CN103319746B - Preparation method for spherical cellulose aerogel - Google Patents
Preparation method for spherical cellulose aerogel Download PDFInfo
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- CN103319746B CN103319746B CN201310294233.2A CN201310294233A CN103319746B CN 103319746 B CN103319746 B CN 103319746B CN 201310294233 A CN201310294233 A CN 201310294233A CN 103319746 B CN103319746 B CN 103319746B
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Abstract
The invention provides a preparation method for a spherical cellulose aerogel, which relates to a preparation method for an aerogel. The objective of the invention is to overcome the problems that the phenomena of structure collapse and volume contraction of a conventional cellulose aerogel frequently occur and the specific surface area of an obtained aerogel is small. The method comprises the following steps: 1, putting vegetable fiber in a mixed solution of urea and NaOH and carrying out stirring after refrigeration for formation of a solution so as to obtain a vegetable fiber/alkaline urea solution; 2, mixing trichloromethane with ethyl acetate and then adding glacial acetic acid so as to obtain an organic solution; 3, titrating the vegetable fiber/alkaline urea solution into the organic solution of glacial acetic acid and carrying out ageing so as to obtain a gel; 4, putting the gel into a glacial acetic acid solution for solidification; and 5, replacing a hydrogel successively with absolute ethyl alcohol and tert-butyl alcohol and carrying out refrigeration and freeze-drying so as to obtain the aerogel. According to the invention, the phenomena of structure collapse and volume contraction of an aerogel in the process of drying are overcome, and the prepared cellulose aerogel has low density and a specific surface area of more than 240 m<2>/g.
Description
Technical field
The present invention relates to a kind of preparation method of aerogel.
Background technology
Aerogel is to be mutually gathered into nanoporous network structure by colloidal particle or high-polymer molecular, and in hole, is full of a kind of high dispersive solid-state material of gaseous state dispersion medium.Common preparation method mainly contains sol-gel method and solution regenerative method etc.Compared with solution regenerative method, the cost compare of sol-gel method is high.In addition, in the preparation process of aerogel, conventionally understand the phenomenons such as recurring structure subsides, volumetric shrinkage, make the structure of aerogel be subject to serious destruction, and then affect its high performance performance.
Summary of the invention
The object of the invention is to be prone in order to solve existing cellulose aerogels the phenomenon of structural collapse and volumetric shrinkage, and the low problem of the specific surface area of the aerogel obtaining, and a kind of preparation method of ball shaped cellulose aerogel is provided.
The preparation method of ball shaped cellulose aerogel of the present invention realizes according to the following steps:
One, the vegetable fibre that takes 1.00～3.00g is put into the mixing solutions of urea and NaOH, obtain mixed system, mixed system is placed at the temperature of-18～-20 DEG C and takes out after freezing 2～4h, at room temperature thaw, then stir into solution and obtain vegetable fibre/alkali urea solution;
Two, the trichloromethane of 100～200mL is mixed with the ethyl acetate of 100～200mL, and then the Glacial acetic acid of interpolation 20～40mL obtains the organic solution of Glacial acetic acid;
Three, the vegetable fibre/alkali urea solution with titration apparatus, step 1 being obtained is titrated in the organic solution of Glacial acetic acid of step 2, forms pearl body, then pearl body is placed in after the aging 5～15min of organic solution of Glacial acetic acid of step 2, obtains white spherical gel;
Four, the spherical gel of white step 3 being obtained is put into glacial acetic acid solution and is solidified 22～26h, is washed till neutrality with distilled water, obtains spherical fiber hydrogel;
Five, spherical fiber hydrogel step 4 being obtained is dipped into and in dehydrated alcohol, carries out solvent exchange, every 10～13h changes a dehydrated alcohol, replace altogether 4～5 times, from dehydrated alcohol, take out spherical fiber hydrogel, with the trimethyl carbinol, spherical fiber hydrogel is carried out to dehydrated alcohol displacement again, every 10～13h changes a trimethyl carbinol, replace altogether 4～5 times, obtain ball shaped cellulose alcogel, ball shaped cellulose alcogel is freezing 22～26h at the temperature of-16～-20 DEG C, then obtains ball shaped cellulose aerogel through the vacuum lyophilization of 22～26h.
