CN107141504A - A kind of preparation method of cellulose composite aerogel - Google Patents
A kind of preparation method of cellulose composite aerogel Download PDFInfo
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- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
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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
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Abstract
It is an object of the invention to provide a kind of preparation method of cellulose composite aerogel, the present invention is using durian shell as raw material, carboxylated nano-cellulose is prepared by ammonium persulfate oxidative degradation, then the carboxylated nano-cellulose prepared and cellulose dissolution liquid are combined, cellulose composite aerogel is prepared by certain process conditions.Production process environmental protection of the present invention, the cellulose aerogels prepared have higher intensity and larger specific surface area.
Description
Technical field
The invention belongs to natural macromolecular material synthesis field, and in particular to a kind of preparation side of cellulose composite aerogel
Method.
Background technology
Cellulose is as one of natural polymer biological material of rich reserves in nature, and it has preferably biological
Compatibility, recyclability and biodegradability, have caused people widely to pay close attention to, and cellulose base aeroge is a kind of three-dimensional
Network, is that, by a kind of highly porous material formed by liquid flux therein removing, current cellulose base aeroge is gradually walked
Enter the various aspects of people's life, be widely used in terms of cosmetics, catalysis, organ transplant, absorption, medical carrier, but
Be pure cellulose aerogels have the shortcomings that poor toughness, specific surface area are smaller in terms of.
The content of the invention
It is an object of the invention to provide a kind of preparation method of cellulose composite aerogel, the present invention is using durian shell as original
Material, prepares carboxylated nano-cellulose, then by the carboxylated nano-cellulose prepared by ammonium persulfate oxidative degradation
It is combined with cellulose dissolution liquid, cellulose composite aerogel is prepared by certain process conditions.The present invention was produced
Journey environmental protection, the cellulose aerogels prepared have higher intensity and larger specific surface area.
The present invention is that the technical scheme for solving above-mentioned technical problem use is：A kind of preparation side of cellulose composite aerogel
Method, step is as follows：
Step 1: the pretreatment of durian shell：The discarded durian shell of collection is uniformly cut into small pieces, then to the dirt on its surface
Cleaned, be dried in vacuo at 40 DEG C ~ 60 DEG C, drying time is 24h ~ 36h, and pulverization process, mistake are carried out in pulverizer
Sieve, filters out the shell powder that particle diameter is 100 ~ 200 mesh, stand-by；
Step 2: the preparation of carboxylated nano-cellulose：The shell powder in a certain amount of step one is taken, is immersed in ammonium persulfate solution
12h ~ 36h, carries out ultrasonic agitation 6h ~ 12h at 60 DEG C ~ 80 DEG C, obtains suspension, a certain amount of distilled water is added in suspension
It is diluted, is then 6000r.min in rotating speed-1~12000r.min-1Centrifuge in centrifuged, centrifugation to after neutrality
4000 r.min-1~7000 r.min-1Upper strata colloid is collected under rotating speed, obtained colloid is put into freeze drying box, -20
DEG C ~ -10 DEG C of progress vacuum freeze drying 12h ~ 48h, and powdery carboxylated nano-cellulose is obtained, it is stand-by；
Step 3: the preparation of cellulose composite aerogel：
（1）, a certain amount of distilled water be added to step 2 obtained in powdery carboxylated nano-cellulose, ultrasonically treated 1h ~ 3h,
Obtain disperseing more uniform colloid, it is stand-by；
（2）, a certain amount of cellulose is added in alkali-urea-water compound system, then add a certain amount of epoxychloropropane, stir
Cellulose dissolution liquid is obtained after mixing dissolving, with a certain amount of step（1）In colloid mixed, 30 DEG C ~ 50 DEG C carry out 1h ~ 3h
Cross-linking reaction, obtains cellulose complex liquid；
（3）, by step（2）In cellulose complex liquid pour into certain mould, 0.5h ~ 12h in solidification liquid is put into, after the demoulding
Gel is put into 24h ~ 48h in distilled water, cellulose composite aquogel is obtained, by cellulose composite aquogel at -20 DEG C ~ -10 DEG C
Freezing processing is carried out, processing time is 12h ~ 36h, then carry out vacuumizing freeze-drying under conditions of -40 DEG C ~ -20 DEG C, do
The dry time is 24h ~ 72h, obtains cellulose composite aerogel.
