CN107365427A - A kind of method that Frozen-thawed cycled method prepares aeroge - Google Patents
A kind of method that Frozen-thawed cycled method prepares aeroge Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
- C08J9/286—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum the liquid phase being a solvent for the monomers but not for the resulting macromolecular composition, i.e. macroporous or macroreticular polymers
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
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- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/06—Pectin; Derivatives thereof
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- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
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- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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Abstract
The invention discloses a kind of method that Frozen-thawed cycled method prepares aeroge, macromolecule hydrogel or ice gel are formed using the method for Frozen-thawed cycled first, then hydrogel or ice gel are transferred in the organic solvent of low boiling, low-surface-energy and carry out exchange of solvent, after the completion of exchange of solvent, by the gel of gained at a temperature of close to room temperature constant pressure and dry.Aeroge of the present invention is not in structure collapses during constant pressure and dry, and method is simple to operate, and drying temperature is relatively low, less energy consumption and is easy to continuous production, thus advantageously reduces the production cost of aeroge.
Description
Technical field
The present invention relates to a kind of preparation method of aeroge, more particularly to a kind of Frozen-thawed cycled method prepares the side of aeroge
Method.
Background technology
Aeroge is a kind of novel porous materials using air as medium.Aeroge is the minimum material of the density being currently known
One of material, the minimum reachable 0.16kg/m of density3.Aeroge has a low-density, high porosity, high-specific surface area, and heat-proof quality is excellent
The features such as different, thus it is widely used in the fields such as building, the energy, environmental protection, electronics, space flight.Common aerogel material has titanium dioxide
Silicon, titanium dioxide, polyimides, phenolic resin, cellulosic material etc..
Preparing the process of aeroge needs to remove solvent in gel（Water or other organic solvents）To reach dry mesh
's.Currently used drying means is supercritical drying and freeze-drying.Supercritical drying needs to carry out at high temperature under high pressure, and
Freeze-drying needs to carry out under low-temp low-pressure environment, thus conventional drying means energy consumption is very high and less environmentally friendly, so as to
Cause very high production cost.
In order to realize the industrialization of aeroge, atmosphere pressure desiccation is a kind of better method.Atmosphere pressure desiccation is in positive normal pressure
Carried out under power, simple to operate, drying temperature is relatively low, less energy consumption and is easy to continuous production, thus advantageously reduces aeroge
Production cost.Yet with capillary force, during constant pressure and dry, aerogel structure is easy to cave in, so as to cause production
Aeroge density is higher, and quality is relatively low.Aerogel structure caused by this capillarity caves in phenomenon for hydrophilic height
Molecule, especially boiomacromolecule are especially notable.Therefore, atmosphere pressure desiccation prepares hydrophilic macromolecule aeroge and seldom reported
Road.
The content of the invention
It is an object of the invention to solve the technology of structure collapses during hydrophilic macromolecule aeroge constant pressure and dry to ask
Topic, there is provided a kind of method that Frozen-thawed cycled method prepares aeroge, aeroge are not in structure collapses during constant pressure and dry,
Method is simple to operate, and drying temperature is relatively low, less energy consumption and is easy to continuous production, thus advantageously reduces being produced into for aeroge
This.
The technical solution adopted for the present invention to solve the technical problems is：
A kind of method that Frozen-thawed cycled method prepares aeroge, comprises the following steps：
（1）High molecular dispersion liquid prepares：
One of following scheme is taken in the preparation of high molecular dispersion liquid：
Scheme 1：Hydrophilic high molecular material is dispersed in water or in the mixed solvent secures satisfactory grades sub- dispersion liquid；
Scheme 2：Hydrophilic high molecular material and auxiliary material are dispersed in water or in the mixed solvent secures satisfactory grades sub- dispersion liquid；
Mixed solvent described in scheme 1 and scheme 2 is that water and water-miscible organic solvent A are mixed；
（2）Frozen-thawed cycled：Dispersion liquid is subjected to Frozen-thawed cycled 1-10 times, when in the 2-10 times circulation, walked in the jelly of circulation
It is rapid or melt step and terminate, finally give gel or frozen glue；The present invention only carries out obtaining gel during 1 Frozen-thawed cycled, when progress two
During secondary above Frozen-thawed cycled, it can terminate in the circulation of last time freezing step or melting step, freeze step and terminate to obtain frozen glue,
Melt step to terminate to obtain gel；
Frozen-thawed cycled is specific as follows：
Freeze step：By dispersion liquid at 0 DEG C Dao -196 DEG C（Preferably -10 DEG C Dao -100 DEG C, more preferably -20 DEG C to -78 DEG C）It is cold
Freeze solidification, form frozen glue, cooling time is 1 second to 24 hours（It is preferably 1 minute to 10 hours, more preferably 10 minutes small to 1
When）；
Melt step：By frozen glue at 1 DEG C to 90 DEG C（Preferably 10 DEG C to 80 DEG C, more preferably 20 DEG C to 40 DEG C）In the environment of solve
Freeze, obtain gel, thawing time is 1 minute to 24 hours（It is preferably 5 minutes to 5 hours, more preferably 10 minutes small to 1
When）.
