CN108579626A - The preparation method of Cellulose nanocrystal body/graphene/polyvinyl alcohol aeroge - Google Patents
The preparation method of Cellulose nanocrystal body/graphene/polyvinyl alcohol aeroge Download PDFInfo
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- CN108579626A CN108579626A CN201810383752.9A CN201810383752A CN108579626A CN 108579626 A CN108579626 A CN 108579626A CN 201810383752 A CN201810383752 A CN 201810383752A CN 108579626 A CN108579626 A CN 108579626A
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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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Abstract
The present invention relates to a kind of preparation methods of Cellulose nanocrystal body/graphene/enhanced aeroge of polyvinyl alcohol tri compound, including：1）It is prepared by Cellulose nanocrystal body；2）It is prepared by Cellulose nanocrystal body/graphene mixed solution；3）It is prepared by Cellulose nanocrystal body/graphene/polyvinyl alcohol tri compound solution；4）Inorganic Salt treatment；5）Alcoholic solution is replaced；6）Freeze-drying.Advantage：1）By rationally adjusting Cellulose nanocrystal body, graphene and the ratio of polyvinyl alcohol, the better aeroge of processability.2）Gained aeroge large specific surface area, aperture is small, density is low, excellent adsorption.3）Graphene oxide layer improves Mechanical Properties of Aerogels, and polyvinyl alcohol system improves the biocompatibility of product, degradability.5）Spherical aerogel has larger effective adsorption area and higher adsorption efficiency.6）Gas and the recycling of solid waste are effectively combined with water environmental control with improvement, circular economy is conducive to.
Description
Technical field
The present invention is a kind of Cellulose nanocrystal body/graphene/polyvinyl alcohol aeroge preparation method, belongs to nano material
Manufacture and technical field of modification.
Background technology
Cellulose nanocrystal body aeroge is a kind of organic aerogel, other than having the characteristics that low-density and high porosity,
Because its abundant raw material is cheap, the excellent specific properties such as biodegradable, be widely used in biomedical, catalyst and sorbent-loaded and
The numerous areas such as ecological protection.Have newly because of its nano-scale by cellulose aerogels prepared by cellulose dissolution regeneration
Effect and characteristic, but its mechanical property is relatively low, prepares the aeroge with stronger mechanical property and has broad application prospects.Mesh
Before, there are process complexity, the structures of aeroge to be difficult to regulate and control the defects of receiving for the preparation of cellulose base aeroge.
Cellulose nanocrystal body surface face carries great amount of hydroxy group, can preferably disperse in water-soluble polymer, play nanometer
The effect of enhancing, can be substantially improved the mechanical property of polyvinyl alcohol hydrogel, and the mechanical property and heat of polymer can be improved
Performance.Cellulose nanocrystal body with polyvinyl alcohol is compound prepares hydrogel, the mechanical property of polyvinyl alcohol hydrogel can be substantially improved
Can, improve biocompatibility and degradability and mechanical property.In addition Cellulose nanocrystal body further promotes polyvinyl alcohol hydrogel
The swelling of glue.The mechanical strength of cellulose aerogels depends primarily on the internal network skeleton intensity of itself, introduces inorganic enhancing
Its mechanical property can be improved in phase --- graphene, because with the hydrogen bond system of Cellulose nanocrystal body phase can occur for graphene sheet layer
Interaction, provides new reactivity site, and to assign the specific surface area of aeroge bigger, reactivity agent more good
Mechanical strength.It is significantly carried using graphene sheet layer as the cellulose composite aerogel of reinforced phase, compression modulus and compressive strength
It is high.Stronger hydrogen bond action can be formed between ternary component, therefore its compressive strength is far above Cellulose nanocrystal body/graphene film
Layer Binary-phase composite aerogel and Cellulose nanocrystal body aeroge.
Invention content
Proposed by the present invention is a kind of Cellulose nanocrystal body/graphene/enhanced aeroge of polyvinyl alcohol tri compound
Preparation method, that its object is to the mechanical properties for Cellulose nanocrystal body aeroge in the prior art is relatively low, prepared
The defects of journey complexity, the structure of aeroge are difficult to passes through structure design, controlledly synthesis and functionalization and assembles, and prepares a kind of
High-specific surface area, high adsorption, small-bore, low-density, reusable Cellulose nanocrystal body/graphene/polyvinyl alcohol
The enhanced composite aerogel of ternary.
