CN102432912B - Preparation method of cellulose/metal oxide composite aerogel - Google Patents
Preparation method of cellulose/metal oxide composite aerogel Download PDFInfo
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- CN102432912B CN102432912B CN 201110239314 CN201110239314A CN102432912B CN 102432912 B CN102432912 B CN 102432912B CN 201110239314 CN201110239314 CN 201110239314 CN 201110239314 A CN201110239314 A CN 201110239314A CN 102432912 B CN102432912 B CN 102432912B
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Abstract
The invention discloses a preparation method of cellulose/metal oxide composite aerogel. The preparation method comprises the following steps of: (1) preparing a cellulose film; (2) using deionized water to clean the cellulose film obtained in the step (1), and using an organic solvent A to replace moisture in the cellulose; (3) immersing the cellulose film obtained in the step (2) into alcohol solution of inorganic metal salt, simultaneously adding an epoxy compound, standing for reaction, and obtaining the cellulose/metal oxide composite aerogel, wherein the volume of the epoxy compound is 5-20% of the volume of the alcohol solution of the inorganic metal salt; (4) using the deionized water to clean a gel film obtained in the step (3), and then using an organic solvent B to replace the moisture in the gel film; and (5) freezing and drying or drying critically the gel film obtained in the step (4) and obtaining the cellulose/metal oxide composite aerogel. The composite aerogel obtained by the preparation method has higher specific area.
Description
Technical field
The present invention relates to the aerogel material preparing technical field, be specifically related to a kind of method for preparing Mierocrystalline cellulose complex metal oxides aerogel.
Background technology
Aerogel is a kind of porous material with nanostructure, and its porosity is up to more than 90%, and density is minimum can be to 0.001g/cm
3, be present one of the lightest solid material in the world.It obviously is different from pore space structure at micron and millimetre-sized porous material, has great specific surface area.Because its distinctive nanoporous, three-dimensional net structure, make it have the performance of many uniquenesses, especially show the aspects such as high porosity, low density, lower thermal conductivity, can be widely used in the fields such as lagging material, light transmissive material, insulating material, sound-proof material.
Mierocrystalline cellulose is renewable organic resource the abundantest on the present earth, and itself is nontoxic, can be decomposed into very soon CO at occurring in nature after the cellulosefilm of making is discarded
2And H
2O, very little to the pollution of environment, belong to environmentally friendly macromolecular material.In recent years reported from the calcium thiocyanide aqueous solution, N-methylmorpholine-N-oxide compound (NMMO), ionic liquid and the NaOH aqueous solution and prepared cellulose aerogels, derivatived cellulose such as cellulose acetate butyrate and cellulose acetate are by also obtaining aerogel after crosslinked.The cellulose base aerogel has a wide range of applications aspect the building energy conservation as lagging material.
In aerogel, add metal oxide and can greatly expand its purposes, as increasing the compressive strength of composite aerogel, can make composite aerogel have magnetic performance and electric property, composite aerogel is all had broad application prospects at aspects such as absorption of electromagnetic wave, hull cell electrode and lithium ion battery separators.
Application number is the preparation method that the patent documentation of CN200810033022.2 discloses a kind of transition metal base aerogel, transition metal oxide silica aerogel, composite transition metal oxide silica aerogel, the method needs aging for a long time, and the SEM image of the aerogel product for preparing shows, solid matter in the aerogel is in conjunction with comparatively tight, hole quantity is few, and volume of voids is little.The metal oxide aerogel intensity that conventional sol-gel process obtains is lower.
Summary of the invention
For above-mentioned technical problem, the invention discloses a kind of preparation method of cellulose/metal oxide composite aerogel.The present invention mixes the metal oxide alkoxide take Mierocrystalline cellulose as skeleton, and the composite aerogel for preparing has higher specific surface area.
Technical scheme of the present invention is as follows:
The preparation method of cellulose/metal oxide composite aerogel, concrete preparation process is as follows:
(1) preparation cellulose membrane;
(2) cellulose membrane that obtains with deionized water washing step (1) displaces moisture in the cellulose membrane with organic solvent A again;
(3) cellulose membrane that step (2) is obtained is immersed in the alcoholic solution of inorganic metal salt, add simultaneously epoxy compounds, standing and reacting obtains cellulose/metal oxide plural gel film, the volume of described epoxy compounds be inorganic metal salt alcoholic solution volume 5 ~ 20%;
(4) gel-film that obtains with deionized water washing step (3) displaces moisture in the gel-film with organic solvent B again;
(5) gel-film that step (4) is obtained obtains cellulose/metal oxide composite aerogel through lyophilize or critical drying.