Further, described alkali-urea-water compound system is sodium hydroxide-urea-water, lithium hydroxide-urea-water, hydrogen
In sodium oxide molybdena-urea-thiocarbamide-water, lithium hydroxide-urea-thiocarbamide-water, sodium hydroxide-thiocarbamide-water, lithium hydroxide-thiocarbamide-water
One kind；Wherein, the content of alkali is 4% ~ 9%, and the content of urea is 7% ~ 18%, and the content of water is 89% ~ 73%.
Further, described alkali-urea-water compound system is certain bar pretreated by certain condition, described
Part refer to by by certain mass than alkali and urea in distilled water is dissolved in, obtain alkali-urea-aqueous solution under normal temperature, then by alkali-
Urea-aqueous solution carries out freezing 24h ~ 48h at -20 DEG C ~ -10 DEG C, obtains alkali-urea-water compound system.
Further, described cellulose is one kind in bamboo fibre, cotton fiber, grass fiber.
Further, the mass ratio that described solidification liquid is distilled water, mass fraction is 5% dilute sulfuric acid, ethanol and methanol is
1:One kind in 1 mixed liquor, straight alcohol, pure methanol.
Further, the mass ratio of described cellulose and alkali-urea-water compound system is 1:100~12:100.
Further, volume mL/quality g ratios of described epoxychloropropane and alkali-urea-water compound system are 0.5：100
~3: 100。
Further, the mass ratio of described powdery carboxylated nano-cellulose and cellulose is 0.001:1~0.1:1.
Further, the concentration of described ammonium persulfate solution is the mol/L of 1.5mol/L ~ 3.
Beneficial effects of the present invention are mainly manifested in the following aspects：
1. durian is increasingly favored as " king of fruit " by people, durian shell is accounted in the 2/3 of durian gross weight, durian shell
Containing compositions such as abundant cellulose, hemicellulose, lignin, but durian shell is lost often as a kind of discarded object by people
Abandon, resource is so wasted significantly, the present invention is prepared by raw material of durian shell by ammonium persulfate solution direct oxidation degraded
The report of carboxylated nano-cellulose, at home and abroad also rarer this respect；
2. the cellulose dissolution liquid of the carboxylated nano-cellulose prepared and alkali-urea-water compound system dissolving is combined,
Because nano-cellulose has the network structure of nanoscale, and it has larger draw ratio so that it can be with reinforcing material
Mechanical strength and reinforcing material toughness, and nano-cellulose will not be to original when being mixed with other materials
The other properties for carrying out material carry out large effect, simultaneously because it has abundance and with biodegradability, at this
In invention, carboxylated nano-cellulose is prepared by ammonium persulfate solution oxidative degradation durian shell, obtained carboxylated is received
Rice cellulose is combined with cellulose dissolution liquid, and demoulding processing is carried out in solidification liquid, is then removed in distilled water
The purified treatments such as other solvents, then process freeze-drying process obtains cellulose composite aerogel under certain condition, the fiber
Plain composite aerogel is because the addition of carboxylated nano-cellulose, there is larger change in compressive strength and specific surface area
It is kind.
Embodiment
Present invention is described in detail in conjunction with the embodiments, the present embodiment is given premised on technical solution of the present invention
Go out detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following embodiments.