Technical solution of the invention：A kind of Cellulose nanocrystal body/graphene/polyvinyl alcohol tri compound is enhanced
The preparation method of aeroge, includes the following steps：
（1）The preparation of Cellulose nanocrystal body；
（2）The preparation of Cellulose nanocrystal body/graphene mixed solution；
（3）The preparation of Cellulose nanocrystal body/graphene/polyvinyl alcohol tri compound solution；
（4）Inorganic Salt treatment；
（5）Alcoholic solution is replaced；
（6）Freeze-drying.
Beneficial effects of the present invention：
1）By Reasonable Regulation And Control graphene fiber element nanocrystal, the ratio of polyvinyl alcohol and the mixing of Cellulose nanocrystal body ---
M (graphene)/m（Cellulose nanocrystal body）=0.5%-1%, and m (polyvinyl alcohol)/m（Cellulose nanocrystal body）=
1%-2% can prepare the enhanced aeroge of required specific surface area.
2）The gained Cellulose nanocrystal body/enhanced aeroge large specific surface area of graphene/polyvinyl alcohol tri compound, hole
Diameter is small, density is low, excellent adsorption, can effectively adsorb methyl orange, greasy dirt, toluene, pernicious gas, the substances such as heavy metal.
3）Graphene oxide layer occurs interaction with cellulose surface hydroxyl and forms hydrogen bond, constitutes network structure, has
Effect improves the intensity of aeroge skeleton structure, and excellent in mechanical performance, compression modulus and compressive strength also significantly improve.
4）Polyvinyl alcohol is added and prepares hydrogel, the mechanical property of polyvinyl alcohol hydrogel can be substantially improved, improve simultaneously
Biocompatibility, degradability and the mechanical property of product.
5）Under identical adsorption conditions, the ball shaped cellulose nanocrystal/graphene/enhanced gas of polyvinyl alcohol tri compound
Gel has larger effective adsorption area, higher adsorption efficiency compared with column aeroge, and volume is relatively small, has wide
Wealthy application field.
6）The recycling of gas and solid waste in contamination control is combined with water environmental control with improvement,
The treatment of wastes with processes of wastes against one another forms new clearer production technology, is conducive to develop a circular economy, have a good application prospect.
Description of the drawings
Attached drawing 1 is the stereoscan photograph of aeroge sample.
Attached drawing 2 is N2Adsorption isotherm map.
A is the pure nano-cellulose aerogel sample of 1.7wt% in figure, and B is 1 gained sample of embodiment, and C is 2 institute of embodiment
Sample is obtained, D is 3 gained sample of embodiment.
Specific implementation mode
A kind of preparation method of Cellulose nanocrystal body/graphene/enhanced aeroge of polyvinyl alcohol tri compound, including
Following steps：
（1）The preparation of Cellulose nanocrystal body；
（2）The preparation of Cellulose nanocrystal body/graphene mixed solution；
（3）The preparation of Cellulose nanocrystal body/graphene/polyvinyl alcohol tri compound solution；
（4）Inorganic Salt treatment；
（5）Alcoholic solution is replaced；
（6）Freeze-drying.
The step（1）The preparation of Cellulose nanocrystal body：With the sulfuric acid treatment microcrystalline cellulose of concentration 64%, matches and be
Microcrystalline cellulose：H2SO4=1g：9.8ml, constant temperature stirs 1h at 45 DEG C；It is supreme with centrifuge 4 times or more after having handled
Layer clear liquid pH value is 6；It is put into after dialysing 3 days in distilled water, outwells supernatant liquor and be ultrasonically treated 4h（16KHz, gap 1.5s）, obtain
To 0.4wt% -1.7wt% Cellulose nanocrystal liquid suspensions.
The step（2）The preparation of Cellulose nanocrystal body/graphene mixed solution：By above-mentioned gained Cellulose nanocrystal
Liquid suspension and graphene are according to a certain percentage：M (graphene)/m（Cellulose nanocrystal body）=0.5%-1%（Mass ratio）Uniformly
Mixing.
The step（3）The preparation of Cellulose nanocrystal body/graphene/polyvinyl alcohol tri compound solution：Weigh poly- second
Enol is added in deionized water, and 100 DEG C of 3 h of stirring obtain the polyvinyl alcohol water solution of 10 wt% to being completely dissolved；According to m
(polyvinyl alcohol)/m（Cellulose nanocrystal body）The ratio of=1%-2%, by Cellulose nanocrystal body/graphene mixed solution
Be added in polyvinyl alcohol water solution and obtain Cellulose nanocrystal body/graphene/polyvinyl alcohol tri compound solution, addition go from
Polyvinyl alcohol concentration in the sub- final mixed system of water management is 7%；By Cellulose nanocrystal body/graphene/polyvinyl alcohol three
First composite solution ultrasonic mixing, 16KHz, gap 1.5s, ultrasonic 20-40 min.