（3）Exchange of solvent：
By step（2）The frozen glue or gel obtained by Frozen-thawed cycled is transferred to progress solvent friendship in water-miscible organic solvent B
Change until the water in frozen glue or gel is replaced and obtains water-miscible organic solvent B gels completely by water-miscible organic solvent B；
Or by step（2）The frozen glue or gel obtained by Frozen-thawed cycled, which is transferred in water-miscible organic solvent B, to be carried out once
Exchange of solvent is replaced and obtains water-miscible organic solvent B gels completely up to the water in frozen glue or gel by water-miscible organic solvent B,
Water-miscible organic solvent B gels are then transferred to carry out secondary solvent exchange in organic solvent C until water-miscible organic solvent B quilts
Organic solvent C is replaced completely obtains organic solvent C gels；
In some cases, in order to ensure dry when aerogel structure do not cave in, gel need carry out secondary solvent exchange.It is used
Solvent is the effumability solvent that surface tension is lower, boiling point is lower.Exchange of solvent can be carried out at -40 DEG C to 60 DEG C.
（4）Constant pressure and dry：
By step（3）The gel obtained after exchange of solvent, which is placed in baking oven, carries out constant pressure and dry acquisition aerogel products, dries temperature
Spend for 10 ~ 150 DEG C, preferably drying temperature is 20 ~ 100 DEG C, and more preferably temperature is 40 ~ 80 DEG C, and drying time is 1 minute ~ 48
Hour, preferably drying time is 5 minutes to 24 hours, and more preferably drying time is 10 minutes ~ 1 hour.
Whole operation process of the present invention can be carried out with serialization.High molecular dispersion liquid can spread over poly terephthalic acid
On the film such as glycol ester film or aluminium foil, Frozen-thawed cycled, exchange of solvent and drying are then carried out.Dry the aeroge of gained
It is continuous thin airsetting film.Whole process can be operated by volume to volume and is carried out continuously.Just obtained after the completion of drying low close
The polymer aerogel of degree, density can be controlled in 250g ~ 500kg/m3In the range of, porosity can reach more than 99%, aperture
It can be controlled in 50 nanometers to 100 microns.
Preferably, the hydrophilic high molecular material is selected from chitin（Can be chitin nano fiber, chitin
Nano microcrystalline）, cellulose（Paper pulp, methylcellulose, ethyl cellulose, hydroxypropyl methyl cellulose, regenerated cellulose, carboxylic first
Base cellulose, microcrystalline cellulose, fento cellulose, nano-cellulose etc.）, chitosan, sodium alginate, gelatin, pectin, I
Primary glue, xanthans, starch, nano-starch, collagen, hyaluronic acid, chondroitin sulfate, agar, dermatan sulfate, heparin,
Heparan sulfate, glucan, polyfructosan, glutelin, alcohol soluble protein, albumin, globulin, histone, protamine, synthesis
The organic polymer of class（Polyvinyl alcohol, polyethylene glycol, polyacrylamide, polyvinylpyrrolidone, poly- 2- hydroxyethyl methyls propylene
Acid, polyacrylic acid, polymethylacrylic acid）In one or more of combinations.
Preferably, the auxiliary material is selected from graphene, graphene oxide, CNT, silica, titanium dioxide, oxygen
Change one or more of combinations in zinc, iron oxide, ferroso-ferric oxide, graphite.Auxiliary material act as aeroge obtained by enhancing
Mechanical strength assigns gained aeroge excellent electromagnetic performance or heat conductivility, as magnetic ferroferric oxide can assign airsetting
Glue magnetic, graphene can strengthen the electrical and thermal conductivity performance of aeroge.These auxiliary material components can with nano particle, micron particles,
The forms such as aqueous liquid dispersion, predecessor and hydrophilic macromolecule are compounded to form aeroge.