Step 3 of the present invention, by adopting the glue head dropper of different sizes, is titrated to vegetable fibre/alkali urea solution in the organic solution of Glacial acetic acid, prepares the ball shaped cellulose aerogel of different size.
Method that the present invention adopts solution regenerative method to combine with titration suspension method, the solvent using the trimethyl carbinol as gel, has prepared the ball shaped cellulose aerogel of low density, high porosity by lyophilize.The present invention is by adopting solvent exchange, and the solvent using the little trimethyl carbinol of volume change when freezing as ball shaped cellulose aerogel, has overcome the phenomenons such as aerogel recurring structure in drying process subsides, volumetric shrinkage, has kept its original constitutional features.
The ball shaped cellulose aerogel that adopts the inventive method to prepare, easy and simple to handle, cost is low, and the ball shaped cellulose aerogel of preparing has low density, and specific surface area can reach 240m
2g
-1above, porosity is higher.The present invention is mainly used in catalytic field and adsorbing domain.
Brief description of the drawings
Fig. 1 is the macro morphology figure of the ball shaped cellulose aerogel that obtains of embodiment mono-;
Fig. 2 is the Fourier transform infrared spectrogram of the ball shaped cellulose aerogel that obtains of embodiment mono-, and wherein a represents the infrared line of bamboo fibers, and b represents the infrared line of ball shaped cellulose aerogel;
Fig. 3 is the surface topography scanning electron microscope diagram of the ball shaped cellulose aerogel prepared of embodiment mono-;
Fig. 4 is the cross-section morphology scanning electron microscope diagram of the ball shaped cellulose aerogel prepared of embodiment mono-.
Embodiment
Embodiment one: the preparation method of present embodiment ball shaped cellulose aerogel realizes according to the following steps:
One, the vegetable fibre that takes 1.00～3.00g is put into the mixing solutions of urea and NaOH, obtain mixed system, mixed system is placed at the temperature of-18～-20 DEG C and takes out after freezing 2～4h, at room temperature thaw, then stir into solution and obtain vegetable fibre/alkali urea solution;
Two, the trichloromethane of 100～200mL is mixed with the ethyl acetate of 100～200mL, and then the Glacial acetic acid of interpolation 20～40mL obtains the organic solution of Glacial acetic acid;
Three, the vegetable fibre/alkali urea solution with titration apparatus, step 1 being obtained is titrated in the organic solution of Glacial acetic acid of step 2, forms pearl body, then pearl body is placed in after the aging 5～15min of organic solution of Glacial acetic acid of step 2, obtains white spherical gel;
Four, the spherical gel of white step 3 being obtained is put into glacial acetic acid solution and is solidified 22～26h, is washed till neutrality with distilled water, obtains spherical fiber hydrogel;
Five, spherical fiber hydrogel step 4 being obtained is dipped into and in dehydrated alcohol, carries out solvent exchange, every 10～13h changes a dehydrated alcohol, replace altogether 4～5 times, from dehydrated alcohol, take out spherical fiber hydrogel, with the trimethyl carbinol, spherical fiber hydrogel is carried out to dehydrated alcohol displacement again, every 10～13h changes a trimethyl carbinol, replace altogether 4～5 times, obtain ball shaped cellulose alcogel, ball shaped cellulose alcogel is freezing 22～26h at the temperature of-16～-20 DEG C, then obtains ball shaped cellulose aerogel through the vacuum lyophilization of 22～26h.
Present embodiment step 1 freezing and step 5 at the temperature of-18～-20 DEG C is freezing at the temperature of-16～-20 DEG C is all freezing in refrigerator, and the stirring in step 1 is to use magnetic stirring apparatus to stir.Step 5 cements out the ethanol in cellulose gel by the trimethyl carbinol.