Embodiment one,
A kind of preparation method of cellulose composite aerogel, step is as follows：
Step 1: the pretreatment of durian shell：The discarded durian shell of collection is uniformly cut into small pieces, then to the dirt on its surface
Cleaned, be dried in vacuo at 45 DEG C, drying time is 24h ~ 36h, and pulverization process is carried out in pulverizer, sieved, sieve
The shell powder that particle diameter is 100 ~ 200 mesh is selected, it is stand-by；
Step 2: the preparation of carboxylated nano-cellulose：The shell powder in a certain amount of step one is taken, is immersed in ammonium persulfate solution
24h, a certain amount of distilled water is added in suspension and is diluted, and is then 12000r.min in rotating speed-1Centrifuge in enter
Row centrifugation, in 8000 r.min after centrifugation to neutrality-1Upper strata colloid is collected under rotating speed, obtained colloid is put into freeze drying box
In, vacuum freeze drying 12h ~ 48h is carried out at -20 DEG C ~ -10 DEG C, powdery carboxylated nano-cellulose is obtained, it is stand-by；
Step 3: the preparation of cellulose composite aerogel：
（1）, a certain amount of distilled water be added to step 2 obtained in powdery carboxylated nano-cellulose, ultrasonically treated 1h ~ 3h,
Obtain disperseing more uniform colloid, it is stand-by；
（2）, a certain amount of cellulose is added in alkali-urea-water compound system, then add a certain amount of epoxychloropropane, stir
Cellulose dissolution liquid is obtained after mixing dissolving, with a certain amount of step（1）In colloid mixed, 30 DEG C ~ 50 DEG C carry out 1h ~ 3h
Cross-linking reaction, obtains cellulose complex liquid；
（3）, by step（2）In cellulose complex liquid pour into certain mould, 0.5h ~ 12h in solidification liquid is put into, after the demoulding
Gel is put into 24h ~ 48h in distilled water, cellulose composite aquogel is obtained, obtained hydrogel is immersed in the pure tert-butyl alcohol
In, and the pure tert-butyl alcohol is changed once every 6h, until the water in cellulose composite aquogel is all replaced as the tert-butyl alcohol, it is made
Cellulose is combined alcogel, and cellulose then is combined into alcogel carries out precooling 24h at a temperature of -20 DEG C, then -40
DEG C ~ -20 DEG C under conditions of carry out vacuumizing freeze-drying, drying time is 24h ~ 72h, obtains cellulose composite aerogel, tertiary fourth
On the one hand alcohol be, because the freezing point of the tert-butyl alcohol is high, to be easier to easily carry out precooling processing, the opposing party to gel as displacement solvent
Face is, because the surface tension of the tert-butyl alcohol is smaller than water, the water in hydrogel can be made into the hair in gel pore by tert-butyl alcohol displacement
Thin blood vessel power reduces, and the destruction to gel networks is reduced during gel drying, so that the shrinkage factor of aeroge
Reduction, maintains the preferable tridimensional network of gel, improves the specific surface area of aeroge；
Further, described alkali-urea-water compound system is sodium hydroxide-urea-water, lithium hydroxide-urea-water, hydroxide
One in sodium-urea-thiocarbamide-water, lithium hydroxide-urea-thiocarbamide-water, sodium hydroxide-thiocarbamide-water, lithium hydroxide-thiocarbamide-water
Kind；Wherein, the content of alkali is 4% ~ 9%, and the content of urea is 7% ~ 18%, and the content of water is 89% ~ 73%；
Further, described alkali-urea-water compound system is that certain condition pretreated by certain condition, described is
Refer to by by certain mass than alkali and urea in distilled water is dissolved in, obtain alkali-urea-aqueous solution under normal temperature, then by alkali-urea-
The aqueous solution carries out freezing 24h ~ 48h at -20 DEG C ~ -10 DEG C, obtains alkali-urea-water compound system；
Further, described cellulose is one kind in bamboo fibre, cotton fiber, grass fiber；
Further, the mass ratio that described solidification liquid is distilled water, mass fraction is 5% dilute sulfuric acid, ethanol and methanol is 1:1
One kind in mixed liquor, straight alcohol, pure methanol；
Further, the mass ratio of described cellulose and alkali-urea-water compound system is 1:100~12:100；
Further, volume mL/quality g ratios of described epoxychloropropane and alkali-urea-water compound system are 0.5：100~3:
100；
Further, the mass ratio of described powdery carboxylated nano-cellulose and cellulose is 0.005:1~0.1:1；
Further, the concentration of described ammonium persulfate solution is the mol/L of 1.5mol/L ~ 3；
The compressive strength of obtained cellulose composite aerogel improves 64% than pure cellulose aeroge, and specific surface area is improved
96%；Described pure cellulose aeroge is：Without step 3 in step 3（1）In colloid carry out be combined this step
Suddenly, directly by cellulose dissolution liquid according to step 3（2）、（3）The pure cellulose airsetting that normal manufacturing condition is prepared
Glue.