The step（4）Inorganic Salt treatment：It draws prepared Cellulose nanocrystal body aaerosol solution and rotates and at the uniform velocity drip
Enter in the culture dish equipped with 0.2mol/L salting liquids, instills 0.2 mL every time, be stored at room temperature 24 h molding fibers derived above
Plain nanocrystal/graphene/polyvinyl alcohol tri compound hydrogel bead.It is molded in inorganic salt solution, electrolyte changes former
The distribution of charges of beginning sol system is to make cellulosic molecule be more easy to form gel close to aggregation.Inorganic salts are solidifying to cellulose solution
The basic reason of gelatinization induction and facilitation is the stability that inorganic salts destroy sol system.
The step（5）Alcoholic solution is replaced：By molding Cellulose nanocrystal body/graphene/polyvinyl alcohol tri compound
Hydrogel bead is placed in 30%-100%（Every 30% or 40% is a gradient）Alcoholic solution in carry out gradient displacement, bath temperature 40
DEG C, each gradient-heated is for 24 hours.Relative to water, alcoholic solution has higher solidification point (25 DEG C) and vapour pressure, can not only
Rate of drying is improved, and generated surface tension is small in sublimation process, can preferably preserve gel inner space network
Structure.
The step（6）Freeze-drying：Cellulose nanocrystal body/graphene/polyvinyl alcohol tri compound hydrogel is small
It is placed in refrigerator after ball sealing（- 10 DEG C or less）It after freezing 1h, moves into freeze drier, -40 DEG C to -60 DEG C freeze-dryings
36h（Vacuum 30MPa）, obtain Cellulose nanocrystal body/graphene/enhanced aeroge of polyvinyl alcohol tri compound.
The step（3）In Cellulose nanocrystal body/graphene/polyvinyl alcohol tri compound solution, m (graphene)/m
（Cellulose nanocrystal body）=0.5%-1%, and m (polyvinyl alcohol)/m（Cellulose nanocrystal body）=1%-2%
The step（4）In, inorganic salts are one kind in sodium chloride, potassium chloride, calcium chloride, potassium bromide, potassium nitrate.
The step（5）In, alcoholic solution is one kind in ethyl alcohol, propyl alcohol, butanol.
Technical solution of the present invention is further illustrated below in conjunction with the accompanying drawings.
As shown in Fig. 1, the interior microscopic form of four kinds of aeroges shows as " soft is spongy " structure, and is covered with
Continuous and random countless hole illustrates that aeroge made from this experiment is a kind of sorbing material that porosity is high.It is modified
There are a small amount of micropores for aeroge, and the presence of micropore is more advantageous to the fixation to adsorption molecule.With graphene and PVA concentration
Increase it is fine and close, the nanofiber quantity in unit area increases, and hole is finer and close, specific surface area bigger, is wound more between fiber
Consolidation, physical mechanics intensity improve.
As shown in Fig. 2, aeroge made from this experiment meets the feature of the IIth class Adsorption Isotherms（Anti- S types are inhaled
Attached thermoisopleth）, illustrate that aeroge characterization of adsorption is identical as unmodified ball shaped nano cellulose aerogels, still inhaled with polymolecular layer
Based on attached.It is abundant to show that the inside of composite aerogel equally has equally close to II type of hysteresis loop for the type of adsorption hysteresis ring
Central hole structure.