Preferably, the water-miscible organic solvent A be selected from methanol, ethanol, propyl alcohol, isopropanol, n-butanol, isobutanol,
The tert-butyl alcohol, acetone, tetrahydrofuran, dimethylformamide, dimethyl acetamide, methyl pyrrolidone, acetonitrile, glycerine, 1,5- penta
Glycol, ethylene glycol, propane diols, 1,3 butylene glycol, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, diethylene glycol list isobutyl ether,
One or more of groups in triethylene glycol monomethyl ether, TRIGLYME, Tripropylene glycol monomethyl Ether, tripropylene glycol dimethyl ether
Close.
Preferably, step（3）Water-miscible organic solvent B used is selected from methanol, ethanol, propyl alcohol, different in exchange of solvent
Propyl alcohol, n-butanol, isobutanol, the tert-butyl alcohol, ethylene glycol, propane diols, 1,3 butylene glycol, acetone, tetrahydrofuran, dimethyl formyl
One or more of combinations in amine, acetonitrile.Exchange of solvent is repeatable 1 ~ 10 time.
Preferably, step（3）Organic solvent C used is selected from hexane, heptane, hexamethylene, octane, nonyl in exchange of solvent
One or more of combinations in alkane.Secondary solvent exchanges repeatable 1 ~ 10 time.
Preferably, in scheme 1：When solvent is water, hydrophilic high molecular material content is 0.05% ~ 30%, water 70%
~ 99.95%, preferably macromolecule content 0.5% ~ 20%, water content be 80% ~ 99.5%, more preferably macromolecule content 1% ~
10%, water content is 90% ~ 99%.
Preferably, in scheme 1：When solvent is mixed solvent, hydrophilic high molecular material content is 0.05 ~ 30%,
Water 10% ~ 98%, water-miscible organic solvent A contents are 1% ~ 80%；Preferably macromolecule 0.5% ~ 20%, water 40% ~ 90%, You Jirong
Agent A is 5% ~ 50%；More preferably macromolecule 1% ~ 10%, water 70% ~ 80%, organic solvent A are 10% ~ 20%.
Preferably, in scheme 2：When solvent is water, hydrophilic high molecular material content is 0.05% ~ 30%, and auxiliary material contains
Measure as 0.01% ~ 20%, water is 70% ~ 99.94%, preferably macromolecule content 0.5% ~ 20%, and auxiliary material content is that 0.1% ~ 10% water contains
Measure as 80% ~ 99%；More preferably macromolecule content 1% ~ 10%, auxiliary material are that 1% ~ 5% water content is 90% ~ 98%.
Preferably, in scheme 2：When solvent is mixed solvent, hydrophilic high molecular material content is 0.05 ~ 30%, auxiliary
It is 0.01% ~ 20% to expect content, water 10% ~ 98%, and water-miscible organic solvent A contents are 1.0% ~ 80%；Preferably macromolecule 0.5%
~ 20%, auxiliary material is 0.1% ~ 10%, water 40% ~ 90%, and organic solvent A is 5% ~ 40%；More preferably macromolecule 1% ~ 10%, auxiliary material 1% ~
5%, water 70% ~ 80%, organic solvent A is 10% ~ 20%.
With conventional aeroge preparation method（Such as supercritical drying or freeze-drying）Compare, method of the invention, have
There is apparent advantage：
1st, the equipment that constant pressure and dry need not be complicated, simplifies technological process, preparation process is simple to operate, is easily controlled.
2nd, HTHP or low-temp low-pressure are not needed, in the absence of the operating process of danger, energy consumption is low, safety and environmental protection.
3rd, whole flow process can be improved efficiency, reduced cost with continuous production.
4th, solvent for use is cheap, is easily recycled.
5th, the present invention is applied widely, available for preparing a variety of hydrophilic macromolecule aeroges.Raw material range is wide, first used
Shell element or cellulose can be from industrial and agricultural production discarded objects, as obtained in crab shell, shrimp shell, waste paper.
Embodiment
Below by specific embodiment, technical scheme is described in further detail.
In the present invention, if not refering in particular to, used raw material and equipment etc. are commercially available or commonly used in the art.
Method in following embodiments, it is the conventional method of this area unless otherwise instructed.