Embodiment two,
A kind of preparation method of cellulose composite aerogel, step is as follows：
Step 1: the pretreatment of durian shell：The discarded durian shell of collection is uniformly cut into small pieces, then to the dirt on its surface
Cleaned, be dried in vacuo at 50 DEG C, drying time is 30h, pulverization process is carried out in pulverizer, sieved, filter out
Particle diameter is the shell powder of 100 ~ 200 mesh, stand-by；
Step 2: the preparation of carboxylated nano-cellulose：The shell powder in a certain amount of step one is taken, is immersed in ammonium persulfate solution
24h, carries out the heating ultrasonic agitation of three phases, first stage：It it is 80 DEG C in temperature, ultrasonic power is super under conditions of 750w
Sound 2h, second stage：It it is 70 DEG C in temperature, ultrasonic power is ultrasound 2h, phase III under conditions of 750w：It is 60 in temperature
DEG C, ultrasonic power is ultrasound 2h under conditions of 250w, obtains suspension, and the purpose that heating ultrasonic agitation is carried out stage by stage is：The
One stage heating-up temperature highest, ultrasonic power is also maximum, because containing more cellulose, hemicellulose, wood in durian shell
The compositions such as quality, initially, with needing stronger reaction condition during ammonium persulfate solution reaction, temperature rise can be favourable
In the progress of reaction, on the one hand higher ultrasonic power, has refined the particle diameter of the composition of each in durian shell, higher ultrasonic power
Stronger energy is generated by cavitation, the progress of reaction has been further speeded up.Second stage, reduces the temperature of reaction
Degree, at this moment ammonium persulfate solution is by the most composition oxidative degradation in addition to cellulose in durian shell, reduction temperature
Weakly reactive activity, phase III can be subtracted, while reducing temperature and ultrasonic power, at this moment ammonium persulfate solution will be removed
Composition substantially oxidative degradation beyond cellulose is fallen, and at this moment reduces temperature and ultrasonic power, it is therefore an objective to carry out cellulose
Carboxylated, while the carboxylated cellulose element of preparation is carried out into nanoscale, obtains suspension, is added in suspension a certain amount of
Distilled water is diluted, and is then 10000r.min in rotating speed-1Centrifuge in centrifuged, centrifugation to after neutrality 7000
r.min-1Upper strata colloid is collected under rotating speed, obtained colloid is put into freeze drying box, it is cold to carry out vacuum at -20 DEG C ~ -10 DEG C
Dry 12h ~ 48h is freezed, powdery carboxylated nano-cellulose is obtained, it is stand-by；
Step 3: the preparation of cellulose composite aerogel：
（1）, a certain amount of distilled water be added to step 2 obtained in powdery carboxylated nano-cellulose, ultrasonically treated 1h ~ 3h,
Obtain disperseing more uniform colloid, it is stand-by；
（2）, a certain amount of cellulose is added in alkali-urea-water compound system, then add a certain amount of epoxychloropropane, stir
Cellulose dissolution liquid is obtained after mixing dissolving, with a certain amount of step（1）In colloid mixed, 30 DEG C ~ 50 DEG C carry out 1h ~ 3h
Cross-linking reaction, obtains cellulose complex liquid；
（3）, by step（2）In cellulose complex liquid pour into certain mould, 0.5h ~ 12h in solidification liquid is put into, after the demoulding
Gel is put into 24h ~ 48h in distilled water, cellulose composite aquogel is obtained, by cellulose composite aquogel at -20 DEG C ~ -10 DEG C
Freezing processing is carried out, processing time is 12h ~ 36h, then carry out vacuumizing freeze-drying under conditions of -40 DEG C ~ -20 DEG C, do
The dry time is 24h ~ 72h, obtains cellulose composite aerogel；
Further, described alkali-urea-water compound system is sodium hydroxide-urea-water, lithium hydroxide-urea-water, hydroxide
One in sodium-urea-thiocarbamide-water, lithium hydroxide-urea-thiocarbamide-water, sodium hydroxide-thiocarbamide-water, lithium hydroxide-thiocarbamide-water
Kind；Wherein, the content of alkali is 4% ~ 9%, and the content of urea is 7% ~ 18%, and the content of water is 89% ~ 73%；
Further, described alkali-urea-water compound system is that certain condition pretreated by certain condition, described is
Refer to by by certain mass than alkali and urea in distilled water is dissolved in, obtain alkali-urea-aqueous solution under normal temperature, then by alkali-urea-
The aqueous solution carries out freezing 24h ~ 48h at -20 DEG C ~ -10 DEG C, obtains alkali-urea-water compound system；
Further, described cellulose is one kind in bamboo fibre, cotton fiber, grass fiber；
Further, the mass ratio that described solidification liquid is distilled water, mass fraction is 5% dilute sulfuric acid, ethanol and methanol is 1:1
One kind in mixed liquor, straight alcohol, pure methanol；
Further, the mass ratio of described cellulose and alkali-urea-water compound system is 1:100~12:100；
Further, volume mL/quality g ratios of described epoxychloropropane and alkali-urea-water compound system are 0.5：100~3:
100；
Further, the mass ratio of described powdery carboxylated nano-cellulose and cellulose is 0.005:1~0.1:1；
Further, the concentration of described ammonium persulfate solution is the mol/L of 1.5mol/L ~ 3；
The compressive strength of obtained cellulose composite aerogel improves 81% than pure cellulose aeroge, and specific surface area is improved
36%；Described pure cellulose aeroge is：Without step 3 in step 3（1）In colloid carry out be combined this step
Suddenly, directly by cellulose dissolution liquid according to step 3（2）、（3）The pure cellulose airsetting that normal manufacturing condition is prepared
Glue.