Embodiment 1
Cellulose nanocrystal body/graphene/polyvinyl alcohol tri compound enhances aeroge, carries out according to the following steps：
（1）The preparation of Cellulose nanocrystal body：With the sulfuric acid treatment microcrystalline cellulose of concentration 64%, match as microcrystalline cellulose：
H2SO4=1g：9.8ml, constant temperature stirs 1h at 45 DEG C；With centrifuge 4 times or more, until supernatant liquor pH value is 6, then put
It dialyses 3 days in distilled water, then outwells supernatant liquor and be ultrasonically treated 4h（16KHz, gap 1.5s）, obtain 0.4wt% -1.7wt%
（Wt, i.e.,：Mass fraction ratio）Cellulose nanocrystal liquid suspension；
（2）Graphene mixes：By 5.970g, 1.7wt% Cellulose nanocrystal body hydrogels pass through grinder 20Hz with 0.030g,
Graphene ground 10min, according to m (graphene)/m（Cellulose nanocrystal body）=0.5% proportional arrangement, it is uniformly mixed
It closes；
（3）Polyvinyl alcohol：A certain amount of polyvinyl alcohol is weighed, deionized water is added, 100 DEG C of uniform stirring 3h extremely dissolve,
Configure the polyvinyl alcohol water solution of w=10%.According to m (polyvinyl alcohol)/m（Cellulose nanocrystal body）=1%（M is solid
Liquid mixing quality）, w=10% is added in a certain amount of Cellulose nanocrystal body hydrogel and graphene ultrasonic mixing liquid（Polyethylene
Alcohol solid accounts for the mass ratio of poly-vinyl alcohol solution）Polyvinyl alcohol water solution in, add appropriate amount of deionized water to control final mixture
W (polyvinyl alcohol)=7% in system, then by Cellulose nanocrystal body/graphene mixed solution and polyvinyl alcohol ultrasonic mixing,
The ultrasonic power of 16KHz, gap 1.5s, ultrasonic disperse 20min；
（4）Inorganic Salt treatment：It is molten that prepared Cellulose nanocrystal body suspension is drawn with the glass syringe that specification is 5 mL
Liquid simultaneously rotates instillation equipped with 0.2mol l CaCl2In the culture dish of solution, each infusion volume is about 0.2 mL, is stored at room temperature
24 h or more are to get shaping fiber element nanocrystal/graphene/polyvinyl alcohol tri compound hydrogel bead；
（5）The tert-butyl alcohol is replaced：Molding hydrogel bead is placed in the alcoholic solution of 30%-100% and carries out gradient displacement, water-bath temperature
40 DEG C of degree, each gradient-heated is for 24 hours；
（6）Freeze-drying：Above-mentioned hydrogel bead is sealed with preservative film, is placed in refrigerator（- 10 DEG C or less）1h is freezed, is being protected
Several apertures are pricked on the surface of fresh film, are put into freeze drier, and 36h is freeze-dried（Vacuum 30MPa）.
Embodiment 2
Cellulose nanocrystal body/graphene/polyvinyl alcohol tri compound enhances aeroge, carries out according to the following steps：
（1）The preparation of Cellulose nanocrystal body：With the sulfuric acid treatment microcrystalline cellulose of concentration 64%, match as microcrystalline cellulose：
H2SO4=1g：9.8ml, constant temperature stirs 1h at 45 DEG C；With centrifuge 4 times or more, until supernatant liquor pH value is 6, then put
It dialyses 3 days in distilled water, then outwells supernatant liquor and be ultrasonically treated 4h（16KHz, gap 1.5s）, obtain 0.4wt% -1.7wt%
（Wt, i.e.,：Mass fraction ratio）Cellulose nanocrystal liquid suspension；
（2）Graphene mixes：By 6.965g, 1.7wt% Cellulose nanocrystal body hydrogels pass through grinder 20Hz with 0.035g,
Graphene ground 10min, according to m (graphene)/m（Cellulose nanocrystal body）=0.5% proportional arrangement, it is uniformly mixed
It closes；
（3）Polyvinyl alcohol：A certain amount of polyvinyl alcohol is weighed, deionized water is added, 100 DEG C of uniform stirring 3h extremely dissolve,
Configure the polyvinyl alcohol water solution of w=10%.According to m (polyvinyl alcohol)/m（Cellulose nanocrystal body）=1%（M is solid
Liquid mixing quality）, w=10% is added in a certain amount of Cellulose nanocrystal body hydrogel and graphene ultrasonic mixing liquid（Polyethylene