Total embodiment：
A kind of method that Frozen-thawed cycled method prepares aeroge, comprises the following steps：
（1）High molecular dispersion liquid prepares：
One of following scheme is taken in the preparation of high molecular dispersion liquid：
Scheme 1：Hydrophilic high molecular material is dispersed in water or in the mixed solvent secures satisfactory grades sub- dispersion liquid；
In scheme 1：When solvent is water, hydrophilic high molecular material content is 0.05% ~ 30%, and water is 70% ~ 99.95%, preferably
For macromolecule content 0.5% ~ 20%, water content is 80% ~ 99.5%, and more preferably macromolecule content 1% ~ 10%, water content is
90%~99%.When solvent is mixed solvent, hydrophilic high molecular material content is 0.05 ~ 30%, and water 10% ~ 98% is water-soluble
Organic solvent A content is 1% ~ 80%；Preferably macromolecule 0.5% ~ 20%, water 40% ~ 90%, organic solvent A are 5% ~ 50%；More preferably
For macromolecule 1% ~ 10%, water 70% ~ 80%, organic solvent A is 10% ~ 20%.
Scheme 2：Hydrophilic high molecular material and auxiliary material are dispersed in water or in the mixed solvent secures satisfactory grades sub- dispersion liquid；
In scheme 2：When solvent is water, hydrophilic high molecular material content is 0.05% ~ 30%, and auxiliary material content is 0.01% ~ 20%,
Water is 70% ~ 99.94%, and preferably macromolecule content 0.5% ~ 20%, auxiliary material content are that 0.1% ~ 10% water content is 80% ~ 99%；More
Preferably macromolecule content 1% ~ 10%, auxiliary material are that 1% ~ 5% water content is 90% ~ 98%.When solvent is mixed solvent, hydrophily
High polymer material content is 0.05 ~ 30%, and auxiliary material content is 0.01% ~ 20%, water 10% ~ 98%, water-miscible organic solvent A contents
For 1.0% ~ 80%；Preferably macromolecule 0.5% ~ 20%, auxiliary material are 0.1% ~ 10%, and water 40% ~ 90%, organic solvent A is 5% ~ 40%；
More preferably macromolecule 1% ~ 10%, auxiliary material 1% ~ 5%, water 70% ~ 80%, organic solvent A are 10% ~ 20%.
Mixed solvent described in scheme 1 and scheme 2 is that water and water-miscible organic solvent A are mixed.
The hydrophilic high molecular material is selected from chitin（Can be chitin nano fiber, chitin nano microcrystalline）、
Cellulose（It is paper pulp, methylcellulose, ethyl cellulose, hydroxypropyl methyl cellulose, regenerated cellulose, carboxymethyl cellulose, micro-
Crystalline cellulose, fento cellulose, nano-cellulose etc.）, chitosan, sodium alginate, gelatin, pectin, Arabic gum, xanthan
Glue, starch, nano-starch, collagen, hyaluronic acid, chondroitin sulfate, agar, dermatan sulfate, heparin, acetyl sulfate liver
Element, glucan, polyfructosan, glutelin, alcohol soluble protein, albumin, globulin, histone, protamine, synthesis class it is organic high
Molecule（Polyvinyl alcohol, polyethylene glycol, polyacrylamide, polyvinylpyrrolidone, poly 2-hydroxyethyl methacrylate, polypropylene
Acid, polymethylacrylic acid）In one or more of combinations.
The auxiliary material is selected from graphene, graphene oxide, CNT, silica, titanium dioxide, zinc oxide, oxidation
One or more of combinations in iron, ferroso-ferric oxide, graphite.
The water-miscible organic solvent A is selected from methanol, ethanol, propyl alcohol, isopropanol, n-butanol, isobutanol, the tert-butyl alcohol, third
Ketone, tetrahydrofuran, dimethylformamide, dimethyl acetamide, methyl pyrrolidone, acetonitrile, glycerine, 1,5- pentanediols, second two
Alcohol, propane diols, 1,3 butylene glycol, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, diethylene glycol list isobutyl ether, triethylene glycol
One or more of combinations in monomethyl ether, TRIGLYME, Tripropylene glycol monomethyl Ether, tripropylene glycol dimethyl ether.
（2）Frozen-thawed cycled：Dispersion liquid is subjected to Frozen-thawed cycled 1-10 times, from the 2nd circulation, walked in the jelly of Frozen-thawed cycled
It is rapid or melt step and terminate, finally give gel or frozen glue.
