CN102417606B - Preparation method of chitin aerogel - Google Patents
Preparation method of chitin aerogel Download PDFInfo
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- CN102417606B CN102417606B CN201110221079.7A CN201110221079A CN102417606B CN 102417606 B CN102417606 B CN 102417606B CN 201110221079 A CN201110221079 A CN 201110221079A CN 102417606 B CN102417606 B CN 102417606B
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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 preparation method who the present invention relates to a kind of chitin aerogel, belongs to field of new.
Technical background
Aerogel 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 be also called " cigarette freezing ".
Aerogel has the nanoporous three-dimensional net structure of high-permeability, very high porosities, extra-low density, high-specific surface area, structure and performance are obviously different from pore space structure at the porous material of micron and millimeter magnitude, at aspects such as separation, absorption, catalysis, photoelectricity, sensor, biological medicines, have a wide range of applications.
Aerogel is as a kind of advanced material of developed recently, conventionally from inorganic pioneer, by sol-gel method or from organic precursor, by polyreaction, make wet gel, then utilize the technology such as supercritical drying to remove the liquid in wet gel, and keep network structure substantially constant.
Conventionally using silicon sol as nanometre glue, doping colloid Pt, Au, carbon black, zeolite, TiO
2, the synthetic silica aerogel matrix material such as porous chalcogen semiconductor (CdS, CdSe, ZnS, PbS); The organic aerogel being formed by resorcin/formaldehyde, melamine/formaldehyde and phenol/formaldehyde etc. is prepared carbon aerogels through high temperature pyrolysis.
Yet the aerogel of having reported at present remains in weak point, if inorganic aerogels is to moisture-sensitive, easily crisp, need carries out hydrophobically modified and be cross-linked and improve physical strength with polymer; Organic aerogel synthesis condition is comparatively complicated, and does not possess biocompatibility.In recent years, from natural polymer raw material, as Mierocrystalline cellulose and chitin synthetic gas gel also attract wide attention.
Chitin is the 2-acetylaminohydroxyphenylarsonic acid 2-deoxidation-callose of Isosorbide-5-Nitrae-keyed jointing, is extensively present in insect, Crustaceans and fungal cell wall.On the annual earth, by biosynthetic chitin, can reach hundred million tons of hundreds ofs, be that occurring in nature is only second to the renewable natural polymer of cellulosic second largest class.Chitin can occur deacetylated under alkaline condition, is called chitosan when deacetylation is greater than 50%.The molecular structure of their this uniquenesses, gives its charming biological activity.Large quantity research shows, chitin and chitosan is except having the performances such as nontoxic, good biocompatibility, biodegradability, also has hemostasis, analgesia, promotion wound healing, the property such as antibacterial.But, because chitin degree of crystallinity is high, contain in a large amount of molecules and intermolecular hydrogen bonding, water insoluble and conventional organic solvent, thus limited the application of chitin.Known chitin solvent, as 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 large, seriously polluted, even make degradation of chitin, the expensive production cost that causes is too high.EP051421 be take strong acid trichoroacetic acid(TCA) as solvent, and corrodibility is stronger.The double solvents that US4029727 forms with amide solvent and LiCl dissolves chitin, and solvent price is high, and production cost is high.As chitin is dissolved in, in 6%LiCl/DMAc, obtain concentration and be 1.9% chitin solution, treat that its gelation after washing obtains chitin hydrogel, with methyl alcohol displacement, then pass through supercritical CO
2be dried and obtain chitin aerogel, 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, separated, purifying and reclaim the 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 further provide chitin solution thus to prepare the preparation method of chitin aerogel and carbon aerogels.
The present invention, for solving the problems of the technologies described above, first provides the preparation method of chitin solution:
The solvent system adopting 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, above freezing thawing, obtains chitin solution.
Preferably chitin solution is dissolved in NaOH/ aqueous solution of urea and is made by chitin as one, and wherein NaOH concentration is 2～25wt%, is preferably 6～14wt%; Urea concentration is 0.1～20wt%, is preferably 4～12wt%; Surplus is water.
Preferred as another, chitin solution is dissolved in LiOH/ aqueous solution of urea and is made by chitin, and wherein LiOH concentration is 3～10wt%, is preferably 4～8wt%; Urea concentration is 0.1～20wt%, is preferably 4～12wt%; Surplus is water.
Preferred as another, chitin solution is dissolved in NaOH/ thiourea solution and is made by chitin, and wherein NaOH concentration is 2～25wt%, is preferably 6～14wt%; Thiourea concentration is 0.1～10wt%, is preferably 3～6wt%; Surplus is water.
Preferred as another, chitin solution is dissolved in LiOH/ thiourea solution and is made by chitin, and wherein LiOH concentration is 3～10wt%, is preferably 4～8wt%; Thiourea concentration is 0.1～10wt%, is preferably 3～6wt%; Surplus is water.
