree be 92% chitin powder with commercially available chitin.The mixed solvent precooling of 6g NaOH, 12g urea and 82g water to-12 ℃, is added after 8g chitin powder stirs, keep 12h at-20 ℃.At room temperature thaw, promptly obtain transparent chitin solution.On sheet glass, take casting method to obtain the thick chitin solution of 1mm, chitin solution is immersed 5wt%H
2SO
4/ 10wt%Na
2SO
4Place in the aqueous solution and made its gelation in 10 minutes, again with trimethyl carbinol displacement, make the chitin gas gel after the washing through lyophilize.It is 346m that nitrogen adsorption-desorption test obtains chitin gas gel specific surface area
2/ g, porosity 89%, density are 0.21g/cm
3
Embodiment 6
With the rare HCl soaking at room temperature of 5wt% 12h, filtering the washing back, to use oven dry behind the 4wt%NaOH aqueous solution soaking 12h to obtain the acetyl degree be 92% chitin powder with commercially available chitin.The mixed solvent precooling of 14g NaOH, 4g urea and 82g water to-12 ℃, is added after 8g chitin powder stirs, keep 12h at-20 ℃.At room temperature thaw, promptly obtain transparent chitin solution.On sheet glass, take casting method to obtain the thick chitin solution of 1mm; Made its gelation in 20 minutes with placing in the chitin solution immersion water; After the washing chitin hydrogel is placed under the liquid nitrogen temperature freezingly, with freeze drier lyophilize 12h, other steps are identical.It is 302m that nitrogen adsorption-desorption test obtains chitin gas gel specific surface area
2/ g, porosity 86%, density are 0.23g/cm
3
Embodiment 7
With the rare HCl soaking at room temperature of 5wt% 12h, filtering the washing back, to use oven dry behind the 4wt%NaOH aqueous solution soaking 12h to obtain the acetyl degree be 92% chitin powder with commercially available chitin.The mixed solvent precooling of 10g NaOH, 10g urea and 80g water to-12 ℃, is added after 8g chitin powder stirs, keep 12h at-20 ℃.At room temperature thaw, promptly obtain transparent chitin solution.Is that the syringe needle of 0.3mm dropwise splashes into the ETHYLE ACETATE with chitin solution from diameter, leaves standstill and makes its gelation in 30 minutes, obtains spherical chitin hydrogel, and other steps are with embodiment 1.It is 418m that nitrogen adsorption-desorption test obtains chitin gas gel specific surface area
2/ g, porosity 93%, density are 0.17g/cm
3
Embodiment 8
With the rare HCl soaking at room temperature of 5wt% 12h, filtering the washing back, to use oven dry behind the 4wt%NaOH aqueous solution soaking 12h to obtain the acetyl degree be 92% chitin powder with commercially available chitin.The mixed solvent precooling of 8g NaOH, 4.5g thiocarbamide and 87.5g water to-5 ℃, is added after 7g chitin powder stirs, keep 12h at-20 ℃.At room temperature thaw, promptly obtain transparent chitin solution.On sheet glass, take casting method to obtain the thick chitin solution of 1mm, made its gelation in 10 minutes with placing in the chitin solution immersion absolute ethyl alcohol, other steps are with embodiment 1.It is 452m that nitrogen adsorption-desorption test obtains chitin gas gel specific surface area
2/ g, porosity 94%, density are 0.16g/cm
3The stereoscan photograph of obtained chitin gas gel is as shown in Figure 1.