Alcohol solid accounts for the mass ratio of poly-vinyl alcohol solution）Polyvinyl alcohol water solution in, add appropriate amount of deionized water to control final mixture
W (polyvinyl alcohol)=7% in system, then by Cellulose nanocrystal body/graphene mixed liquor and polyvinyl alcohol ultrasonic mixing,
The ultrasonic power of 16KHz, gap 1.5s, 40 min of ultrasonic disperse；
（4）Inorganic Salt treatment：It is prepared with the glass syringe absorption that specification is 5 mL
Cellulose nanocrystal body aaerosol solution and rotate instillation be equipped with 0.2moll CaCl2It is molten
In the culture dish of liquid, each infusion volume is about 0. 2 mL, and it is nanocrystalline to get shaping fiber element to be stored at room temperature 24 h or more
Body/graphene/polyvinyl alcohol tri compound hydrogel bead；
（5）The tert-butyl alcohol is replaced：Molding hydrogel bead is placed in the alcoholic solution of 30%-100% and carries out gradient displacement, water-bath temperature
40 DEG C of degree, each gradient-heated is for 24 hours；
（6）Freeze-drying：Above-mentioned hydrogel bead is sealed with preservative film, is placed in refrigerator（- 10 DEG C or less）1h is freezed, is being protected
Several apertures are pricked on the surface of fresh film, are put into freeze drier, and 36h is freeze-dried（Vacuum 30MPa）；
Embodiment 3
Cellulose nanocrystal body/graphene/polyvinyl alcohol tri compound enhances aeroge, carries out according to the following steps：
（1）The preparation of Cellulose nanocrystal body：With the sulfuric acid treatment microcrystalline cellulose of concentration 64%, match as microcrystalline cellulose：
H2SO4=1g：9.8ml, constant temperature stirs 1h at 45 DEG C；With centrifuge 4 times or more, until supernatant liquor pH value is 6, then put
It dialyses 3 days in distilled water, then outwells supernatant liquor and be ultrasonically treated 4h（16KHz, gap 1.5s）, obtain 0.4wt% -1.7wt%
（Wt, i.e.,：Mass fraction ratio）Cellulose nanocrystal liquid suspension；
（2）Graphene mixes：By 9.900g, 1.7wt% Cellulose nanocrystal body hydrogels pass through grinder 20Hz with 0.100g,
Graphene ground 30min, according to m (graphene)/m（Cellulose nanocrystal body）=0.5% proportional arrangement, it is uniformly mixed
It closes；
（3）Polyvinyl alcohol：A certain amount of polyvinyl alcohol is weighed, deionized water is added, 100 DEG C of uniform stirring 3h extremely dissolve,
Configure the polyvinyl alcohol water solution of w=10%.According to m (polyvinyl alcohol)/m（Cellulose nanocrystal body）=1%（M is solid
Liquid mixing quality）, w=10% is added in a certain amount of Cellulose nanocrystal body hydrogel and graphene ultrasonic mixing liquid（Polyethylene
Alcohol solid accounts for the mass ratio of poly-vinyl alcohol solution）Polyvinyl alcohol water solution in, add appropriate amount of deionized water to control final mixture
W (polyvinyl alcohol)=7% in system, then by Cellulose nanocrystal body/graphene mixed solution and polyvinyl alcohol, 16KHz
Ultrasonic power, gap 1.5s, ultrasonic disperse 40min；
（4）Inorganic Salt treatment：It is prepared with the glass syringe absorption that specification is 5 mL
Cellulose nanocrystal body aaerosol solution and rotate instillation be equipped with 0.2moll CaCl2It is molten
In the culture dish of liquid, each infusion volume is about 0. 2 mL, and it is nanocrystalline to get shaping fiber element to be stored at room temperature 24 h or more
Body/graphene/polyvinyl alcohol tri compound hydrogel bead；
（5）The tert-butyl alcohol is replaced：Molding hydrogel bead is placed in the alcoholic solution of 30%-100% and carries out gradient displacement, water-bath temperature
40 DEG C of degree, each gradient-heated is for 24 hours；
（6）Freeze-drying：Above-mentioned hydrogel bead is sealed with preservative film, is placed in refrigerator（- 10 DEG C or less）1h is freezed,
Several apertures are pricked on the surface of preservative film, is put into freeze drier, is freeze-dried 36h（Vacuum 30MPa）.