As above-mentioned chitin source, can be the halobiontic shells such as shrimp, crab, cuttlefish, the epidermis of the insects such as cockroach, silkworm chrysalis, and one or more of the chitin in mushroom cell.Use the front method purifying through known technology and have no particular limits.As calcium salt is removed in acid treatment, alkaline purification is except Deproteinization, oxide treatment decolouring etc.
The method that the chitin solution being prepared above by the present invention is prepared chitin aerogel is:
Chitin solution is immersed in peptizer, and regeneration, obtains chitin hydrogel after washing; Water in chitin hydrogel is replaced into organic liquid and obtains chitin organogel; Remove liquid by chitin hydrogel or organogel are dry, obtain chitin aerogel.
Chitin solution is immersed in peptizer, and regeneration, obtains chitin hydrogel after washing; Chitin hydrogel is deacetylated, after washing, obtain aquagel; Water in aquagel is replaced into organic liquid and obtains chitosan organogel; Remove liquid by aquagel or organogel are dry, obtain chitosan aerogel.
Described chitin hydrogel is deacetylated is by excessive NaOH solution soaking for chitin hydrogel, cooling, removes remaining NaOH, obtains aquagel.The concentration of described NaOH solution is 20wt%～45wt%, at 40～110 ℃, soaks 1～48h.
Above in the preparation process of chitin aerogel and chitosan aerogel,
Described peptizer can be that water content is lower than 50wt%, preferably lower than the nonpolar organic liquid of lower boiling of 10wt%.In a preferred preparation technology, liquid water content is lower than 5wt%.The example of the suitable peptizer of this class 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 character that viscosity is low, is conducive to solidifying of chitin solution.In addition, in the process reclaiming at peptizer, be conducive to separation.
Peptizer can be also water or add cationic water, preferably contains for example H of monovalent cation
+, NH
4 +, Li
+, Na
+or K
+the aqueous solution, such solution can be such as water-soluble and make by hydrochloric acid, sulfuric acid, nitric acid, acetic acid, ammonium sulfate, ammonium acetate, lithium chloride, sodium sulfate, potassium sulfate etc.
Described 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 for replacing the organic solvent of chitin, aquagel, or the mixture of aforementioned all kinds of SOLVENTS.In the organic solvent of enumerating in the above, in test, find, from improving performance and the cost angle of chitin of the present invention, chitosan material, consider, preferably use alkanes, alcohols and ketone compounds, more preferably use methyl alcohol, ethanol or acetone.
Above in the preparation process of chitin aerogel and chitosan aerogel, described dry link can be utilized conventional drying means, for example, usining carbonic acid gas, methyl alcohol, ethanol, acetone carries out supercritical drying as supercutical fluid, or carries out constant pressure and dry and liquid medium is removed in lyophilize.
Chitin aerogel or chitosan aerogel, under inert atmosphere protection, are obtained to carbon aerogels after 150 ℃ of above thermal treatments.
Inert atmosphere does not refer to and reacts with chitin, chitosan, prevents gas or gaseous mixture that chitin, chitosan material at high temperature burn.Experiment shows, following gas is especially applicable to being used as inert atmosphere: nitrogen, carbonic acid gas, helium, neon and argon gas.Also can use the mixture of these gases.Appropriate sour gas, as HCl can catalysis chitin, the carbonization of chitosan.
The test of nitrogen adsorption-desorption obtains chitin, chitosan aerogel specific surface area reaches 300m
2/ g, reaches 350m preferably
2/ g, the higher 400m that is greater than
2/ g.The test of nitrogen adsorption-desorption obtains carbon aerogels specific surface area and reaches 300m
2/ g, reaches 600m preferably
2/ g, the higher 1000m that is greater than
2/ g.
At chitin and chitosan hydrogel of the present invention, can also carry out surface hydroxyl or amino modification to it, as carboxymethylation, hydroxyethylation, hydroxypropylation, quaternized etc.Can in chitin and chitosan hydrogel, synthesize or add inorganics, polymer, filler etc.Inorganics is as silicon-dioxide, ferric oxide, Z 250, clay, titanium dioxide etc.Polymer is as Mierocrystalline cellulose, collagen, Lalgine, poly(lactic acid), polyacrylate(s), PVA etc.Filler is as carbon black, glycerine, propylene glycol, butyleneglycol or PEG400 etc.Also can add fiber reinforced material as glass fibre, carbon fiber, cellulose whiskers, chitin whisker etc.Can synthesize or add at least one of these additives or filler.
The invention provides a kind of inexpensive, pollution-free, easy method and obtain high-quality chitin solution, and utilize this chitin solution to adopt corresponding method preparation to there is chitin, chitosan aerogel and the carbon aerogels thereof of high-specific surface area.The invention has the advantages that: the solvent adopting is NaOH, LiOH, urea (and/or thiocarbamide) and water, and production process is nontoxic, pollution-free, is conducive to environment protection and operator ' s health; With respect to organic solvents such as NMMO, ionic liquid and LiCl/DMAc, be to there is method more easy to operate, that cost is effectively prepared chitin, chitosan aerogel, low price, green non-pollution, simple to operation, saved resource and the energy; Chitin/chitosan aerogel 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.