Embodiment 9
With the rare HCl soaking at room temperature of 5wt% 12h, filtering the washing back, to use oven dry behind the 4wt%NaOH aqueous solution soaking 12h to obtain the acetyl degree be 92% chitin powder with commercially available chitin.The mixed solvent precooling of 2g NaOH, 10g thiocarbamide and 88g water to-5 ℃, is added after 1g chitin powder stirs, keep 12h at-20 ℃.At room temperature thaw, promptly obtain transparent chitin solution.Is that the syringe needle of 0.3mm is extruded and got into the 90wt% aqueous ethanolic solution with chitin solution from diameter, leaves standstill after 10 minutes and obtains chitin hydrogel, and other steps are with embodiment 1.It is 426m that nitrogen adsorption-desorption test obtains chitin gas gel specific surface area
2/ g, porosity 96%, density are 0.08g/cm
3
Embodiment 10
The mixed solvent precooling of 25g NaOH, 0.1g thiocarbamide and 79.9g water to-5 ℃, is added after the commercially available chitin powder of 2g stirs, keep 12h at-20 ℃.At room temperature thaw, promptly obtain transparent chitin solution.On sheet glass, take casting method to obtain the thick chitin solution of 1mm; Made its gelation in 10 minutes with placing in the chitin solution immersion 5wt%KCl aqueous solution; Again successively with acetone and toluene displacement, make the chitin gas gel after the washing through constant pressure and dry (40 ℃ of temperature).It is 301m that nitrogen adsorption-desorption test obtains chitin gas gel specific surface area
2/ g, porosity 82%, density are 0.12g/cm
3
Embodiment 11
With the rare HCl soaking at room temperature of 5wt% 12h, filtering the washing back, to use oven dry behind the 4wt%NaOH aqueous solution soaking 12h to obtain the acetyl degree be 92% chitin powder with commercially available chitin.The mixed solvent precooling of 6g NaOH, 6g thiocarbamide and 88g water to-5 ℃, is added after 7g chitin powder stirs, keep 12h at-20 ℃.At room temperature thaw, promptly obtain transparent chitin solution.On sheet glass, take casting method to obtain the thick chitin solution of 1mm, with chitin solution immerse methanol/ethanol (1: 1, place in v/v) and made its gelation in 10 minutes, other steps are with embodiment 1.It is 361m that nitrogen adsorption-desorption test obtains chitin gas gel specific surface area
2/ g, porosity 92%, density are 0.18g/cm
3
Embodiment 12
With the rare HCl soaking at room temperature of 5wt% 12h, filtering the washing back, to use oven dry behind the 4wt%NaOH aqueous solution soaking 12h to obtain the acetyl degree be 92% chitin powder with commercially available chitin.The mixed solvent precooling of 14g NaOH, 3g thiocarbamide and 83g water to-5 ℃, is added after 5g chitin powder stirs, keep 12h at-20 ℃.At room temperature thaw, promptly obtain transparent chitin solution.
Embodiment 13
With the rare HCl soaking at room temperature of 5wt% 12h, filtering the washing back, to use oven dry behind the 4wt%NaOH aqueous solution soaking 12h to obtain the acetyl degree be 92% chitin powder with commercially available chitin.The mixed solvent precooling of 10g NaOH, 4.5g thiocarbamide and 85.5g water to-5 ℃, is added after 5g chitin powder stirs, keep 12h at-20 ℃.At room temperature thaw, promptly obtain transparent chitin solution.
Embodiment 14
With the rare HCl soaking at room temperature of 5wt% 12h, filtering the washing back, to use oven dry behind the 4wt%NaOH aqueous solution soaking 12h to obtain the acetyl degree be 92% chitin powder with commercially available chitin.With 8g LiOHH
2The mixed solvent precooling of O (being 4.6g LiOH), 4g urea and 88g water after adding 8g chitin powder stirs, keeps 8hs at-25 ℃ to-12 ℃.At room temperature thaw, promptly obtain transparent chitin solution.On sheet glass, take casting method to obtain the thick chitin solution of 1mm, place in the immersion methyl alcohol and made its gelation in 10 minutes, replace with absolute ethyl alcohol again after the washing, through supercritical CO
2Dry (40 ℃ of temperature, pressure 100kg/cm
2) make the chitin gas gel.It is 399m that nitrogen adsorption-desorption test obtains chitin gas gel specific surface area
2/ g, porosity 92%, density are 0.19g/cm
3
(comparative example 3)
Chitin solution among the embodiment 14 is obtained the chitin cross-linked hydrogel with the linking agent epoxy chloropropane through chemical reaction, be similar to jelly.Hydrogel intensity is merely tens of kPa.After absolute ethyl alcohol and trimethyl carbinol displacement, volumetric shrinkage reaches more than 90%, can't obtain gas gel.