Frozen-thawed cycled is specific as follows：
Freeze step：By dispersion liquid at 0 DEG C Dao -196 DEG C（Preferably -10 DEG C Dao -100 DEG C, more preferably -20 DEG C to -78 DEG C）It is cold
Freeze solidification, form frozen glue, cooling time is 1 second to 24 hours（It is preferably 1 minute to 10 hours, more preferably 10 minutes small to 1
When）；
Melt step：By frozen glue at 1 DEG C to 90 DEG C（Preferably 10 DEG C to 80 DEG C, more preferably 20 DEG C to 40 DEG C）In the environment of solve
Freeze, obtain gel, thawing time is 1 minute to 24 hours（It is preferably 5 minutes to 5 hours, more preferably 10 minutes small to 1
When）.
（3）Exchange of solvent：
By step（2）The frozen glue or gel obtained by Frozen-thawed cycled is transferred to progress solvent friendship in water-miscible organic solvent B
Change until the water in frozen glue or gel is replaced and obtains water-miscible organic solvent B gels completely by water-miscible organic solvent B；
Or by step（2）The frozen glue or gel obtained by Frozen-thawed cycled, which is transferred in water-miscible organic solvent B, to be carried out once
Exchange of solvent is replaced and obtains water-miscible organic solvent B gels completely up to the water in frozen glue or gel by water-miscible organic solvent B,
Water-miscible organic solvent B gels are then transferred to carry out secondary solvent exchange in organic solvent C until water-miscible organic solvent B quilts
Organic solvent C is replaced completely obtains organic solvent C gels.
Water-miscible organic solvent B be selected from methanol, ethanol, propyl alcohol, isopropanol, n-butanol, isobutanol, the tert-butyl alcohol, ethylene glycol,
One or more of combinations in propane diols, 1,3 butylene glycol, acetone, tetrahydrofuran, dimethylformamide, acetonitrile.Solvent is handed over
Change repeatable 1 ~ 10 time.One or more of combinations of the organic solvent C in hexane, heptane, hexamethylene, octane, nonane.Two
Secondary exchange of solvent is repeatable 1 ~ 10 time.
（4）Constant pressure and dry：
By step（3）The gel obtained after exchange of solvent, which is placed in baking oven, carries out constant pressure and dry acquisition aerogel products, dries temperature
Spend for 10 ~ 150 DEG C, preferably drying temperature is 20 ~ 100 DEG C, and more preferably temperature is 40 ~ 80 DEG C, and drying time is 1 minute ~ 48
Hour, preferably drying time is 5 minutes to 24 hours, and more preferably drying time is 10 minutes ~ 1 hour.
Embodiment 1
（1）Chitin nano fiber（It is commercially available or with reference to existing method prepare）It is dispersed in water, wherein chitin nano fiber contains
Measure as 0.5 ~ 1%, water content is 99 ~ 99.5%.The nanofiber length of chitin can be 100 nanometers to 20 microns；A diameter of 1 receives
Rice is to 100 nanometers.
（2）Chitin nano fiber dispersion liquid is freezed to solidification 12 hours in -20 DEG C, obtains frozen glue.
（3）Being thawed at a temperature of the frozen glue of chitin nano fiber is placed on into 25 DEG C, thawing time is 24 hours,
Obtain gel.
（4）Repeat step（2）And step（3）Each 1 time, finally give gel.
（5）By step（4）Gained gel, which is placed in alcohol solvent, carries out exchange of solvent.A solvent was changed every 30 minutes,
Exchange of solvent repeats 1 ~ 10 time, until water is replaced completely.
（6）Chitin nano fiber ethanol gel after the completion of exchange of solvent is placed in 60 DEG C of constant pressure and dries, obtains crust
Plain nanofiber aeroge.Gained aeroge density is about 10 kg/m3.Porosity is more than 99%, and aperture is 1 ~ 40 microns.
Embodiment 2
（1）Chitin nano fiber and polyvinyl alcohol are scattered in the in the mixed solvent of water and the tert-butyl alcohol, wherein chitin nanometer
Fiber content is 2%, polyvinyl alcohol 1%, water content 87%, the tert-butyl alcohol 10%.
（2）Dispersion liquid solidifies 12 hours in -20 DEG C of freezings, obtains frozen glue.
（3）Being thawed at a temperature of the frozen glue of chitin nano fiber is placed on into 25 DEG C, thawing time is 12 hours,
Obtain gel.