Accompanying drawing explanation
Fig. 1 shows the stereoscan photograph of the embodiment of the present invention 8 chitin aerogels;
Fig. 2 shows the stereoscan photograph of the embodiment of the present invention 24 chitosan aerogels;
Fig. 3 illustrates the stereoscan photograph of the carbon aerogels after embodiment 32 chitin aerogel carbonizations.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is described further:
Embodiment 1
By the rare HCl soaking at room temperature of 5wt% 12h for commercially available chitin, filtering after washing and obtaining acetyl degree by 4wt%NaOH aqueous solution soaking 12h post-drying is 92% chitin powder.The mixed solvent of 11g NaOH, 4g urea and 85g water is chilled to-12 ℃ in advance, after adding 6g chitin powder to stir, at-20 ℃, keeps 12h.At room temperature thaw, obtain transparent chitin solution.On sheet glass, take casting method to obtain the chitin solution that 1mm is thick, immerse 5wt%H
2sO
4in the aqueous solution, place and make its gelation in 10 minutes, after washing, with dehydrated alcohol, replace again, through supercritical CO
2dry (40 ℃ of temperature, pressure 100kg/cm
2) make chitin aerogel.It is 376m that the test of nitrogen adsorption-desorption obtains chitin aerogel specific surface area
2/ g, porosity 89%, density is 0.24g/cm
3.
Embodiment 2
Chitin hydrogel in embodiment 1, with after trimethyl carbinol displacement, is made to chitin aerogel through lyophilize, and other steps are identical.It is 336m that the test of nitrogen adsorption-desorption obtains chitin aerogel specific surface area
2/ g, porosity 87%, density is 0.22g/cm
3.
(comparative example 1)
Chitin solution in embodiment 1 is obtained to chitin cross-linked hydrogel with linking agent epoxy chloropropane through chemical reaction, be similar to jelly.Hydrogel intensity is only tens of kPa.After dehydrated alcohol and trimethyl carbinol displacement, volumetric shrinkage reaches more than 90%, cannot obtain aerogel.
(comparative example 2)
Chitin solution in embodiment 1 is obtained to chitin cross-linked hydrogel with linking agent epoxy chloropropane through chemical reaction, be similar to jelly.Hydrogel intensity is only tens of kPa.Hydrogel be placed in freezing under liquid nitrogen temperature after, be placed in the dry 12h of freeze drier, obtain macroporous chitin foam.It is 146m that the test of nitrogen adsorption-desorption obtains macroporous chitin foam specific surface area
2/ g.
Embodiment 3
By the rare HCl soaking at room temperature of 5wt% 12h for commercially available chitin, filtering after washing and obtaining acetyl degree by 4wt%NaOH aqueous solution soaking 12h post-drying is 92% chitin powder.The mixed solvent of 2g NaOH, 20g urea and 78g water is chilled to-12 ℃ in advance, after adding 0.5g chitin powder to stir, at-20 ℃, keeps 12h.At room temperature thaw, obtain transparent chitin solution.On sheet glass, take casting method to obtain the chitin solution that 1mm is thick, chitin solution is immersed in the 5wt%HCl aqueous solution and places and make its gelation in 10 minutes, after washing, with anhydrous methanol, replace again, through supercritical CO
2dry (40 ℃ of temperature, pressure 100kg/cm
2) make chitin aerogel.It is 375m that the test of nitrogen adsorption-desorption obtains chitin aerogel specific surface area
2/ g, porosity 97%, density is 0.04g/cm
3.
Embodiment 4
The mixed solvent of 25g NaOH, 0.1g urea and 79.9g water is chilled to-12 ℃ in advance, after adding the commercially available chitin powder of 1g to stir, at-20 ℃, keeps 12h.At room temperature thaw, obtain transparent chitin solution.On sheet glass, take casting method to obtain the chitin solution that 1mm is thick, chitin solution is immersed to 10wt%NH
4in the Cl aqueous solution, place and make its gelation in 10 minutes, after washing, with acetone, replace again, through supercritical CO
2dry (40 ℃ of temperature, pressure 100kg/cm
2) make chitin aerogel.It is 406m that the test of nitrogen adsorption-desorption obtains chitin aerogel specific surface area
2/ g, porosity 96%, density is 0.06g/cm
3.
Embodiment 5
By the rare HCl soaking at room temperature of 5wt% 12h for commercially available chitin, filtering after washing and obtaining acetyl degree by 4wt%NaOH aqueous solution soaking 12h post-drying is 92% chitin powder.The mixed solvent of 6g NaOH, 12g urea and 82g water is chilled to-12 ℃ in advance, after adding 8g chitin powder to stir, at-20 ℃, keeps 12h.At room temperature thaw, obtain transparent chitin solution.On sheet glass, take casting method to obtain the chitin solution that 1mm is thick, chitin solution is immersed to 5wt%H
2sO
4/ 10wt%Na
2sO
4in the aqueous solution, place and make its gelation in 10 minutes, after washing, again with trimethyl carbinol displacement, through lyophilize, make chitin aerogel.It is 346m that the test of nitrogen adsorption-desorption obtains chitin aerogel specific surface area
2/ g, porosity 89%, density is 0.21g/cm
3.