Step (1) preparation cellulose membrane can use cuprammonium process, or viscose process, or uses the solvent of dissolving cellulos that natural cellulose is dissolved, obtain cellulose solution, again with the cellulose solution curtain coating or apply into membranaceous, by solidify regeneration and the washing, be prepared into cellulose membrane.
The solvent of described dissolving cellulos is: lithium chloride/N,N-dimethylacetamide, N-methylmorpholine oxynitride/water, sodium hydroxide, lithium hydroxide, sodium hydroxide/urea, sodium hydroxide/thiocarbamide, sodium hydroxide/urea/sulphur urea, lithium hydroxide/urea, lithium hydroxide/thiocarbamide, lithium hydroxide/urea/sulphur urea, sodium hydroxide/polyvinyl alcohol, lithium hydroxide/polyvinyl alcohol, sodium hydroxide/urea/ZnCl
2, lithium hydroxide/urea/ZnCl
2In a kind of.
When the polymerization degree of the natural cellulose that adopts be 450 ~ 550, when dissolving natural cellulose with NaOH/ urea or LiOH/ urea solvent system, the concentration of the cellulose solution for preparing is controlled at 4wt%～6wt%; When the polymerization degree of the natural cellulose that adopts be 450 ~ 550, when dissolving natural cellulose with the LiCl/DMAC solvent system, the concentration of the cellulose solution for preparing is controlled at 6wt%～12wt%.
The organic solvent A of described step (2) and the described organic solvent B of step (4) are respectively a kind of in methyl alcohol, ethanol, the acetone.
The described inorganic metal salt of step (3) comprises FeCl
2, FeSO
4, Fe (NO
3)
3, FeCl
3, Fe
2(SO
4)
3, CoCl
2, Co (NO
3)
2, NiCl
2, CuSO
4, CuCl
2, MnCl
2, Mn (NO
3), MnSO
4, Mn (CH
3COO)
2At least a.The described epoxy compounds of step (3) is: a kind of in oxyethane, propylene oxide, epoxy monochloroethane, the epoxy chloropropane.The temperature of reaction of step (3) is 20 ~ 60 ℃.
The method for preparing cellulose membrane in the step (1) can be selected any preparation method.The polymerization degree according to natural cellulosic feedstocks is different, and the solvent of dissolving natural cellulose is different, the concentration of cellulose solution that being used for of obtaining prepares cellulose membrane is also different, but in order to guarantee the quality of cellulose membrane, the concentration of cellulose solution need to be controlled.
The concentration of the cellulose solution for preparing is too low, and the poor-performing of the resulting cellulose/metal oxide plural gel of follow-up preparation film easily breaks in the solidification process and frills; When the cellulose solution concentration for preparing was too high, cellulose dissolution was insufficient, cellulose solution poor fluidity, easily gelation.Preferred cellulose dissolution solvent is: lithium chloride/N,N-dimethylacetamide (LiCl/DMAC), NaOH/ urea or LiOH/ urea.
When employing sodium hydroxide/polyvinyl alcohol, when lithium hydroxide/polyvinyl alcohol equal solvent system is dissolved natural cellulose, the polymerization degree of polyvinyl alcohol should be less than 500.
Step (3) is gelation reaction.Inorganic metal salt is dissolved in methyl alcohol or the alcohol solvent in advance, and according to the different solubility of different inorganic metal salts in ethanol or methyl alcohol, the concentration of the general inorganic metal salt that adopts is lower than its maxima solubility in methyl alcohol or alcohol solvent.The volume of epoxy compounds solvent be inorganic metal salt alcoholic solution volume 5% ~ 50%, preferably 5 ~ 20%.
The consumption of cellulose membrane is controlled at can be immersed in fully in the used mixing solutions (cumulative volume of epoxy compounds and inorganic metal alcoholic solution) and gets final product.
The epoxy compounds that adds in the step (3) is the epoxy compounds of organic molecule, such as oxyethane, and propylene oxide, epoxy monochloroethane, epoxy chloropropane etc.The use of epoxies organic micromolecule compound can impel gelation reaction to occur.
The temperature that raises within the specific limits can promote the generation of gelation reaction, and the temperature of reaction of step (3) is 20 ~ 60 ℃, and preferred temperature of reaction is 20 ~ 40 ℃.