（4）First repeat step（2）And step（3）Each 4 times, finally repeat a step（2）Terminate, finally give jelly
Glue.
（5）By step（4）Gained frozen glue, which is placed in isopropanol solvent, carries out exchange of solvent.Changed once every 30 minutes molten
Agent, exchange of solvent repeat 1 ~ 10 time, until water is replaced completely.
（6）By step（5）The gel of middle gained is placed in progress secondary solvent exchange in hexane solvent.One was changed every 30 minutes
Secondary solvent, exchange of solvent repeat 1 ~ 10 time, until isopropanol is replaced completely.
（7）Gel after the completion of exchange of solvent is placed in 25 DEG C of constant pressure and dries, obtains chitin nano fiber/polyvinyl alcohol
Composite aerogel.Gained aeroge density is less than 40 kg/m3.Porosity is more than 96%, and aperture is 100 nm ~ 5 micron.
Embodiment 3
（1）By fento cellulose and Nano particles of silicon dioxide（20 nm）It is dispersed in water, wherein fibrillation content of cellulose
For 7%, Nano particles of silicon dioxide content is 10%, water content 83%.
（2）Dispersion liquid is in dry ice ethanol bath（-72℃）Middle freezing solidification 5 minutes, obtains frozen glue.
（3）Thawed at a temperature of frozen glue is placed on into 40 DEG C, thawing time is 1 hour, obtains gel.
（4）By step（3）Gained gel, which is placed in isopropanol solvent, carries out exchange of solvent.Changed once every 30 minutes molten
Agent, exchange of solvent repeat 1 ~ 10 time, until water is replaced completely.
（5）By step（4）The gel of middle gained is placed in progress secondary solvent exchange in hexane solvent.One was changed every 30 minutes
Secondary solvent, exchange of solvent repeat 1 ~ 10 time, until isopropanol is replaced completely.
（6）Gel after the completion of exchange of solvent is placed in 25 DEG C of constant pressure and dries, fento cellulose/silica is obtained and receives
Rice corpuscles composite aerogel.Gained aeroge density is less than 200 kg/m3.Porosity is more than 80%, and aperture is that 20 nm ~ 2 are micro-
Rice.
Embodiment 4
（1）Pectin is soluble in water, and solid concentration is controlled the 2 ~ 6% of gross mass.
（2）Aqueous pectin solution is in dry ice ethanol bath（-72℃）Middle freezing solidification 5 minutes, obtains frozen glue.
（3）Thawed at a temperature of frozen glue is placed on into 25 DEG C, thawing time is 24 hours, obtains gel.
（4）First repeat step（2）And step（3）Each 1 time, finally repeat a step（2）Terminate, finally give jelly
Glue.
（5）By step（4）Gained frozen glue, which is placed in alcohol solvent, carries out exchange of solvent.A solvent was changed every 30 minutes,
Exchange of solvent repeats 1 ~ 10 time, until water is replaced completely.
（6）Pectin ethanol gel after the completion of exchange of solvent is placed in 25 DEG C of constant pressure and dries, obtains pectin aeroge, density
Less than 60 kg/m3.Porosity is more than 95%, and aperture is the microns of 100 nm ~ 2.
Embodiment described above is a kind of preferable scheme of the present invention, not the present invention is made any formal
Limitation, there are other variants and remodeling on the premise of without departing from the technical scheme described in claim.