(comparative example 4)
Chitin solution among the embodiment 14 is obtained the chitin cross-linked hydrogel with the linking agent epoxy chloropropane through chemical reaction, be similar to jelly.Hydrogel intensity is merely tens of kPa.Hydrogel place under the liquid nitrogen temperature freezing after, place the dry 12h of freeze drier, obtain the macroporous chitin foam.It is 58m that nitrogen adsorption-desorption test obtains macroporous chitin foam specific surface area
2/ g.
Embodiment 15
With the rare HCl soaking at room temperature of 5wt% 12h, filtering the washing back, to use oven dry behind the 4wt%NaOH aqueous solution soaking 12h to obtain the acetyl degree be 92% chitin powder with commercially available chitin.With 5.2g LiOHH
2The mixed solvent precooling of O (being 3g LiOH), 20g urea and 74.8g water after adding 1g chitin powder stirs, keeps 8hs at-25 ℃ to-12 ℃.At room temperature thaw, promptly obtain transparent chitin solution.On sheet glass, take casting method to obtain the thick chitin solution of 1mm, chitin solution is immersed 50wt% ethanol (moisture 50%) placement made its gelation in 10 minutes, again with the absolute ethyl alcohol displacement, other steps are with embodiment 1 after the washing.It is 392m that nitrogen adsorption-desorption test obtains chitin gas gel specific surface area
2/ g, porosity 94%, density are 0.07g/cm
3
Embodiment 16
With the rare HCl soaking at room temperature of 5wt% 12h, filtering the washing back, to use oven dry behind the 4wt%NaOH aqueous solution soaking 12h to obtain the acetyl degree be 92% chitin powder with commercially available chitin.With 17.5g LiOHH
2The mixed solvent precooling of O (being 10g LiOH), 0.1g urea and 87.7g water after adding 3g chitin powder stirs, keeps 8hs at-25 ℃ to-12 ℃.At room temperature thaw, promptly obtain transparent chitin solution.On sheet glass, take casting method to obtain the thick chitin solution of 1mm, made its gelation in 20 minutes with placing in the chitin solution immersion water, again with the absolute ethyl alcohol displacement, other steps are with embodiment 1 after the washing.It is 353m that nitrogen adsorption-desorption test obtains chitin gas gel specific surface area
2/ g, porosity 90%, density are 0.12g/cm
3
Embodiment 17
With the rare HCl soaking at room temperature of 5wt% 12h, filtering the washing back, to use oven dry behind the 4wt%NaOH aqueous solution soaking 12h to obtain the acetyl degree be 92% chitin powder with commercially available chitin.With 7g LiOHH
2The mixed solvent precooling of O (being 4g LiOH), 12g urea and 81g water after adding 7g chitin powder stirs, keeps 8hs at-25 ℃ to-12 ℃.At room temperature thaw, promptly obtain transparent chitin solution.
Embodiment 18
With the rare HCl soaking at room temperature of 5wt% 12h, filtering the washing back, to use oven dry behind the 4wt%NaOH aqueous solution soaking 12h to obtain the acetyl degree be 92% chitin powder with commercially available chitin.With 14g LiOHH
2The mixed solvent precooling of O (being 8g LiOH), 4g urea and 85.5g water after adding 12g chitin powder stirs, keeps 8hs at-25 ℃ to-12 ℃.At room temperature thaw, promptly obtain transparent chitin solution.
Embodiment 19
With the rare HCl soaking at room temperature of 5wt% 12h, filtering the washing back, to use oven dry behind the 4wt%NaOH aqueous solution soaking 12h to obtain the acetyl degree be 92% chitin powder with commercially available chitin.With 5.2g LiOHH
2The mixed solvent precooling of O (being 3g LiOH), 10g thiocarbamide and 84.8g water after adding 1g chitin powder stirs, keeps 8hs at-25 ℃ to-5 ℃.At room temperature thaw, promptly obtain transparent chitin solution.