Embodiment 4
Cellulose nanocrystal body/graphene/polyvinyl alcohol tri compound enhances aeroge, carries out according to the following steps：
（1）The preparation of Cellulose nanocrystal body:With the sulfuric acid treatment microcrystalline cellulose of concentration 64%, match as microcrystalline cellulose：
H2SO4=1g：9.8ml, constant temperature stirs 1h at 45 DEG C；With centrifuge 4 times or more, until supernatant liquor pH value is 6, then put
It dialyses 3 days in distilled water, then outwells supernatant liquor and be ultrasonically treated 4h（16KHz, gap 1.5s）, obtain 0.4wt% -1.7wt%
（Wt, i.e.,：Mass fraction ratio）Cellulose nanocrystal liquid suspension；
（2）Graphene mixes：By 7.920g, 1.7wt% Cellulose nanocrystal body hydrogels pass through grinder 20Hz with 0.080g,
Graphene ground 30min is according to m (graphene)/m（Cellulose nanocrystal body）=1% proportional arrangement uniformly mixes；
（3）Polyvinyl alcohol：A certain amount of polyvinyl alcohol is weighed, deionized water is added, 100 DEG C of uniform stirring 3h extremely dissolve,
Configure the polyvinyl alcohol water solution of w=10%.According to m (polyvinyl alcohol)/m（Cellulose nanocrystal body）=2%（M is solid
Liquid mixing quality）, w=10% is added in a certain amount of Cellulose nanocrystal body hydrogel and graphene ultrasonic mixing liquid（Polyethylene
Alcohol solid accounts for the mass ratio of poly-vinyl alcohol solution）Polyvinyl alcohol water solution in, add appropriate amount of deionized water to control final mixture
W (polyvinyl alcohol)=7% in system, then by Cellulose nanocrystal body/graphene mixed solution and polyvinyl alcohol, 16KHz
Ultrasonic power, gap 1.5s, ultrasonic disperse 20min；
（4）Inorganic Salt treatment：It is prepared with the glass syringe absorption that specification is 5 mL
Cellulose nanocrystal body aaerosol solution and rotate instillation be equipped with 0.2moll CaCl2 It is molten
In the culture dish of liquid, each infusion volume is about 0. 2 mL, and it is nanocrystalline to get shaping fiber element to be stored at room temperature 24 h or more
Body/graphene/polyvinyl alcohol tri compound hydrogel bead；
（5）The tert-butyl alcohol is replaced：Molding hydrogel bead is placed in the alcoholic solution of 30%-100% and carries out gradient displacement, water-bath temperature
40 DEG C of degree, each gradient-heated is for 24 hours；
（6）Freeze-drying：Above-mentioned hydrogel bead is sealed with preservative film, is placed in refrigerator（- 10 DEG C or less）1h is freezed, is being protected
Several apertures are pricked on the surface of fresh film, are put into freeze drier, and 36h is freeze-dried（Vacuum 30MPa）.
Embodiment 5
Cellulose nanocrystal body/graphene/polyvinyl alcohol prepares composite aerogel, carries out according to the following steps：
（1）The preparation of Cellulose nanocrystal body：With the sulfuric acid treatment microcrystalline cellulose of concentration 64%, match as microcrystalline cellulose：
H2SO4=1g：9.8ml, constant temperature stirs 1h at 45 DEG C；With centrifuge 4 times or more, until supernatant liquor pH value is 6, then put
It dialyses 3 days in distilled water, then outwells supernatant liquor and be ultrasonically treated 4h（16KHz, gap 1.5s）, obtain 0.4wt% -1.7wt%
（Wt, i.e.,：Mass fraction ratio）Cellulose nanocrystal liquid suspension；
（2）Graphene mixes：By 7.92g, 1.7wt% Cellulose nanocrystal body hydrogels pass through grinder 20Hz with 0.08g,
Graphene ground 30min, according to m (graphene)/m（Cellulose nanocrystal body）=1% proportional arrangement uniformly mixes；
（3）Polyvinyl alcohol：A certain amount of polyvinyl alcohol is weighed, deionized water is added, 100 DEG C of uniform stirring 3h extremely dissolve,
Configure the polyvinyl alcohol water solution of w=10%.According to m (polyvinyl alcohol)/m（Cellulose nanocrystal body）=2%（M is solid
Liquid mixing quality）, w=10% is added in a certain amount of Cellulose nanocrystal body hydrogel and graphene ultrasonic mixing liquid（Polyethylene
Alcohol solid accounts for the mass ratio of poly-vinyl alcohol solution）Polyvinyl alcohol water solution in, add appropriate amount of deionized water to control final mixture
W (polyvinyl alcohol)=7% in system, then by Cellulose nanocrystal body/graphene mixed solution and polyvinyl alcohol, 16KHz
Ultrasonic power, gap 1.5s, ultrasonic disperse 40min；
（4）Inorganic Salt treatment：It is prepared with the glass syringe absorption that specification is 5 mL
Cellulose nanocrystal body aaerosol solution and rotate instillation be equipped with 0.2moll CaCl2It is molten
In the culture dish of liquid, each infusion volume is about 0. 2 mL, and it is nanocrystalline to get shaping fiber element to be stored at room temperature 24 h or more
Body/graphene/polyvinyl alcohol tri compound hydrogel bead；
（5）The tert-butyl alcohol is replaced：Molding hydrogel bead is placed in the alcoholic solution of 30%-100% and carries out gradient displacement, water-bath temperature
40 DEG C of degree, each gradient-heated is for 24 hours；
（6）Freeze-drying：Above-mentioned hydrogel bead is sealed with preservative film, is placed in refrigerator（- 10 DEG C or less）1h is freezed, is being protected
Several apertures are pricked on the surface of fresh film, are put into freeze drier, and 36h is freeze-dried（Vacuum 30MPa）.