Embodiment three,
A kind of preparation method of cellulose composite aerogel, step is as follows：
Step 1: the pretreatment of durian shell：The discarded durian shell of collection is uniformly cut into small pieces, then to the dirt on its surface
Cleaned, be dried in vacuo at 60 DEG C, drying time is 36h, pulverization process is carried out in pulverizer, sieved, filter out
Particle diameter is the shell powder of 100 ~ 200 mesh, stand-by；
Step 2: the preparation of carboxylated nano-cellulose：The shell powder in a certain amount of step one is taken, is immersed in ammonium persulfate solution
36h, carries out ultrasonic agitation 6h at 80 DEG C, obtains suspension, a certain amount of distilled water is added in suspension and is diluted, then
It is 12000r.min in rotating speed-1Centrifuge in centrifuged, centrifugation to after neutrality in 8000 r.min-1On being collected under rotating speed
Layer colloid, obtained colloid is put into freeze drying box, is carried out vacuum freeze drying 12h ~ 48h at -20 DEG C ~ -10 DEG C, is obtained powder
Shape carboxylated nano-cellulose, it is stand-by；
Step 3: the preparation of cellulose composite aerogel：
（1）, a certain amount of distilled water be added to step 2 obtained in powdery carboxylated nano-cellulose, ultrasonically treated 1h ~ 3h,
Obtain disperseing more uniform colloid, it is stand-by；
（2）, a certain amount of cellulose is added in alkali-urea-water compound system, then add a certain amount of epoxychloropropane, stir
Cellulose dissolution liquid is obtained after mixing dissolving, with a certain amount of step（1）In colloid mixed, 30 DEG C ~ 50 DEG C carry out 1h ~ 3h
Cross-linking reaction, obtains cellulose complex liquid；
（3）, by step（2）In cellulose complex liquid pour into certain mould, 0.5h ~ 12h in solidification liquid is put into, after the demoulding
Gel is put into 24h ~ 48h in distilled water, cellulose composite aquogel is obtained, by cellulose composite aquogel at -20 DEG C ~ -10 DEG C
Freezing processing is carried out, processing time is 12h ~ 36h, then carry out vacuumizing freeze-drying under conditions of -40 DEG C ~ -20 DEG C, do
The dry time is 24h ~ 72h, obtains cellulose composite aerogel；
Further, described alkali-urea-water compound system is sodium hydroxide-urea-water, lithium hydroxide-urea-water, hydroxide
One in sodium-urea-thiocarbamide-water, lithium hydroxide-urea-thiocarbamide-water, sodium hydroxide-thiocarbamide-water, lithium hydroxide-thiocarbamide-water
Kind；Wherein, the content of alkali is 4% ~ 9%, and the content of urea is 7% ~ 18%, and the content of water is 89% ~ 73%；
Further, described alkali-urea-water compound system is that certain condition pretreated by certain condition, described is
Refer to by by certain mass than alkali and urea in distilled water is dissolved in, obtain alkali-urea-aqueous solution under normal temperature, then by alkali-urea-
The aqueous solution carries out freezing 24h ~ 48h at -20 DEG C ~ -10 DEG C, obtains alkali-urea-water compound system；
Further, described cellulose is one kind in bamboo fibre, cotton fiber, grass fiber；
Further, the mass ratio that described solidification liquid is distilled water, mass fraction is 5% dilute sulfuric acid, ethanol and methanol is 1:1
One kind in mixed liquor, straight alcohol, pure methanol；
Further, the mass ratio of described cellulose and alkali-urea-water compound system is 1:100~12:100；
Further, volume mL/quality g ratios of described epoxychloropropane and alkali-urea-water compound system are 0.5：100~3:
100；
Further, the mass ratio of described powdery carboxylated nano-cellulose and cellulose is 0.001:1~0.1:1；
Further, the concentration of described ammonium persulfate solution is the mol/L of 1.5mol/L ~ 3；
The compressive strength of obtained cellulose composite aerogel improves 48% than pure cellulose aeroge, and specific surface area is improved
34%；Described pure cellulose aeroge is：Without step 3 in step 3（1）In colloid carry out be combined this step
Suddenly, directly by cellulose dissolution liquid according to step 3（2）、（3）The pure cellulose airsetting that normal manufacturing condition is prepared
Glue.