Technique effect of the present invention: the present invention is take cellulose membrane as support, cellulose membrane has good 3-D solid structure, its physical strength and toughness are also very high, be doped into therein the metal oxide molecule and prepare composite aerogel, can effectively avoid using separately the metal oxide molecule to be difficult to the defective of gel and moulding.Mix the metal oxide alkoxide, the composite aerogel for preparing has higher specific surface area, porosity and lower thermal conductivity, the premium propertiess such as the transparency of existing cellulose aerogels, high strength, high tenacity, high thermal insulation, electric property, magnetic performance of inorganic metal salt etc. are arranged again, and its range of application is more extensive.Preparation process of the present invention is simple, processing ease, and the prices of raw and semifnished materials of employing are cheap, easily are applied to suitability for industrialized production.
Description of drawings
Fig. 1 is the SEM image of four kinds of cellulose/metal oxide composite aerogels preparing of embodiment 1 ~ 4.Among the figure: a, embodiment 1; B, embodiment 2; C, embodiment 3; D, embodiment 4.
Embodiment
Embodiment 1
First with LiOH/ urea (7wt%/12wt%, wt% represents mass percent) solution is cooled to-12 ℃, then be that 500 natural cellulosic feedstocks drops into wherein with the polymerization degree, at room temperature by mechanical stirring natural cellulose is dissolved rapidly, obtain the cellulose solution of 4wt%, this solution is coated in it on sheet glass by casting method through after the evacuation and centrifugal degassing, then be immersed in the sulphuric acid soln of 5wt% and solidify regeneration, wash at last and can obtain regenerated cellulose film.
Cellulose membrane progressively displaces wherein water with methanol solvate after inorganic salt and other impurity are removed in washing.It is immersed in the CoCl of 50 mL
2Concentration is in the methanol solution of 0.0126 mol/L, adds simultaneously 10ml oxyethane, obtains tan compound cellulose gel-film after leaving standstill 2 hours under 20 ℃.Then the plural gel film displaces water in the composite membrane with ethanol with deionized water wash for several times first.Obtain the composite aerogel of Mierocrystalline cellulose/cobalt oxide through supercritical drying.
Embodiment 2
(the solvent system solvent polymerization degree of 7wt%/12wt%) is that 500 natural cellulose obtains cellulose membrane, and method is identical with embodiment 1 by adopting NaOH/ urea.
Cellulose membrane progressively displaces wherein water with alcohol solvent after inorganic salt and other impurity are removed in washing.It is immersed in the CoCl of 50 mL
2Concentration is in the methanol solution of 0.0084 mol/L, adds simultaneously the 10ml propylene oxide, obtains tan compound cellulose gel-film after leaving standstill 24 hours under 40 ℃.Then the plural gel film displaces water in the composite membrane with ethanol with deionized water wash for several times first.Obtain the composite aerogel of Mierocrystalline cellulose/cobalt oxide through supercritical drying.
Embodiment 3
(the solvent system solvent polymerization degree of 7wt%/12wt%) is that 500 natural cellulose obtains cellulose membrane, and method is identical with embodiment 1 by adopting NaOH/ urea.
Cellulose membrane progressively displaces wherein water with methanol solvate after inorganic salt and other impurity are removed in washing.It is immersed in the CoCl of 50 mL
2Concentration is in the methanol solution of 0.0168 mol/L, adds simultaneously the 10ml propylene oxide, obtains tan compound cellulose gel-film after leaving standstill 36 hours under 40 ℃.Then the plural gel film displaces water in the composite membrane with methyl alcohol with deionized water wash for several times first.Obtain the composite aerogel of Mierocrystalline cellulose/cobalt oxide through supercritical drying.
Embodiment 4
Be that 500 natural cellulosic feedstocks is carried out activation treatment with N,N-dimethylacetamide with the polymerization degree at first, namely first Mierocrystalline cellulose be immersed in the N,N-dimethylacetamide solution 100
oKept under the C 24 hours, and then took out and remove after the N,N-dimethylacetamide in the Mierocrystalline cellulose for subsequent use.A certain amount of Mierocrystalline cellulose is joined lithium chloride/N, in the N-dimethylacetamide solvent, stirring and dissolving obtains the 10wt% cellulose solution under 150 ℃ temperature, this solution is through after the evacuation and centrifugal degassing, by casting method it is coated on the sheet glass, then be immersed in and solidify regeneration in the ethanolic soln, wash at last and can obtain regenerated cellulose film.
Cellulose membrane progressively displaces wherein water with alcohol solvent after inorganic salt and other impurity are removed in washing.CoCl with its submergence 50 mL
2Concentration is in the methanol solution of 0.0252 mol/L, adds simultaneously 10ml oxyethane, obtains tan compound cellulose gel-film after leaving standstill 72 hours under 40 ℃.Then the plural gel film displaces water in the composite membrane with acetone with deionized water wash for several times first.Obtain the composite aerogel of Mierocrystalline cellulose/cobalt oxide through supercritical drying.