Embodiment 6：
Cellulose nanocrystal body/graphene/polyvinyl alcohol prepares composite aerogel, carries out according to the following steps：
（1）The preparation of Cellulose nanocrystal body：With the sulfuric acid treatment microcrystalline cellulose of concentration 64%, match as microcrystalline cellulose：
H2SO4=1g：9.8ml, constant temperature stirs 1h at 45 DEG C；With centrifuge 4 times or more, until supernatant liquor pH value is 6, then put
It dialyses 3 days in distilled water, then outwells supernatant liquor and be ultrasonically treated 4h（16KHz, gap 1.5s）, obtain 0.4wt% -1.7wt%
（Wt, i.e.,：Mass fraction ratio）Cellulose nanocrystal liquid suspension；
（2）Graphene mixes：By 9.9g, 1.7wt% Cellulose nanocrystal body hydrogels pass through grinder 20Hz, 30min with 0.1g
Ground graphene, according to m (graphene)/m（Cellulose nanocrystal body）=0.5% proportional arrangement uniformly mixes；
（3）Polyvinyl alcohol：A certain amount of polyvinyl alcohol is weighed, deionized water is added, 100 DEG C of uniform stirring 3h extremely dissolve,
Configure the polyvinyl alcohol water solution of w=10%.According to m (polyvinyl alcohol)/m（Cellulose nanocrystal body）=2%（M is solid
Liquid mixing quality）, w=10% is added in a certain amount of Cellulose nanocrystal body hydrogel and graphene ultrasonic mixing liquid（Polyethylene
Alcohol solid accounts for the mass ratio of poly-vinyl alcohol solution）Polyvinyl alcohol water solution in, add appropriate amount of deionized water to control final mixture
W (polyvinyl alcohol)=7% in system, then by Cellulose nanocrystal body/graphene mixing and polyvinyl alcohol, 16KHz's is super
Acoustical power, gap 1.5s, ultrasonic disperse 40min；
（4）Inorganic Salt treatment：It is prepared with the glass syringe absorption that specification is 5 mL
Cellulose nanocrystal body aaerosol solution and rotate instillation be equipped with 0.2moll CaCl2It is molten
In the culture dish of liquid, each infusion volume is about 0.2 mL, and it is nanocrystalline to get shaping fiber element to be stored at room temperature 24 h or more
Body/graphene/polyvinyl alcohol tri compound hydrogel bead；
（5）The tert-butyl alcohol is replaced：Molding hydrogel bead is placed in the alcoholic solution of 30%-100% and carries out gradient displacement（Every 30%
For a gradient）, 40 DEG C of bath temperature, each gradient-heated is for 24 hours；
（6）Freeze-drying：Above-mentioned hydrogel bead is sealed with preservative film, is placed in refrigerator（- 10 DEG C or less）1h is freezed, is being protected
Several apertures are pricked on the surface of fresh film, are put into freeze drier, and 36h is freeze-dried（Vacuum 30MPa）.
Claims (10)
1. a kind of preparation method of Cellulose nanocrystal body/graphene/polyvinyl alcohol aeroge, it is characterised in that including walking as follows
Suddenly：
（1）The preparation of Cellulose nanocrystal body；
（2）The preparation of Cellulose nanocrystal body/graphene mixed solution；
（3）The preparation of Cellulose nanocrystal body/graphene/polyvinyl alcohol tri compound solution；
（4）Inorganic Salt treatment；
（5）Alcoholic solution is replaced；
（6）Freeze-drying.