Claims (10)
1. a kind of method that Frozen-thawed cycled method prepares aeroge, it is characterised in that comprise the following steps：
（1）High molecular dispersion liquid prepares：
One of following scheme is taken in the preparation of high molecular dispersion liquid：
Scheme 1：Hydrophilic high molecular material is dispersed in water or in the mixed solvent secures satisfactory grades sub- dispersion liquid；
Scheme 2：Hydrophilic high molecular material and auxiliary material are dispersed in water or in the mixed solvent secures satisfactory grades sub- dispersion liquid；
Mixed solvent described in scheme 1 and scheme 2 is that water and water-miscible organic solvent A are mixed；
（2）Frozen-thawed cycled：Dispersion liquid is subjected to Frozen-thawed cycled 1-10 times, when in the 2-10 times circulation, walked in the jelly of circulation
It is rapid or melt step and terminate, finally give gel or frozen glue；
Frozen-thawed cycled is specific as follows：
Freeze step：Dispersion liquid is solidified in 0 DEG C to -196 DEG C freezing, forms frozen glue, cooling time is 1 second to 24 hours；
Melt step：Frozen glue is thawed in the environment of 1 DEG C to 90 DEG C, obtains gel, thawing time is 1 minute to 24 hours；
（3）Exchange of solvent：
By step（2）The frozen glue or gel obtained by Frozen-thawed cycled is transferred to progress solvent friendship in water-miscible organic solvent B
Change until the water in frozen glue or gel is replaced and obtains water-miscible organic solvent B gels completely by water-miscible organic solvent B；
Or by step（2）The frozen glue or gel obtained by Frozen-thawed cycled, which is transferred in water-miscible organic solvent B, to be carried out once
Exchange of solvent is replaced and obtains water-miscible organic solvent B gels completely up to the water in frozen glue or gel by water-miscible organic solvent B,
Water-miscible organic solvent B gels are then transferred to carry out secondary solvent exchange in organic solvent C until water-miscible organic solvent B quilts
Organic solvent C is replaced completely obtains organic solvent C gels；
（4）Constant pressure and dry：
By step（3）The gel obtained after exchange of solvent, which is placed in baking oven, carries out constant pressure and dry acquisition aerogel products, dries temperature
Spend for 10 ~ 150 DEG C, drying time is 1 minute ~ 48 hours.
2. according to the method for claim 1, it is characterised in that the hydrophilic high molecular material is selected from chitin, fiber
Element, chitosan, sodium alginate, gelatin, pectin, Arabic gum, xanthans, starch, nano-starch, collagen, hyaluronic acid,
Chondroitin sulfate, agar, dermatan sulfate, heparin, Heparan sulfate, glucan, polyfructosan, glutelin, alcohol soluble protein,
Albumin, globulin, histone, protamine, synthesize class organic polymer in one or more of combinations.
3. according to the method for claim 1, it is characterised in that the auxiliary material is selected from graphene, graphene oxide, nano-sized carbon
One or more of combinations in pipe, silica, titanium dioxide, zinc oxide, iron oxide, ferroso-ferric oxide, graphite.
4. according to the method for claim 1, it is characterised in that the water-miscible organic solvent A is selected from methanol, ethanol, third
Alcohol, isopropanol, n-butanol, isobutanol, the tert-butyl alcohol, acetone, tetrahydrofuran, dimethylformamide, dimethyl acetamide, methyl pyrrole
Pyrrolidone, acetonitrile, glycerine, 1,5- pentanediols, ethylene glycol, propane diols, 1,3 butylene glycol, diethylene glycol monomethyl ether, DPG
Monomethyl ether, diethylene glycol list isobutyl ether, triethylene glycol monomethyl ether, TRIGLYME, Tripropylene glycol monomethyl Ether, tripropylene glycol
One or more of combinations in dimethyl ether.
5. according to the method for claim 1, it is characterised in that step（3）It is water-soluble organic molten used in exchange of solvent
Agent B is selected from methanol, ethanol, propyl alcohol, isopropanol, n-butanol, isobutanol, the tert-butyl alcohol, ethylene glycol, propane diols, 1,3 butylene glycol, third
One or more of combinations in ketone, tetrahydrofuran, dimethylformamide, acetonitrile.
6. according to the method for claim 1, it is characterised in that step（3）Organic solvent C used is selected from exchange of solvent
One or more of combinations in hexane, heptane, hexamethylene, octane, nonane.
7. according to the method for claim 1, it is characterised in that in scheme 1：When solvent is water, hydrophilicity macromolecule material
It is 0.05% ~ 30% to expect content, and water is 70% ~ 99.95%.
8. according to the method for claim 1, it is characterised in that in scheme 1：When solvent is mixed solvent, hydrophily is high
Molecular material content is 0.05 ~ 30%, water 10% ~ 98%, and water-miscible organic solvent A contents are 1% ~ 80%.
9. according to the method for claim 1, it is characterised in that in scheme 2：When solvent is water, hydrophilicity macromolecule material
It is 0.05% ~ 30% to expect content, and auxiliary material content is 0.01% ~ 20%, and water is 70% ~ 99.94%.
10. according to the method for claim 1, it is characterised in that in scheme 2：When solvent is mixed solvent, hydrophily is high
Molecular material content is 0.05 ~ 30%, and auxiliary material content is 0.01% ~ 20%, water 10% ~ 98%, and water-miscible organic solvent A contents are
1.0%~80%。
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