Embodiment 5
Adopt lithium chloride/N,N-dimethylacetamide dissolution with solvents Mierocrystalline cellulose, method is identical with embodiment 4.
Cellulose membrane progressively displaces wherein water with methanol solvate after inorganic salt and other impurity are removed in washing.It is immersed in the Mn (CH of 50 mL
3COO)
2Concentration is in the ethanolic soln of 0.2 mol/L, adds 5ml epoxy monochloroethane, leaves standstill 24 hours and can obtain tan plural gel film under 60 ℃.Then this composite membrane displaces water in the composite membrane with acetone with deionized water wash for several times.Obtain the composite aerogel of Mierocrystalline cellulose/trimanganese tetroxide through supercritical drying.
Embodiment 6
Adopt lithium chloride/N,N-dimethylacetamide dissolution with solvents Mierocrystalline cellulose, method is identical with embodiment 4.
Cellulose membrane progressively displaces wherein water with acetone solvent after inorganic salt and other impurity are removed in washing.It is immersed in the Mn (CH of 50 mL
3COO)
2Concentration be 0.5 mol/L ethanolic soln in, add 5ml oxyethane, under 60 ℃, leave standstill and can obtain tan plural gel film in 36 hours.Then this composite membrane displaces water in the composite membrane with ethanol with deionized water wash for several times.Obtain the composite aerogel of Mierocrystalline cellulose/trimanganese tetroxide through supercritical drying.
Embodiment 7
(after 9.5wt%/4.5wt%) solvent is chilled to-5 ℃ in advance, be rapidly that 500 natural cellulose drops into wherein with a certain amount of polymerization degree, at room temperature stirring makes its dissolving obtain the cellulose solution of 4wt % with the NaOH/ thiocarbamide.This solution is coated in it on sheet glass by casting method through after evacuation and centrifugal degassing, then is immersed in the sulphuric acid soln of 5wt% to solidify regeneration, washes at last and can obtain regenerated cellulose film.
Cellulose membrane progressively displaces wherein water with alcohol solvent after inorganic salt and other impurity are removed in washing.It is immersed in the FeCl of 50 mL
3Concentration is in the ethanolic soln of 0.2 mol/L, adds 3ml oxyethane, leaves standstill under 45 ℃ and can obtain brown Mierocrystalline cellulose plural gel film in 2 hours.Then this composite membrane displaces water in the composite membrane with ethanol with deionized water wash for several times.Obtain the composite aerogel of Mierocrystalline cellulose/ferric oxide through lyophilize.
Embodiment 8
(the solvent system dissolving cellulos of 9.5wt%/4.5wt%), method is identical with embodiment 7 to adopt the NaOH/ thiocarbamide.
Cellulose membrane progressively displaces wherein water with acetone solvent after inorganic salt and other impurity are removed in washing.It is immersed in the FeCl of 50 mL
2Concentration is in the ethanolic soln of 0.2 mol/L, adds the 5ml epoxy chloropropane, leaves standstill under 40 ℃ and can obtain jade-green plural gel film in 2 hours.Then this composite membrane displaces water in the composite membrane with ethanol with deionized water wash for several times, and this moment, the plural gel film can become brown or black, obtained the composite aerogel of Mierocrystalline cellulose/ferric oxide through supercritical drying.
The SEM scan image of embodiment 1 ~ 4 resulting composite aerogel as shown in Figure 1.
Specific surface area and the mean pore size of embodiment 1 ~ 8 resulting composite aerogel are shown in Table 1, and the data communication device of specific surface and mean pore size is crossed Quantachrome NOVA 4200e surface analysis instrument and adopted isothermal nitrogen adsorption-desorption method to obtain in the table 1.
Table 1
By data in the table 1 as seen, gained composite aerogel of the present invention has great specific surface area, and the distribution of mean pore size is comparatively concentrated.