Embodiment two: what present embodiment was different from embodiment one is that vegetable fibre is bamboo fibers, lumber fibre or stalk fibre.Other step and parameter are identical with embodiment one.
In the mixing solutions of embodiment three: what present embodiment was different from embodiment one or two is step 1 urea and NaOH, the mass ratio of NaOH, urea and water is 7: 12: 81.Other step and parameter are identical with embodiment one or two.
Embodiment four: the solution that stirs into described in step 1 that what present embodiment was different from one of embodiment one to three is is to stir with the speed of 400～800r/min.Other step and parameter are identical with one of embodiment one to three.
Embodiment five: the titration apparatus that what present embodiment was different from one of embodiment one to four is in step 3 is glue head dropper or needle tubing.Other step and parameter are identical with one of embodiment one to four.
Embodiment six: that present embodiment is different from one of embodiment one to five is step 5 ball shaped cellulose alcogel freezing 24h at the temperature of-18 DEG C.Other step and parameter are identical with one of embodiment one to five.
Embodiment mono-: the preparation method of the present embodiment ball shaped cellulose aerogel realizes according to the following steps:
One, the bamboo fibers that takes 2.00g is put into the urea of 100mL and the mixing solutions of NaOH, obtain mixed system, mixed system is placed at the temperature of-18 DEG C and takes out after freezing 3h, at room temperature thaw, then under magnetic stirring apparatus, stir into solution with the speed of 600r/min and obtain bamboo fibers/alkali urea solution;
Two, the trichloromethane of 150mL is mixed with the ethyl acetate of 150mL, and then interpolation 30mL Glacial acetic acid obtains the organic solution of Glacial acetic acid;
Three, bamboo fibers/alkali urea solution that the glue head dropper that is 2.320mm with 2mL bore obtains step 1 is titrated in the organic solution of Glacial acetic acid of step 2, form pearl body, again pearl body is placed in after the aging 10min of organic solution of Glacial acetic acid of step 2, obtains white spherical gel;
Four, it is that 1% Glacial acetic acid solidifies 24h that the spherical gel of white step 3 being obtained is put into mass concentration, is washed till neutrality with distilled water, obtains spherical fiber hydrogel;
Five, spherical fiber hydrogel step 4 being obtained is dipped into and in dehydrated alcohol, carries out solvent exchange, every 12h changes a dehydrated alcohol, replace altogether 5 times, from dehydrated alcohol, take out spherical fiber hydrogel, with the trimethyl carbinol, spherical fiber hydrogel is carried out to dehydrated alcohol displacement again, every 12h changes a trimethyl carbinol, replace altogether 5 times, obtain ball shaped cellulose alcogel, ball shaped cellulose alcogel is freezing 24h at the temperature of-18 DEG C, then obtains ball shaped cellulose aerogel through the vacuum lyophilization of 24h.
Wherein in the mixing solutions of step 1 urea and NaOH, the mass ratio of NaOH, urea and water is 7: 12: 81.
The macro morphology figure of the ball shaped cellulose aerogel that the present embodiment obtains as shown in Figure 1, Fig. 2 is the Fourier transform infrared spectrogram of ball shaped cellulose aerogel, Fig. 3 is the surface topography scanning electron microscope diagram of ball shaped cellulose aerogel, and Fig. 4 is the cross-section morphology scanning electron microscope diagram of ball shaped cellulose aerogel.