Example IV,
A kind of preparation method of cellulose composite aerogel, step is as follows：
Step 1: the pretreatment of durian shell：The discarded durian shell of collection is uniformly cut into small pieces, then to the dirt on its surface
Cleaned, be dried in vacuo at 40 DEG C, drying time is 24h, pulverization process is carried out in pulverizer, sieved, filter out
Particle diameter is the shell powder of 100 ~ 200 mesh, stand-by；
Step 2: the preparation of carboxylated nano-cellulose：The shell powder in a certain amount of step one is taken, is immersed in ammonium persulfate solution
12h, carries out the heating ultrasonic agitation of three phases, first stage：It it is 80 DEG C in temperature, ultrasonic power is super under conditions of 750w
Sound 6h, second stage：It it is 70 DEG C in temperature, ultrasonic power is ultrasound 6h, phase III under conditions of 750w：It is 60 in temperature
DEG C, ultrasonic power is ultrasound 6h under conditions of 250w, obtains suspension, and the purpose that heating ultrasonic agitation is carried out stage by stage is：The
One stage heating-up temperature highest, ultrasonic power is also maximum, because containing more cellulose, hemicellulose, wood in durian shell
The compositions such as quality, initially, with needing stronger reaction condition during ammonium persulfate solution reaction, temperature rise can be favourable
In the progress of reaction, on the one hand higher ultrasonic power, has refined the particle diameter of the composition of each in durian shell, higher ultrasonic power
Stronger energy is generated by cavitation, the progress of reaction has been further speeded up.Second stage, reduces the temperature of reaction
Degree, at this moment ammonium persulfate solution is by the most composition oxidative degradation in addition to cellulose in durian shell, reduction temperature
Weakly reactive activity, phase III can be subtracted, while reducing temperature and ultrasonic power, at this moment ammonium persulfate solution will be removed
Composition substantially oxidative degradation beyond cellulose is fallen, and at this moment reduces temperature and ultrasonic power, it is therefore an objective to carry out cellulose
Carboxylated, while the carboxylated cellulose element of preparation is carried out into nanoscale, obtains suspension, is added in suspension a certain amount of
Distilled water is diluted, and is then 6000r.min in rotating speed-1Centrifuge in centrifuged, centrifugation to after neutrality 5000
r.min-1Upper strata colloid is collected under rotating speed, obtained colloid is put into freeze drying box, it is cold to carry out vacuum at -20 DEG C ~ -10 DEG C
Dry 12h ~ 48h is freezed, powdery carboxylated nano-cellulose is obtained, it is stand-by；
Step 3: the preparation of cellulose composite aerogel：
（1）, a certain amount of distilled water be added to step 2 obtained in powdery carboxylated nano-cellulose, ultrasonically treated 1h ~ 3h,
Obtain disperseing more uniform colloid, it is stand-by；
（2）, a certain amount of cellulose is added in alkali-urea-water compound system, then add a certain amount of epoxychloropropane, stir
Cellulose dissolution liquid is obtained after mixing dissolving, with a certain amount of step（1）In colloid mixed, 30 DEG C ~ 50 DEG C carry out 1h ~ 3h
Cross-linking reaction, obtains cellulose complex liquid；