Embodiment 20
With the rare HCl soaking at room temperature of 5wt% 12h, filtering the washing back, to use oven dry behind the 4wt%NaOH aqueous solution soaking 12h to obtain the acetyl degree be 92% chitin powder with commercially available chitin.With 17.5g LiOHH
2The mixed solvent precooling of O (being 10g LiOH), 0.1g thiocarbamide and 87.7g water after adding 12g chitin powder stirs, keeps 8hs at-25 ℃ to-5 ℃.At room temperature thaw, promptly obtain transparent chitin solution.
Embodiment 21
With the rare HCl soaking at room temperature of 5wt% 12h, filtering the washing back, to use oven dry behind the 4wt%NaOH aqueous solution soaking 12h to obtain the acetyl degree be 92% chitin powder with commercially available chitin.With 7g LiOHH
2The mixed solvent precooling of O (being 4g LiOH), 6g thiocarbamide and 87g water after adding 5g chitin powder stirs, keeps 8hs at-25 ℃ to-5 ℃.At room temperature thaw, promptly obtain transparent chitin solution.
Embodiment 22
With the rare HCl soaking at room temperature of 5wt% 12h, filtering the washing back, to use oven dry behind the 4wt%NaOH aqueous solution soaking 12h to obtain the acetyl degree be 92% chitin powder with commercially available chitin.With 14g LiOHH
2The mixed solvent precooling of O (being 8g LiOH), 3g thiocarbamide and 86.5g water after adding 5g chitin powder stirs, keeps 8hs at-25 ℃ to-5 ℃.At room temperature thaw, promptly obtain transparent chitin solution.
Embodiment 23
With the rare HCl soaking at room temperature of 5wt% 12h, filtering the washing back, to use oven dry behind the 4wt%NaOH aqueous solution soaking 12h to obtain the acetyl degree be 92% chitin powder with commercially available chitin.With 8.8g LiOHH
2The mixed solvent precooling of O (being 5g LiOH), 4g thiocarbamide and 87.2g water after adding 8g chitin powder stirs, keeps 8hs at-25 ℃ to-5 ℃.At room temperature thaw, promptly obtain transparent chitin solution.
On sheet glass, take casting method to obtain the thick chitin solution of 1mm, immerse 5wt%H
2SO
4Place in the aqueous solution and made its gelation in 10 minutes, replace with absolute ethyl alcohol again after the washing, through supercritical CO
2Dry (40 ℃ of temperature, pressure 100kg/cm
2) make the chitin gas gel.It is 372m that nitrogen adsorption-desorption test obtains chitin gas gel specific surface area
2/ g, porosity 90%, density are 0.16g/cm
3
Embodiment 24
The chitin hydrogel that obtains among the embodiment 8 is immersed in the 20wt%NaOH aqueous solution, and 90 ℃ of heating 48h obtain deacetylation and are 70% aquagel after the washing.After the absolute ethyl alcohol displacement, through supercritical CO
2Dry (40 ℃ of temperature, pressure 100kg/cm
2) make the chitosan gas gel.It is 401m that nitrogen adsorption-desorption test obtains chitosan gas gel specific surface area
2/ g, porosity 92%, density are 0.17g/cm
3The stereoscan photograph of chitosan gas gel is as shown in Figure 2.