Claims (5)
1. the preparation method of cellulose/metal oxide composite aerogel, concrete preparation process is as follows:
(1) preparation cellulose membrane;
(2) cellulose membrane that obtains with deionized water washing step (1) displaces moisture in the cellulose membrane with organic solvent A again;
(3) cellulose membrane that step (2) is obtained is immersed in the alcoholic solution of inorganic metal salt, add simultaneously epoxy compounds, standing and reacting obtains cellulose/metal oxide plural gel film, the volume of described epoxy compounds be inorganic metal salt alcoholic solution volume 5 ~ 20%;
(4) gel-film that obtains with deionized water washing step (3) displaces moisture in the gel-film with organic solvent B again;
(5) gel-film that step (4) is obtained obtains cellulose/metal oxide composite aerogel through lyophilize or critical drying;
The described organic solvent A of step (2) and the described organic solvent B of step (4) are respectively a kind of in methyl alcohol, ethanol, the acetone;
The described inorganic metal salt of step (3) comprises FeCl
2, FeSO
4, Fe (NO
3)
3, FeCl
3, Fe
2(SO
4)
3, CoCl
2, Co (NO
3)
2, NiCl
2, CuSO
4, CuCl
2, MnCl
2, MnSO
4, Mn (CH
3COO)
2At least a;
The described epoxy compounds of step (3) is: a kind of in oxyethane, propylene oxide, epoxy monochloroethane, the epoxy chloropropane.
2. the preparation method of cellulose/metal oxide composite aerogel according to claim 1, it is characterized in that: step (1) preparation cellulose membrane comprises the use cuprammonium process, or viscose process, or use the solvent of dissolving cellulos that natural cellulose is dissolved this three kinds of methods, obtain cellulose solution, again with the cellulose solution curtain coating or apply into membranaceous, by solidify regeneration and the washing, be prepared into cellulose membrane.
3. the preparation method of cellulose/metal oxide composite aerogel according to claim 2, it is characterized in that: the solvent of described dissolving cellulos is: lithium chloride/N,N-dimethylacetamide, N-methylmorpholine oxynitride/water, sodium hydroxide, lithium hydroxide, sodium hydroxide/urea, sodium hydroxide/thiocarbamide, sodium hydroxide/urea/sulphur urea, lithium hydroxide/urea, lithium hydroxide/thiocarbamide, lithium hydroxide/urea/sulphur urea, sodium hydroxide/polyvinyl alcohol, lithium hydroxide/polyvinyl alcohol, sodium hydroxide/urea/ZnCl
2, lithium hydroxide/urea/ZnCl
2In a kind of.
4. the preparation method of cellulose/metal oxide composite aerogel according to claim 2, it is characterized in that: when the polymerization degree of the natural cellulose that adopts be 450 ~ 550, when dissolving natural cellulose with NaOH/ urea or LiOH/ urea solvent system, the concentration of the cellulose solution for preparing is controlled at 4wt%～6wt%; When the polymerization degree of the natural cellulose that adopts be 450 ~ 550, when dissolving natural cellulose with the LiCl/DMAC solvent system, the concentration of the cellulose solution for preparing is controlled at 6wt%～12wt%.
5. the preparation method of cellulose/metal oxide composite aerogel according to claim 1, it is characterized in that: the temperature of reaction of step (3) is 20 ~ 60 ℃.
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| CN103319746B (en) * | 2013-07-12 | 2014-12-03 | 东北林业大学 | Preparation method for spherical cellulose aerogel |
| WO2015084696A1 (en) * | 2013-12-04 | 2015-06-11 | Dow Global Technologies Llc | Process for preparing a mixture of a cellulose derivative and a liquid diluent |
| CN105017555B (en) * | 2014-04-29 | 2018-10-02 | 中国科学院化学研究所 | A kind of preparation method of cellulose aerogels and its hybrid aerogel |
| CN104057080B (en) * | 2014-06-26 | 2016-06-22 | 北京理工大学 | The preparation method of carbon nano-fiber/metallic particles composite aerogel that a kind of three-dimensional Bacterial cellulose is derivative |
| CN104629080B (en) * | 2015-03-06 | 2017-11-17 | 武汉理工大学 | A kind of method based on the cellulose hard template synthesis aeroges of ZIF 8 |
| CN105289740B (en) * | 2015-12-04 | 2017-09-29 | 武汉理工大学 | A kind of oxygen reduction catalyst based on carbonization MOF structures and preparation method thereof |
| EP3405514A4 (en) * | 2016-01-21 | 2019-09-25 | North Carolina State University | Cellulose acetate aerogels |
| CN106916340A (en) * | 2017-03-27 | 2017-07-04 | 南通纺织丝绸产业技术研究院 | A kind of machinery enhancing and the preparation method of fire-retardant cellulose aerogels |
| CN107626337B (en) * | 2017-09-30 | 2020-06-02 | 东北林业大学 | Ag/g-C loaded3N4Preparation method of aerogel microspheres |
| CN110548459B (en) * | 2019-09-17 | 2022-02-22 | 南京工业大学 | Preparation method of blocky cellulose-alumina composite aerogel |
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