（3）, by step（2）In cellulose complex liquid pour into certain mould, 0.5h ~ 12h in solidification liquid is put into, after the demoulding
Gel is put into 24h ~ 48h in distilled water, cellulose composite aquogel is obtained, obtained hydrogel is immersed in the pure tert-butyl alcohol
In, and the pure tert-butyl alcohol is changed once every 6h, until the water in cellulose composite aquogel is all replaced as the tert-butyl alcohol, it is made
Cellulose is combined alcogel, and cellulose then is combined into alcogel carries out precooling 24h at a temperature of -20 DEG C, then -40
DEG C ~ -20 DEG C under conditions of carry out vacuumizing freeze-drying, drying time is 24h ~ 72h, obtains cellulose composite aerogel, tertiary fourth
On the one hand alcohol be, because the freezing point of the tert-butyl alcohol is high, to be easier to easily carry out precooling processing, the opposing party to gel as displacement solvent
Face is, because the surface tension of the tert-butyl alcohol is smaller than water, the water in hydrogel can be made into the hair in gel pore by tert-butyl alcohol displacement
Thin blood vessel power reduces, and the destruction to gel networks is reduced during gel drying, so that the shrinkage factor of aeroge
Reduction, maintains the preferable tridimensional network of gel, improves the specific surface area of aeroge；
Further, described alkali-urea-water compound system is sodium hydroxide-urea-water, lithium hydroxide-urea-water, hydroxide
One in sodium-urea-thiocarbamide-water, lithium hydroxide-urea-thiocarbamide-water, sodium hydroxide-thiocarbamide-water, lithium hydroxide-thiocarbamide-water
Kind；Wherein, the content of alkali is 4% ~ 9%, and the content of urea is 7% ~ 18%, and the content of water is 89% ~ 73%；
Further, described alkali-urea-water compound system is that certain condition pretreated by certain condition, described is
Refer to by by certain mass than alkali and urea in distilled water is dissolved in, obtain alkali-urea-aqueous solution under normal temperature, then by alkali-urea-
The aqueous solution carries out freezing 24h ~ 48h at -20 DEG C ~ -10 DEG C, obtains alkali-urea-water compound system；
Further, described cellulose is one kind in bamboo fibre, cotton fiber, grass fiber；
Further, the mass ratio that described solidification liquid is distilled water, mass fraction is 5% dilute sulfuric acid, ethanol and methanol is 1:1
One kind in mixed liquor, straight alcohol, pure methanol；
Further, the mass ratio of described cellulose and alkali-urea-water compound system is 1:100~12:100；
Further, volume mL/quality g ratios of described epoxychloropropane and alkali-urea-water compound system are 0.5：100~3:
100；
Further, the mass ratio of described powdery carboxylated nano-cellulose and cellulose is 0.001:1~0.1:1；
Further, the concentration of described ammonium persulfate solution is the mol/L of 1.5mol/L ~ 3；
The compressive strength of obtained cellulose composite aerogel improves 74% than pure cellulose aeroge, and specific surface area is improved
83%；Described pure cellulose aeroge is：Without step 3 in step 3（1）In colloid carry out be combined this step
Suddenly, directly by cellulose dissolution liquid according to step 3（2）、（3）The pure cellulose airsetting that normal manufacturing condition is prepared
Glue.
Technology is not described in detail for prior art for this programme.