Embodiment 25
The chitin hydrogel that obtains among the embodiment 8 is immersed in the 30wt%NaOH aqueous solution, and 60 ℃ of heating 12h obtain deacetylation and are 89% aquagel after the washing.Aquagel with after the trimethyl carbinol displacement, is made the chitosan gas gel through lyophilize.It is 367m that nitrogen adsorption-desorption test obtains chitosan gas gel specific surface area
2/ g, porosity 89%, density are 0.20g/cm
3
Embodiment 26
The chitin hydrogel that obtains among the embodiment 14 is immersed in the 40wt%NaOH aqueous solution, and 40 ℃ of heating 4h repeat 2 times.Obtain deacetylation after the washing and be 81% aquagel.After the absolute ethyl alcohol displacement, through supercritical CO
2Dry (40 ℃ of temperature, pressure 100kg/cm
2) make the chitosan gas gel.It is 368m that nitrogen adsorption-desorption test obtains chitosan gas gel specific surface area
2/ g, porosity 91%, density are 0.19g/cm
3
Embodiment 27
The chitin hydrogel that obtains among the embodiment 14 is immersed in the 45wt%NaOH aqueous solution, and 110 ℃ of heating 1h obtain deacetylation and are 89% aquagel after the washing.Aquagel is placed under the liquid nitrogen temperature freezing, with freeze drier lyophilize 12h, other steps are identical.It is 327m that nitrogen adsorption-desorption test obtains chitosan gas gel specific surface area
2/ g, porosity 88%, density are 0.22g/cm
3
Embodiment 28
The chitin hydrogel that embodiment 1 is obtained immerse tetraethoxy/ethanolic soln (3: 7, v/v) in 30 minutes, take out and contain the tetraethoxy chitin hydrogel, in 0.1mol/L ammoniacal liquor, placing and making the tetraethoxy complete hydrolysis in 10 minutes is SiO
2Nanoparticle, the chitin hydrogel water white transparency.After this gel washing, be replaced into absolute ethyl alcohol, pass through supercritical CO then
2Drying obtains SiO
2Nanoparticle/chitin composite aerogel.Obtain SiO by nitrogen adsorption-desorption experiment
2The specific surface area of nanoparticle/chitin composite aerogel is 652m
2/ g, density 0.30g/cm
3
Embodiment 29
The chitin hydrogel that embodiment 14 is obtained immerses 1.5mol/L FeCl
3In the aqueous solution 30 minutes, take out and contain FeCl
3Chitin hydrogel, in the 0.1mol/L NaOH aqueous solution, place and made Fe in 10 minutes
3+Complete reaction is hydration Fe
2O
3Nanoparticle.After this gel washing, be replaced into absolute ethyl alcohol, pass through supercritical CO then
2Drying obtains Fe
2O
3Nanoparticle/chitin composite aerogel.Obtain Fe by nitrogen adsorption-desorption experiment
2O
3The specific surface area of nanoparticle/chitin composite aerogel is 268m
2/ g, density 0.26g/cm
3
Embodiment 30
The aquagel that embodiment 14 is obtained immerses 1.5mol/L FeCl
36H
2O/0.75mol/LFeCl
24H
2In the O ethanolic soln 30 minutes, take out and contain FeCl
3And FeCl
2Chitosan gel rubber, in the 0.1mol/L propylene oxide 60 ℃ the heating 30 minutes, make FeCl
3And FeCl
2The complete hydrolysis reaction generates Fe
3O
4Nanoparticle, chitosan gel rubber is a black, has tangible magnetic.After this gel washing, be replaced into absolute ethyl alcohol, pass through supercritical CO then
2Drying obtains Fe
3O nanoparticle/chitosan composite aerogel.Obtain Fe by nitrogen adsorption-desorption experiment
3O
4The specific surface area of nanoparticle/chitosan composite aerogel is 292m
2/ g, density 0.32g/cm
3
Embodiment 31
The aquagel that embodiment 25 is obtained immerses 0.1mol/L AgNO
3In the aqueous solution 30 minutes, take out and contain AgNO
3Aquagel, at 0 ℃ of 0.5wt%NaBH
4Placement made Ag+ be reduced to the Ag nanoparticle fully in 30 minutes in the aqueous solution, and aquagel is yellow.After this hydrogel washing, be replaced into absolute ethyl alcohol, pass through supercritical CO then
2Drying obtains Ag nanoparticle/chitosan composite aerogel.The specific surface area that is obtained composite aerogel by nitrogen adsorption-desorption experiment is 378m
2/ g, density 0.21g/cm
3
Embodiment 32
The chitin gas gel that embodiment 1 is obtained is heated to 600 ℃ from room temperature with 10 ℃/min, and nitrogen obtains black porous carbon gas gel as shielding gas.The specific surface area that is obtained carbon aerogels by nitrogen adsorption-desorption experiment is 608m
2/ g.The stereoscan photograph of carbon aerogels is as shown in Figure 3.