2. a kind of preparation method of Cellulose nanocrystal body/graphene/polyvinyl alcohol aeroge according to claim 1,
It is characterized in that the step（1）The preparation of Cellulose nanocrystal body：Microcrystalline cellulose is put into the sulfuric acid of concentration 64%, proportioning
For microcrystalline cellulose：H2SO4=1g：9.8ml, constant temperature stirs 1h at 45 DEG C；It is washed with centrifuge after having handled, until upper layer is clear
Liquid pH value is 6；It is put into distilled water and dialyses 3 days, outwell supernatant liquor, be ultrasonically treated 4h, 16KHz, gap 1.5s are obtained
0.4wt%-1.7wt% Cellulose nanocrystal liquid suspensions.
3. a kind of preparation method of Cellulose nanocrystal body/graphene/polyvinyl alcohol aeroge according to claim 1,
It is characterized in that the step（2）The preparation of Cellulose nanocrystal body/graphene mixed solution：By above-mentioned gained cellulose nanometer
Crystal suspensions and graphene are uniformly mixed according to the ratio of m graphenes/m Cellulose nanocrystals body=0.5%-1%.
4. a kind of preparation method of Cellulose nanocrystal body/graphene/polyvinyl alcohol aeroge according to claim 1,
It is characterized in that the step（3）The preparation of Cellulose nanocrystal body/graphene/polyvinyl alcohol tri compound solution：It weighs poly-
Vinyl alcohol is added in deionized water, and 100 DEG C of 3 h of stirring obtain the polyvinyl alcohol water solution of 10 wt% to being completely dissolved；According to
Cellulose nanocrystal body/graphene mixed solution is added the ratio of m polyvinyl alcohol/m Cellulose nanocrystals body=1%-2%
To Cellulose nanocrystal body/graphene/polyvinyl alcohol tri compound solution is obtained in polyvinyl alcohol water solution, deionized water is added
It is 7% to control the polyvinyl alcohol concentration in final mixed system；Cellulose nanocrystal body/graphene/polyvinyl alcohol ternary is answered
Close solution ultrasonic mixing, 16KHz, gap 1.5s, ultrasonic 20-40 min.
5. a kind of preparation method of Cellulose nanocrystal body/graphene/polyvinyl alcohol aeroge according to claim 1,
It is characterized in that the step（4）Inorganic Salt treatment：Prepared Cellulose nanocrystal body aaerosol solution is drawn, dress is at the uniform velocity instilled
In the culture dish for there are 0.2mol/L inorganic salt solutions, 0.2 mL is instilled every time, is stored at room temperature 24 h molding fibers derived above
Plain nanocrystal/graphene/polyvinyl alcohol tri compound hydrogel bead.
6. a kind of preparation method of Cellulose nanocrystal body/graphene/polyvinyl alcohol aeroge according to claim 1,
It is characterized in that the step（5）Alcoholic solution is replaced：Molding Cellulose nanocrystal body/graphene/polyvinyl alcohol ternary is answered
Heshui gelled pill, which is placed in the alcoholic solution of 30%-100%, carries out gradient displacement, and every 30% or 40% is a gradient, bath temperature
40 DEG C, each gradient-heated is for 24 hours.
7. a kind of preparation method of Cellulose nanocrystal body/graphene/polyvinyl alcohol aeroge according to claim 1,
It is characterized in that the step（6）Freeze-drying：By Cellulose nanocrystal body/graphene/polyvinyl alcohol tri compound hydrogel
After freezing 1h at -10 DEG C or less after bead sealing, moves into freeze drier, be freeze-dried 36h at -40 DEG C to -60 DEG C, vacuum
30MPa is spent, Cellulose nanocrystal body/graphene/enhanced aeroge of polyvinyl alcohol tri compound is obtained.
8. a kind of preparation method of Cellulose nanocrystal body/graphene/polyvinyl alcohol aeroge according to claim 4,
It is characterized in that the step（3）In Cellulose nanocrystal body/graphene/polyvinyl alcohol tri compound solution, m graphenes/m
Cellulose nanocrystal body=0.5%-1%, m polyvinyl alcohol/m Cellulose nanocrystals body=1%-2%.
9. a kind of preparation method of Cellulose nanocrystal body/graphene/polyvinyl alcohol aeroge according to claim 5,
It is characterized in that step（4）In, the inorganic salts are one kind in sodium chloride, potassium chloride, calcium chloride, potassium bromide, potassium nitrate.
10. a kind of preparation method of Cellulose nanocrystal body/graphene/polyvinyl alcohol aeroge according to claim 6,
It is characterized in that step（5）In, the alcoholic solution is one kind in ethyl alcohol, propyl alcohol, butanol.
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