Embodiment 6
By the rare HCl soaking at room temperature of 5wt% 12h for commercially available chitin, filtering after washing and obtaining acetyl degree by 4wt%NaOH aqueous solution soaking 12h post-drying is 92% chitin powder.The mixed solvent of 14g NaOH, 4g urea and 82g water is chilled to-12 ℃ in advance, after adding 8g chitin powder to stir, at-20 ℃, keeps 12h.At room temperature thaw, obtain transparent chitin solution.On sheet glass, take casting method to obtain the chitin solution that 1mm is thick, chitin solution is immersed in the water to place and within 20 minutes, makes its gelation, after washing, chitin hydrogel is placed under liquid nitrogen temperature freezingly, with freeze drier lyophilize 12h, other steps are identical.It is 302m that the test of nitrogen adsorption-desorption obtains chitin aerogel specific surface area
2/ g, porosity 86%, density is 0.23g/cm
3.
Embodiment 7
By the rare HCl soaking at room temperature of 5wt% 12h for commercially available chitin, filtering after washing and obtaining acetyl degree by 4wt%NaOH aqueous solution soaking 12h post-drying is 92% chitin powder.The mixed solvent of 10g NaOH, 10g urea and 80g water is chilled to-12 ℃ in advance, after adding 8g chitin powder to stir, at-20 ℃, keeps 12h.At room temperature thaw, obtain transparent chitin solution.The syringe needle that is 0.3mm from diameter by chitin solution dropwise splashes into ethyl acetate, within standing 30 minutes, makes its gelation, obtains spherical chitin hydrogel, and other steps are with embodiment 1.It is 418m that the test of nitrogen adsorption-desorption obtains chitin aerogel specific surface area
2/ g, porosity 93%, density is 0.17g/cm
3.
Embodiment 8
By the rare HCl soaking at room temperature of 5wt% 12h for commercially available chitin, filtering after washing and obtaining acetyl degree by 4wt%NaOH aqueous solution soaking 12h post-drying is 92% chitin powder.The mixed solvent of 8g NaOH, 4.5g thiocarbamide and 87.5g water is chilled to-5 ℃ in advance, after adding 7g chitin powder to stir, at-20 ℃, keeps 12h.At room temperature thaw, obtain transparent chitin solution.On sheet glass, take casting method to obtain the chitin solution that 1mm is thick, chitin solution is immersed in dehydrated alcohol and places and within 10 minutes, make its gelation, other steps are with embodiment 1.It is 452m that the test of nitrogen adsorption-desorption obtains chitin aerogel specific surface area
2/ g, porosity 94%, density is 0.16g/cm
3.The stereoscan photograph of obtained chitin aerogel as shown in Figure 1.
Embodiment 9
By the rare HCl soaking at room temperature of 5wt% 12h for commercially available chitin, filtering after washing and obtaining acetyl degree by 4wt%NaOH aqueous solution soaking 12h post-drying is 92% chitin powder.The mixed solvent of 2g NaOH, 10g thiocarbamide and 88g water is chilled to-5 ℃ in advance, after adding 1g chitin powder to stir, at-20 ℃, keeps 12h.At room temperature thaw, obtain transparent chitin solution.The syringe needle that is 0.3mm from diameter by chitin solution is extruded and is entered 90wt% aqueous ethanolic solution, after standing 10 minutes, obtains chitin hydrogel, and other steps are with embodiment 1.It is 426m that the test of nitrogen adsorption-desorption obtains chitin aerogel specific surface area
2/ g, porosity 96%, density is 0.08g/cm
3.
Embodiment 10
The mixed solvent of 25g NaOH, 0.1g thiocarbamide and 79.9g water is chilled to-5 ℃ in advance, after adding the commercially available chitin powder of 2g to stir, at-20 ℃, keeps 12h.At room temperature thaw, obtain transparent chitin solution.On sheet glass, take casting method to obtain the chitin solution that 1mm is thick, chitin solution is immersed in the 5wt%KCl aqueous solution and places and within 10 minutes, make its gelation, after washing, more successively with acetone and toluene displacement, through constant pressure and dry (40 ℃ of temperature), make chitin aerogel.It is 301m that the test of nitrogen adsorption-desorption obtains chitin aerogel specific surface area
2/ g, porosity 82%, density is 0.12g/cm
3.
Embodiment 11
By the rare HCl soaking at room temperature of 5wt% 12h for commercially available chitin, filtering after washing and obtaining acetyl degree by 4wt%NaOH aqueous solution soaking 12h post-drying is 92% chitin powder.The mixed solvent of 6g NaOH, 6g thiocarbamide and 88g water is chilled to-5 ℃ in advance, after adding 7g chitin powder to stir, at-20 ℃, keeps 12h.At room temperature thaw, obtain transparent chitin solution.On sheet glass, take casting method to obtain the chitin solution that 1mm is thick, by chitin solution immerse methanol/ethanol (1: 1, place in v/v) and within 10 minutes, make its gelation, other steps are with embodiment 1.It is 361m that the test of nitrogen adsorption-desorption obtains chitin aerogel specific surface area
2/ g, porosity 92%, density is 0.18g/cm
3.