Embodiment 33
The chitin gas gel that embodiment 1 is obtained is heated to 150 ℃ from room temperature with 10 ℃/min in HCl atmosphere, nitrogen obtains black porous carbon gas gel as shielding gas.The specific surface area that is obtained carbon aerogels by nitrogen adsorption-desorption experiment is 369m
2/ g.
Embodiment 34
The chitosan gas gel that embodiment 25 is obtained is heated to 800 ℃ from room temperature with 10 ℃/min, and nitrogen obtains black porous carbon gas gel as shielding gas.The specific surface area that is obtained carbon aerogels by nitrogen adsorption-desorption experiment is 820m
2/ g.
Embodiment 35
The chitosan gas gel that embodiment 26 is obtained is heated to 1000 ℃ from room temperature with 10 ℃/min, and nitrogen obtains black porous carbon gas gel as shielding gas.The specific surface area that is obtained carbon aerogels by nitrogen adsorption-desorption experiment is 1089m
2/ g.
Embodiment 36
Chitin/Fe that embodiment 29 is obtained
2O
3Composite aerogel is heated to 400 ℃ from room temperature with 10 ℃/min, and nitrogen obtains black porous carbon/Fe as shielding gas
2O
3Composite aerogel.Obtain carbon/Fe by nitrogen adsorption-desorption experiment
2O
3The specific surface area of composite carbon gas gel is 450m
2/ g.
Claims (21)
1. the preparation method of a chitin gas gel is characterized in that: chitin solution is immersed in the peptizer, regenerate, obtain chitin hydrogel after the washing; Water in the chitin hydrogel is replaced into organic liquid obtains the chitin organogel; Chitin hydrogel or organogel drying are removed liquid, obtain the chitin gas gel; Said peptizer is a water, or is added with the water of monovalent cation therein, or water cut is lower than the nonpolar organic liquid of lower boiling of 50 wt%.
2. preparation method according to claim 1 is characterized in that: said monovalent cation is H
+, NH
4 +, Li
+, Na
+Or K
+The nonpolar organic liquid of said lower boiling is alcohol, ketone, ester or its mixture.
3. preparation method according to claim 2 is characterized in that: said alcohol is methyl alcohol, ethanol; Said ketone is acetone; Said ester is an ETHYLE ACETATE.
4. preparation method according to claim 1 and 2; It is characterized in that: the preparation method of said chitin solution; The solvent that adopts is alkali aqueous solution, alkali-aqueous solution of urea, alkali-thiourea solution or its mixing solutions; Solvent mixes with chitin and is refrigerated to below freezingly, obtains chitin solution above freezing thawing.
5. preparation method according to claim 4; It is characterized in that: said chitin solution is to mix with chitin and be refrigerated to below freezingly with the solvent that the water of 2～25 wt% NaOH, 0.1～20 wt% urea and surplus constitutes, and obtains above freezing thawing then.
6. preparation method according to claim 4; It is characterized in that: said chitin solution is to mix with chitin and be refrigerated to below freezingly with the solvent that the water of 3.0～10 wt% LiOH, 0.1～20 wt% urea and surplus constitutes, and obtains above freezing thawing then.
7. preparation method according to claim 4; It is characterized in that: said chitin solution is to mix with chitin and be refrigerated to below freezingly with the solvent that the water of 2～25 wt% NaOH, 0.1～10 wt% thiocarbamide and surplus constitutes, and obtains above freezing thawing then.