Embodiment bis-: the preparation method of the present embodiment ball shaped cellulose aerogel realizes according to the following steps:
One, the bamboo fibers that takes 2.00g is put into the urea of 100mL and the mixing solutions of NaOH, obtain mixed system, mixed system is placed at the temperature of-18 DEG C and takes out after freezing 3h, at room temperature thaw, then under magnetic stirring apparatus, stir into solution with the speed of 600r/min and obtain bamboo fibers/alkali urea solution;
Two, the trichloromethane of 150mL is mixed with the ethyl acetate of 150mL, and then interpolation 30mL Glacial acetic acid obtains the organic solution of Glacial acetic acid;
Three, the bamboo fibers/alkali urea solution with needle tubing, step 1 being obtained is titrated in the organic solution of Glacial acetic acid of step 2, forms pearl body, then pearl body is placed in after the aging 10min of organic solution of Glacial acetic acid of step 2, obtains white spherical gel;
Four, it is that 1% Glacial acetic acid solidifies 24h that the spherical gel of white step 3 being obtained is put into mass concentration, is washed till neutrality with distilled water, obtains spherical fiber hydrogel;
Five, spherical fiber hydrogel step 4 being obtained is dipped into and in dehydrated alcohol, carries out solvent exchange, every 12h changes a dehydrated alcohol, replace altogether 5 times, from dehydrated alcohol, take out spherical fiber hydrogel, with the trimethyl carbinol, spherical fiber hydrogel is carried out to dehydrated alcohol displacement again, every 12h changes a trimethyl carbinol, replace altogether 5 times, obtain ball shaped cellulose alcogel, ball shaped cellulose alcogel is freezing 24h at the temperature of-18 DEG C, then obtains ball shaped cellulose aerogel through the vacuum lyophilization of 24h.
Wherein in the mixing solutions of step 1 urea and NaOH, the mass ratio of NaOH, urea and water is 7: 12: 81.Described in step 3, the syringe needle diameter of needle tubing is 0.130mm.
Embodiment tri-: the preparation method of the present embodiment ball shaped cellulose aerogel realizes according to the following steps:
One, the bamboo fibers that takes 2.00g is put into the urea of 100mL and the mixing solutions of NaOH, obtain mixed system, mixed system is placed at the temperature of-18 DEG C and takes out after freezing 3h, at room temperature thaw, then under magnetic stirring apparatus, stir into solution with the speed of 600r/min and obtain bamboo fibers/alkali urea solution;
Two, the trichloromethane of 150mL is mixed with the ethyl acetate of 150mL, and then interpolation 30mL Glacial acetic acid obtains the organic solution of Glacial acetic acid;
Three, the bamboo fibers/alkali urea solution with glue head dropper, step 1 being obtained is titrated in the organic solution of Glacial acetic acid of step 2, forms pearl body, then pearl body is placed in after the aging 10min of organic solution of Glacial acetic acid of step 2, obtains white spherical gel;
Four, it is that 1% Glacial acetic acid solidifies 24h that the spherical gel of white step 3 being obtained is put into mass concentration, is washed till neutrality with distilled water, obtains spherical fiber hydrogel;
Five, spherical fiber hydrogel step 4 being obtained is dipped into and in dehydrated alcohol, carries out solvent exchange, every 12h changes a dehydrated alcohol, replace altogether 5 times, from dehydrated alcohol, take out spherical fiber hydrogel, with the trimethyl carbinol, spherical fiber hydrogel is carried out to dehydrated alcohol displacement again, every 12h changes a trimethyl carbinol, replace altogether 5 times, obtain ball shaped cellulose alcogel, ball shaped cellulose alcogel is freezing 24h at the temperature of-18 DEG C, then obtains ball shaped cellulose aerogel through the vacuum lyophilization of 24h.
Wherein in the mixing solutions of step 1 urea and NaOH, the mass ratio of NaOH, urea and water is 7: 12: 81.Described in step 3, glue head dropper is that the dropper mouth of the glue head dropper of 5mL is cut into the glue head dropper that bore is 5.085mm.
The characterization data of the ball shaped cellulose aerogel that embodiment mono-, embodiment bis-and embodiment tri-obtain is in table 1;
Table 1
The density of the ball shaped cellulose aerogel of preparing by the known employing the present invention of table 1 is lower, has higher specific surface area simultaneously.