Embodiment 12
By the rare HCl soaking at room temperature of 5wt% 12h for commercially available chitin, filtering after washing and obtaining acetyl degree by 4wt%NaOH aqueous solution soaking 12h post-drying is 92% chitin powder.The mixed solvent of 14g NaOH, 3g thiocarbamide and 83g water is chilled to-5 ℃ in advance, after adding 5g chitin powder to stir, at-20 ℃, keeps 12h.At room temperature thaw, obtain transparent chitin solution.
Embodiment 13
By the rare HCl soaking at room temperature of 5wt% 12h for commercially available chitin, filtering after washing and obtaining acetyl degree by 4wt%NaOH aqueous solution soaking 12h post-drying is 92% chitin powder.The mixed solvent of 10g NaOH, 4.5g thiocarbamide and 85.5g water is chilled to-5 ℃ in advance, after adding 5g chitin powder to stir, at-20 ℃, keeps 12h.At room temperature thaw, obtain transparent chitin solution.
Embodiment 14
By the rare HCl soaking at room temperature of 5wt% 12h for commercially available chitin, filtering after washing and obtaining acetyl degree by 4wt%NaOH aqueous solution soaking 12h post-drying is 92% chitin powder.By 8g LiOHH
2the mixed solvent of O (being 4.6g LiOH), 4g urea and 88g water is chilled to-12 ℃ in advance, after adding 8g chitin powder to stir, at-25 ℃, keeps 8h.At room temperature thaw, obtain transparent chitin solution.On sheet glass, take casting method to obtain the chitin solution that 1mm is thick, immerse in methyl alcohol and place and make its gelation in 10 minutes, after washing, with dehydrated alcohol, replace again, through supercritical CO
2dry (40 ℃ of temperature, pressure 100kg/cm
2) make chitin aerogel.It is 399m that the test of nitrogen adsorption-desorption obtains chitin aerogel specific surface area
2/ g, porosity 92%, density is 0.19g/cm
3.
(comparative example 3)
Chitin solution in embodiment 14 is obtained to chitin cross-linked hydrogel with linking agent epoxy chloropropane through chemical reaction, be similar to jelly.Hydrogel intensity is only tens of kPa.After dehydrated alcohol and trimethyl carbinol displacement, volumetric shrinkage reaches more than 90%, cannot obtain aerogel.
(comparative example 4)
Chitin solution in embodiment 14 is obtained to chitin cross-linked hydrogel with linking agent epoxy chloropropane through chemical reaction, be similar to jelly.Hydrogel intensity is only tens of kPa.Hydrogel be placed in freezing under liquid nitrogen temperature after, be placed in the dry 12h of freeze drier, obtain macroporous chitin foam.It is 58m that the test of nitrogen adsorption-desorption obtains macroporous chitin foam specific surface area
2/ g.
Embodiment 15
By the rare HCl soaking at room temperature of 5wt% 12h for commercially available chitin, filtering after washing and obtaining acetyl degree by 4wt%NaOH aqueous solution soaking 12h post-drying is 92% chitin powder.By 5.2g LiOHH
2the mixed solvent of O (being 3g LiOH), 20g urea and 74.8g water is chilled to-12 ℃ in advance, after adding 1g chitin powder to stir, at-25 ℃, keeps 8h.At room temperature thaw, obtain transparent chitin solution.On sheet glass, take casting method to obtain the chitin solution that 1mm is thick, chitin solution is immersed to 50wt% ethanol (moisture 50%) placement and within 10 minutes, make its gelation, after washing, again with dehydrated alcohol displacement, other steps are with embodiment 1.It is 392m that the test of nitrogen adsorption-desorption obtains chitin aerogel specific surface area
2/ g, porosity 94%, density is 0.07g/cm
3.
Embodiment 16
By the rare HCl soaking at room temperature of 5wt% 12h for commercially available chitin, filtering after washing and obtaining acetyl degree by 4wt%NaOH aqueous solution soaking 12h post-drying is 92% chitin powder.By 17.5g LiOHH
2the mixed solvent of O (being 10g LiOH), 0.1g urea and 87.7g water is chilled to-12 ℃ in advance, after adding 3g chitin powder to stir, at-25 ℃, keeps 8h.At room temperature thaw, obtain transparent chitin solution.On sheet glass, take casting method to obtain the chitin solution that 1mm is thick, chitin solution is immersed in the water to placement and within 20 minutes, makes its gelation, after washing, again with dehydrated alcohol displacement, other steps are with embodiment 1.It is 353m that the test of nitrogen adsorption-desorption obtains chitin aerogel specific surface area
2/ g, porosity 90%, density is 0.12g/cm
3.