Claims (9)
1. a kind of preparation method of cellulose composite aerogel, it is characterised in that：Step is as follows：
Step 1: the pretreatment of durian shell：The discarded durian shell of collection is uniformly cut into small pieces, then to the dirt on its surface
Cleaned, be dried in vacuo at 40 DEG C ~ 60 DEG C, drying time is 24h ~ 36h, and pulverization process, mistake are carried out in pulverizer
Sieve, filters out the shell powder that particle diameter is 100 ~ 200 mesh, stand-by；
Step 2: the preparation of carboxylated nano-cellulose：The shell powder in a certain amount of step one is taken, is immersed in ammonium persulfate solution
12h ~ 36h, carries out ultrasonic agitation 6h ~ 12h at 60 DEG C ~ 80 DEG C, obtains suspension, a certain amount of distilled water is added in suspension
It is diluted, is then 6000r.min in rotating speed-1~12000r.min-1Centrifuge in centrifuged, centrifugation to after neutrality
4000 r.min-1~7000 r.min-1Upper strata colloid is collected under rotating speed, obtained colloid is put into freeze drying box, -20
DEG C ~ -10 DEG C of progress vacuum freeze drying 12h ~ 48h, and powdery carboxylated nano-cellulose is obtained, it is stand-by；
Step 3: the preparation of cellulose composite aerogel：
（1）, a certain amount of distilled water be added to step 2 obtained in powdery carboxylated nano-cellulose, ultrasonically treated 1h ~ 3h,
Obtain disperseing more uniform colloid, it is stand-by；
（2）, a certain amount of cellulose is added in alkali-urea-water compound system, then add a certain amount of epoxychloropropane, stir
Cellulose dissolution liquid is obtained after mixing dissolving, with a certain amount of step（1）In colloid mixed, 30 DEG C ~ 50 DEG C carry out 1h ~ 3h
Cross-linking reaction, obtains cellulose complex liquid；
（3）, by step（2）In cellulose complex liquid pour into certain mould, 0.5h ~ 12h in solidification liquid is put into, after the demoulding
Gel is put into 24h ~ 48h in distilled water, cellulose composite aquogel is obtained, by cellulose composite aquogel at -20 DEG C ~ -10 DEG C
Freezing processing is carried out, processing time is 12h ~ 36h, then carry out vacuumizing freeze-drying under conditions of -40 DEG C ~ -20 DEG C, do
The dry time is 24h ~ 72h, obtains cellulose composite aerogel.
2. a kind of preparation method of cellulose composite aerogel according to claim 1, it is characterised in that：Described alkali-
Urea-water compound system is sodium hydroxide-urea-water, lithium hydroxide-urea-water, sodium hydroxide-urea-thiocarbamide-water, hydroxide
One kind in lithium-urea-thiocarbamide-water, sodium hydroxide-thiocarbamide-water, lithium hydroxide-thiocarbamide-water；Wherein, the content of alkali be 4% ~
9%, the content of urea is 7% ~ 18%, and the content of water is 89% ~ 73%.
3. a kind of preparation method of cellulose composite aerogel according to claim 1, it is characterised in that：Described alkali-
Urea-water compound system be certain condition pretreated by certain condition, described refer to by by certain mass than alkali and
Urea obtains alkali-urea-aqueous solution under normal temperature in distilled water is dissolved in, then by alkali-urea-aqueous solution in -20 DEG C ~ -10 DEG C progress
24h ~ 48h is freezed, alkali-urea-water compound system is obtained.
4. a kind of preparation method of cellulose composite aerogel according to claim 1, it is characterised in that：Described fiber
Element is one kind in bamboo fibre, cotton fiber, grass fiber.
5. a kind of preparation method of cellulose composite aerogel according to claim 1, it is characterised in that：Described solidification
The mass ratio that liquid is distilled water, mass fraction is 5% dilute sulfuric acid, ethanol and methanol is 1:In 1 mixed liquor, straight alcohol, pure methanol
It is a kind of.
6. a kind of preparation method of cellulose composite aerogel according to claim 1, it is characterised in that：Described fiber
The mass ratio of element and alkali-urea-water compound system is 1:100~12:100.
7. a kind of preparation method of cellulose composite aerogel according to claim 1, it is characterised in that：Described epoxy
Volume mL/quality g ratios of chloropropane and alkali-urea-water compound system are 0.5：100~3: 100.
8. a kind of preparation method of cellulose composite aerogel according to claim 1, it is characterised in that：Described powdery
The mass ratio of carboxylated nano-cellulose and cellulose is 0.001:1~0.1:1.
9. a kind of preparation method of cellulose composite aerogel according to claim 1, it is characterised in that：Described over cure
The concentration of acid ammonium solution is the mol/L of 1.5mol/L ~ 3.
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| CN107644988A (en) * | 2017-09-19 | 2018-01-30 | 电子科技大学 | Carbon-based lithium battery aeroge of cellulose in-situ and preparation method thereof |
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| CN109898358A (en) * | 2019-03-07 | 2019-06-18 | 天津科技大学 | A kind of preparation method of plant source sustained-release antibacterial aeroge |
| CN109898358B (en) * | 2019-03-07 | 2021-05-07 | 天津科技大学 | Preparation method of plant-derived slow-release antibacterial aerogel |
| CN111807809A (en) * | 2019-04-10 | 2020-10-23 | 盐城工业职业技术学院 | Preparation method of palm nanofiber-graphene-carbon nanotube composite aerogel |
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