Claims (6)
1. a preparation method for ball shaped cellulose aerogel, is characterized in that the preparation method of ball shaped cellulose aerogel realizes according to the following steps:
One, the vegetable fibre that takes 1.00～3.00g is put into the mixing solutions of urea and NaOH, obtain mixed system, mixed system is placed at the temperature of-18～-20 DEG C and takes out after freezing 2～4h, at room temperature thaw, then stir into solution and obtain vegetable fibre/alkali urea solution;
Two, the trichloromethane of 100～200mL is mixed with the ethyl acetate of 100～200mL, and then the Glacial acetic acid of interpolation 20～40mL obtains the organic solution of Glacial acetic acid;
Three, the vegetable fibre/alkali urea solution with titration apparatus, step 1 being obtained is titrated in the organic solution of Glacial acetic acid of step 2, forms pearl body, then pearl body is placed in after the aging 5～15min of organic solution of Glacial acetic acid of step 2, obtains white spherical gel;
Four, it is that 1% glacial acetic acid solution solidifies 22～26h that the spherical gel of white step 3 being obtained is put into mass concentration, is washed till neutrality with distilled water, obtains spherical fiber hydrogel;
Five, spherical fiber hydrogel step 4 being obtained is dipped into and in dehydrated alcohol, carries out solvent exchange, every 10～13h changes a dehydrated alcohol, replace altogether 4～5 times, from dehydrated alcohol, take out spherical fiber hydrogel, with the trimethyl carbinol, spherical fiber hydrogel is carried out to dehydrated alcohol displacement again, every 10～13h changes a trimethyl carbinol, replace altogether 4～5 times, obtain ball shaped cellulose alcogel, ball shaped cellulose alcogel is freezing 22～26h at the temperature of-16～-20 DEG C, then obtains ball shaped cellulose aerogel through the vacuum lyophilization of 22～26h.
2. the preparation method of a kind of ball shaped cellulose aerogel according to claim 1, is characterized in that vegetable fibre is bamboo fibers, lumber fibre or stalk fibre.
3. the preparation method of a kind of ball shaped cellulose aerogel according to claim 1, is characterized in that the mass ratio of NaOH, urea and water in the mixing solutions of step 1 urea and NaOH is 7: 12: 81.
4. the preparation method of a kind of ball shaped cellulose aerogel according to claim 1, is characterized in that the solution that stirs into described in step 1 is to stir with the speed of 400～800r/min.
5. the preparation method of a kind of ball shaped cellulose aerogel according to claim 1, is characterized in that the titration apparatus in step 3 is glue head dropper or needle tubing.
6. the preparation method of a kind of ball shaped cellulose aerogel according to claim 1, is characterized in that step 5 ball shaped cellulose alcogel freezing 24h at the temperature of-18 DEG C.
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| CN103570967A (en) * | 2013-10-17 | 2014-02-12 | 东北林业大学 | Method for preparing regenerated cellulose spherical aerogel modified through carboxylation |
| CN103756006B (en) * | 2014-01-20 | 2016-01-20 | 东北林业大学 | A kind of preparation method of nanofibrils cellulose aerogel of ultralight, hydrophobic, high oil absorbency |
| CN104017235A (en) * | 2014-06-23 | 2014-09-03 | 东北林业大学 | Preparation method of blocky regenerated cellulose composite phase change energy storage aerogel |
| CN105664948B (en) * | 2016-01-06 | 2018-08-10 | 江苏大学 | A kind of preparation method and application of Ni-based xerogel catalyst |
| CN108359056B (en) * | 2018-03-06 | 2020-04-24 | 中国科学院理化技术研究所 | Self-healing hydrogel of cellulose-dopamine-polymer composite material and preparation method and application thereof |
| CN109762205A (en) * | 2019-01-04 | 2019-05-17 | 江苏泛亚微透科技股份有限公司 | A kind of structure-controllable pure cellulose aeroge and preparation method thereof |
| CN109821484B (en) * | 2019-03-27 | 2020-11-03 | 中国科学院化学研究所 | Dipeptide aerogel and preparation method and application thereof |
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