Embodiment 17
By the rare HCl soaking at room temperature of 5wt% 12h for commercially available chitin, filtering after washing and obtaining acetyl degree by 4wt%NaOH aqueous solution soaking 12h post-drying is 92% chitin powder.By 7g LiOHH
2the mixed solvent of O (being 4g LiOH), 12g urea and 81g water is chilled to-12 ℃ in advance, after adding 7g chitin powder to stir, at-25 ℃, keeps 8h.At room temperature thaw, obtain transparent chitin solution.
Embodiment 18
By the rare HCl soaking at room temperature of 5wt% 12h for commercially available chitin, filtering after washing and obtaining acetyl degree by 4wt%NaOH aqueous solution soaking 12h post-drying is 92% chitin powder.By 14g LiOHH
2the mixed solvent of O (being 8g LiOH), 4g urea and 85.5g water is chilled to-12 ℃ in advance, after adding 12g chitin powder to stir, at-25 ℃, keeps 8h.At room temperature thaw, obtain transparent chitin solution.
Embodiment 19
By the rare HCl soaking at room temperature of 5wt% 12h for commercially available chitin, filtering after washing and obtaining acetyl degree by 4wt%NaOH aqueous solution soaking 12h post-drying is 92% chitin powder.By 5.2g LiOHH
2the mixed solvent of O (being 3g LiOH), 10g thiocarbamide and 84.8g water is chilled to-5 ℃ in advance, after adding 1g chitin powder to stir, at-25 ℃, keeps 8h.At room temperature thaw, obtain transparent chitin solution.
Embodiment 20
By the rare HCl soaking at room temperature of 5wt% 12h for commercially available chitin, filtering after washing and obtaining acetyl degree by 4wt%NaOH aqueous solution soaking 12h post-drying is 92% chitin powder.By 17.5g LiOHH
2the mixed solvent of O (being 10g LiOH), 0.1g thiocarbamide and 87.7g water is chilled to-5 ℃ in advance, after adding 12g chitin powder to stir, at-25 ℃, keeps 8h.At room temperature thaw, obtain transparent chitin solution.
Embodiment 21
By the rare HCl soaking at room temperature of 5wt% 12h for commercially available chitin, filtering after washing and obtaining acetyl degree by 4wt%NaOH aqueous solution soaking 12h post-drying is 92% chitin powder.By 7g LiOHH
2the mixed solvent of O (being 4g LiOH), 6g thiocarbamide and 87g water is chilled to-5 ℃ in advance, after adding 5g chitin powder to stir, at-25 ℃, keeps 8h.At room temperature thaw, obtain transparent chitin solution.
Embodiment 22
By the rare HCl soaking at room temperature of 5wt% 12h for commercially available chitin, filtering after washing and obtaining acetyl degree by 4wt%NaOH aqueous solution soaking 12h post-drying is 92% chitin powder.By 14g LiOHH
2the mixed solvent of O (being 8g LiOH), 3g thiocarbamide and 86.5g water is chilled to-5 ℃ in advance, after adding 5g chitin powder to stir, at-25 ℃, keeps 8h.At room temperature thaw, obtain transparent chitin solution.
Embodiment 23
By the rare HCl soaking at room temperature of 5wt% 12h for commercially available chitin, filtering after washing and obtaining acetyl degree by 4wt%NaOH aqueous solution soaking 12h post-drying is 92% chitin powder.By 8.8g LiOHH
2the mixed solvent of O (being 5g LiOH), 4g thiocarbamide and 87.2g water is chilled to-5 ℃ in advance, after adding 8g chitin powder to stir, at-25 ℃, keeps 8h.At room temperature thaw, obtain transparent chitin solution.
On sheet glass, take casting method to obtain the chitin solution that 1mm is thick, immerse 5wt%H
2sO
4in the aqueous solution, place and make its gelation in 10 minutes, after washing, with dehydrated alcohol, replace again, through supercritical CO
2dry (40 ℃ of temperature, pressure 100kg/cm
2) make chitin aerogel.It is 372m that the test of nitrogen adsorption-desorption obtains chitin aerogel specific surface area
2/ g, porosity 90%, density is 0.16g/cm
3.
Embodiment 24
The chitin hydrogel that obtains in embodiment 8 is immersed in the 20wt%NaOH aqueous solution, and 90 ℃ of heating 48h, obtain deacetylation and are 70% aquagel after washing.With after dehydrated alcohol displacement, through supercritical CO
2dry (40 ℃ of temperature, pressure 100kg/cm
2) make chitosan aerogel.It is 401m that the test of nitrogen adsorption-desorption obtains chitosan aerogel specific surface area
2/ g, porosity 92%, density is 0.17g/cm
3.The stereoscan photograph of chitosan aerogel as shown in Figure 2.
Embodiment 25
The chitin hydrogel that obtains in embodiment 8 is immersed in the 30wt%NaOH aqueous solution, and 60 ℃ of heating 12h, obtain deacetylation and are 89% aquagel after washing.Aquagel, with after trimethyl carbinol displacement, is made to chitosan aerogel through lyophilize.It is 367m that the test of nitrogen adsorption-desorption obtains chitosan aerogel specific surface area
2/ g, porosity 89%, density is 0.20g/cm
3.