8. preparation method according to claim 4; It is characterized in that: said chitin solution is to mix with chitin and be refrigerated to below freezingly with the solvent that the water of 3.0～7 wt% LiOH, 0.1～10 wt% thiocarbamide and surplus constitutes, and obtains above freezing thawing then.
9. preparation method according to claim 1 and 2; It is characterized in that: the organic liquid that is used to replace chitin hydrogel is lower boiling, volatile alkanes, halogenated hydrocarbon, alcohols, phenols, ether and acetals, ketone, acid and anhydrides, ester class, itrogenous organic substance, the organic compound of sulfur-bearing, or aforementioned various mixtures of liquids.
10. preparation method according to claim 1 and 2 is characterized in that: described dry link utilizes supercritical drying, constant pressure and dry or lyophilize to remove liquid medium.
11. the preparation method of a chitosan gas gel is characterized in that: chitin solution is immersed in the peptizer, and regeneration obtains chitin hydrogel after the washing; Chitin hydrogel is deacetylated, obtain aquagel after the washing; Water in the aquagel is replaced into organic liquid obtains the chitosan organogel; Aquagel or organogel drying are removed liquid, obtain the chitosan gas gel; Said peptizer is a water, or is added with the water of monovalent cation therein, or water cut is lower than the nonpolar organic liquid of lower boiling of 50 wt%.
12. preparation method according to claim 11 is characterized in that: said monovalent cation is H
+, NH
4 +, Li
+, Na
+Or K
+The nonpolar organic liquid of said lower boiling is alcohol, ketone, ester or its mixture.
13. preparation method according to claim 12 is characterized in that: said alcohol is methyl alcohol, ethanol; Said ketone is acetone; Said ester is an ETHYLE ACETATE.
14. according to claim 11 or 12 described preparing methods; It is characterized in that: the preparation method of said chitin solution; The solvent that adopts is alkali aqueous solution, alkali-aqueous solution of urea, alkali-thiourea solution or its mixing solutions; Solvent mixes with chitin and is refrigerated to below freezingly, obtains chitin solution above freezing thawing.
15. preparation method according to claim 14; It is characterized in that: said chitin solution is to mix with chitin and be refrigerated to below freezingly with the solvent that the water of 2～25 wt% NaOH, 0.1～20 wt% urea and surplus constitutes, and obtains above freezing thawing then.
16. preparation method according to claim 14; It is characterized in that: said chitin solution is to mix with chitin and be refrigerated to below freezingly with the solvent that the water of 3.0～10 wt% LiOH, 0.1～20 wt% urea and surplus constitutes, and obtains above freezing thawing then.
17. preparation method according to claim 14; It is characterized in that: said chitin solution is to mix with chitin and be refrigerated to below freezingly with the solvent that the water of 2～25 wt% NaOH, 0.1～10 wt% thiocarbamide and surplus constitutes, and obtains above freezing thawing then.
18. preparation method according to claim 14; It is characterized in that: said chitin solution is to mix with chitin and be refrigerated to below freezingly with the solvent that the water of 3.0～10 wt% LiOH, 0.1～10 wt% thiocarbamide and surplus constitutes, and obtains above freezing thawing then.
19. according to claim 11 or 12 described preparing methods; It is characterized in that: the organic liquid that is used to replace chitin hydrogel is lower boiling, volatile alkanes, halogenated hydrocarbon, alcohols, phenols, ether and acetals, ketone, acid and anhydrides, ester class, itrogenous organic substance, the organic compound of sulfur-bearing, or aforementioned various mixtures of liquids.
20. according to claim 11 or 12 described preparing methods, it is characterized in that: described dry link utilizes supercritical drying, constant pressure and dry or lyophilize to remove liquid medium.
21. the preparation method of a carbon aerogels is characterized in that, with the prepared chitin gas gel of claim 1～10 or the prepared chitosan gas gel of claim 11～20 under inert atmosphere protection, 150
oObtain carbon aerogels after the above thermal treatment of C.
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