Embodiment 26
The chitin hydrogel obtaining in embodiment 14 is immersed in the 40wt%NaOH aqueous solution, and 40 ℃ of heating 4h, repeat 2 times.After washing, obtain deacetylation and be 81% aquagel.With after dehydrated alcohol displacement, through supercritical CO
2dry (40 ℃ of temperature, pressure 100kg/cm
2) make chitosan aerogel.It is 368m that the test of nitrogen adsorption-desorption obtains chitosan aerogel specific surface area
2/ g, porosity 91%, density is 0.19g/cm
3.
Embodiment 27
The chitin hydrogel that obtains in embodiment 14 is immersed in the 45wt%NaOH aqueous solution, and 110 ℃ of heating 1h, obtain deacetylation and are 89% aquagel after washing.Aquagel is placed under liquid nitrogen temperature freezing, with freeze drier lyophilize 12h, other steps are identical.It is 327m that the test of nitrogen adsorption-desorption obtains chitosan aerogel specific surface area
2/ g, porosity 88%, density is 0.22g/cm
3.
Embodiment 28
Chitin hydrogel that embodiment 1 is obtained immerse tetraethoxy/ethanolic soln (3: 7, v/v) in 30 minutes, take out and contain tetraethoxy chitin hydrogel, in 0.1mol/L ammoniacal liquor, placing and within 10 minutes, making tetraethoxy complete hydrolysis is SiO
2nanoparticle, chitin hydrogel water white transparency.After this gel washing, be replaced into dehydrated alcohol, then pass through supercritical CO
2the dry SiO that obtains
2nanoparticle/chitin composite aerogel.By the experiment of nitrogen adsorption-desorption, obtain SiO
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 within 10 minutes, make Fe
3+complete reaction is hydration Fe
2o
3nanoparticle.After this gel washing, be replaced into dehydrated alcohol, then pass through supercritical CO
2the dry Fe that obtains
2o
3nanoparticle/chitin composite aerogel.By the experiment of nitrogen adsorption-desorption, obtain Fe
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 O ethanolic soln 30 minutes, take out and contain FeCl
3and FeCl
2chitosan gel rubber, in 0.1mol/L propylene oxide 60 ℃ heating 30 minutes, make FeCl
3and FeCl
2complete hydrolysis reaction generates Fe
3o
4nanoparticle, chitosan gel rubber is black, has obvious magnetic.After this gel washing, be replaced into dehydrated alcohol, then pass through supercritical CO
2the dry Fe that obtains
3o nanoparticle/chitosan composite aerogel.By the experiment of nitrogen adsorption-desorption, obtain Fe
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
4in the aqueous solution, place and within 30 minutes, make Ag+ be reduced to Ag nanoparticle completely, aquagel is yellow.After this hydrogel washing, be replaced into dehydrated alcohol, then pass through supercritical CO
2dry Ag nanoparticle/chitosan composite aerogel that obtains.The specific surface area that is obtained composite aerogel by the experiment of nitrogen adsorption-desorption is 378m
2/ g, density 0.21g/cm
3.
Embodiment 32
The chitin aerogel that embodiment 1 is obtained is heated to 600 ℃ from room temperature with 10 ℃/min, and nitrogen, as shielding gas, obtains black porous carbon aerogel.The specific surface area that is obtained carbon aerogels by the experiment of nitrogen adsorption-desorption is 608m
2/ g.The stereoscan photograph of carbon aerogels as shown in Figure 3.
Embodiment 33
The chitin aerogel that embodiment 1 is obtained, in HCl atmosphere, is heated to 150 ℃ from room temperature with 10 ℃/min, and nitrogen, as shielding gas, obtains black porous carbon aerogel.The specific surface area that is obtained carbon aerogels by the experiment of nitrogen adsorption-desorption is 369m
2/ g.
Embodiment 34
The chitosan aerogel that embodiment 25 is obtained is heated to 800 ℃ from room temperature with 10 ℃/min, and nitrogen, as shielding gas, obtains black porous carbon aerogel.The specific surface area that is obtained carbon aerogels by the experiment of nitrogen adsorption-desorption is 820m
2/ g.
Embodiment 35
The chitosan aerogel that embodiment 26 is obtained is heated to 1000 ℃ from room temperature with 10 ℃/min, and nitrogen, as shielding gas, obtains black porous carbon aerogel.The specific surface area that is obtained carbon aerogels by the experiment of nitrogen adsorption-desorption 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, as shielding gas, obtains black porous carbon/Fe
2o
3composite aerogel.By the experiment of nitrogen adsorption-desorption, obtain carbon/Fe
2o
3the specific surface area of composite carbon aerogel is 450m
2/ g.
Claims (20)
1. a preparation method for chitin aerogel, is characterized in that:
(1) chitin solution is immersed in peptizer, regeneration, obtains chitin hydrogel after washing;
(2) water in chitin hydrogel is replaced into organic liquid and obtains chitin organogel;
(3) remove liquid by (1) gained chitin hydrogel or (2) gained organogel are dry, obtain chitin aerogel; Described peptizer is water, or is added with therein the water of monovalent cation, or water content is lower than the nonpolar organic liquid of lower boiling of 50wt%.
2. preparation method according to claim 1, is characterized in that: described monovalent cation is H
+, NH
4 +, Li
+, Na
+or K
+; The nonpolar organic liquid of described lower boiling is alcohol, ketone, ester or its mixture.
3. preparation method according to claim 2, is characterized in that: described alcohol is methyl alcohol, ethanol; Described ketone is acetone; Described ester is ethyl acetate.
4. preparation method according to claim 1 and 2, it is characterized in that: the preparation method of described chitin solution, the solvent adopting 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, above freezing thawing, obtains chitin solution.
5. preparation method according to claim 4, it is characterized in that: described chitin solution is mix with chitin and be refrigerated to below freezingly with the solvent that the water of 2～25wt%NaOH, 0.1～20wt% urea and surplus forms, and then above freezing thawing, obtains.
6. preparation method according to claim 4, it is characterized in that: described chitin solution is mix with chitin and be refrigerated to below freezingly with the solvent that the water of 3.0～10wt%LiOH, 0.1～20wt% urea and surplus forms, and then above freezing thawing, obtains.
7. preparation method according to claim 4, it is characterized in that: described chitin solution is mix with chitin and be refrigerated to below freezingly with the solvent that the water of 2～25wt%NaOH, 0.1～10wt% thiocarbamide and surplus forms, and then above freezing thawing, obtains.
8. preparation method according to claim 4, it is characterized in that: described chitin solution is mix with chitin and be refrigerated to below freezingly with the solvent that the water of 3.0～7wt%LiOH, 0.1～10wt% thiocarbamide and surplus forms, and then above freezing thawing, obtains.
9. preparation method according to claim 1 and 2, it is characterized in that: for replacing the organic liquid of chitin hydrogel, be the volatile alkanes of lower boiling, halogenated hydrocarbon, alcohols, phenols, ketone, ester class, itrogenous organic substance, sulfurous organic compound, or the mixture of aforementioned various liquid.
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.
The preparation method of 11. 1 kinds of chitosan aerogels, is characterized in that:
(1) chitin solution is immersed in peptizer, regeneration, obtains chitin hydrogel after washing;
(2) chitin hydrogel is deacetylated, after washing, obtain aquagel;
(3) water in aquagel is replaced into organic liquid and obtains chitosan organogel;
(4) remove liquid by (2) gained aquagel or (3) gained organogel are dry, obtain chitosan aerogel; Described peptizer is water, or is added with therein the water of monovalent cation, or water content is lower than the nonpolar organic liquid of lower boiling of 50wt%.
12. preparation methods according to claim 11, is characterized in that: described monovalent cation is H
+, NH
4 +, Li
+, Na
+or K
+; The nonpolar organic liquid of described lower boiling is alcohol, ketone, ester or its mixture.
13. preparation methods according to claim 12, is characterized in that: described alcohol is methyl alcohol, ethanol; Described ketone is acetone; Described ester is ethyl acetate.
14. according to the preparation method described in claim 11 or 12, it is characterized in that: the preparation method of described chitin solution, the solvent adopting 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, above freezing thawing, obtains chitin solution.
15. preparation methods according to claim 14, it is characterized in that: described chitin solution is mix with chitin and be refrigerated to below freezingly with the solvent that the water of 2～25wt%NaOH, 0.1～20wt% urea and surplus forms, and then above freezing thawing, obtains.
16. preparation methods according to claim 14, it is characterized in that: described chitin solution is mix with chitin and be refrigerated to below freezingly with the solvent that the water of 3.0～10wt%LiOH, 0.1～20wt% urea and surplus forms, and then above freezing thawing, obtains.
17. preparation methods according to claim 14, it is characterized in that: described chitin solution is mix with chitin and be refrigerated to below freezingly with the solvent that the water of 2～25wt%NaOH, 0.1～10wt% thiocarbamide and surplus forms, and then above freezing thawing, obtains.
18. preparation methods according to claim 14, it is characterized in that: described chitin solution is mix with chitin and be refrigerated to below freezingly with the solvent that the water of 3.0～10wt%LiOH, 0.1～10wt% thiocarbamide and surplus forms, and then above freezing thawing, obtains.
19. according to the preparation method described in claim 11 or 12, it is characterized in that: for replacing the organic liquid of chitin hydrogel, be the volatile alkanes of lower boiling, halogenated hydrocarbon, alcohols, phenols, ketone, ester class, itrogenous organic substance, sulfurous organic compound, or the mixture of aforementioned various liquid.
20. according to the preparation method described in claim 11 or 12, it is characterized in that: described dry link utilizes supercritical drying, constant pressure and dry or lyophilize to remove liquid medium.
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